One-Pot Synthesis of Spirocyclopenta[ a]indene Derivatives via a Cascade Ring Expansion and Intramolecular Friedel-Crafts-Type Cyclization

Article abstract of DOI:10.1021/acs.joc.9b03126

A one-pot efficient synthetic approach for the rapid construction of spirocyclopenta[a]indene derivatives has been developed via an iodine-initiated cascade ring expansion and intramolecular Friedel-Crafts-type cyclization from propargyl alcohol-tethered alkylidenecyclobutanes under mild conditions with broad substrate scope. This cascade process can be elegantly conducted on a gram scale. A plausible reaction mechanism has been proposed on the basis of a series of deuterium labeling and control experiments.

Full text of DOI:10.1021/acs.joc.9b03126

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Article
A One-pot Synthesis of Spirocyclopenta[a]indene Derivatives via a
Cascade Ring Expansion and Intramolecular Friedel-Crafts-type Cyclization
Quanzhe Li, Jiaxin Liu, Yin Wei, and Min Shi
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b03126 • Publication Date (Web): 26 Dec 2019
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A One-pot Synthesis of Spirocyclopenta[a]indene Derivatives via a Cascade Ring
Expansion and Intramolecular Friedel-Crafts-type Cyclization
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Quanzhe Li,a Jiaxin Liu,b Yin Wei,b and Min Shia,b*
9
a Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry &
Molecular Engineering, East China University of Science and Technology, 130 Mei Long Road,
Shanghai 200237, People’s Republic of China.
b State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular
Synthesis, University of Chinese Academy of Sciences, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, People’s Republic of China.
*E-mail: mshi@mail.sioc.ac.cn
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Ar
I2
Ar
OH
Ar
31 examples
up to 99% yield
Ar
Enyne Cyclization
Ring Expansion
I2
Hydrodeiodination
Ar
Ar
I
*Broad substrate scope
*Mild reaction conditions
*One-pot manner
Friedel-Crafts-type
Cyclization
I
Ar
Ar
Abstract:
A
one-pot efficient synthetic approach for the rapid construction of
spirocyclopenta[a]indene derivatives has been developed via an iodine-initiated cascade ring
expansion and intramolecular Friedel-Crafts-type cyclization from propargyl alcohol-tethered
alkylidenecyclobutanes under mild conditions with broad substrate scope. This cascade process
can be elegantly conducted in a gram-scale. A plausible reaction mechanism has been proposed on
the basis of a series of deuterium labeling and control experiments.
INTRODUCTION
The all-carbon polycyclic scaffolds are the significant structural frameworks in a
series of natural products1 and functional materials.2 Recently, tricyclic [6,5,5]-fused
systems,3 as a unique framework, are attracting the attention of researchers because of the
applications in the synthesis of natural products and functional molecules.4 Among these
different types of tricyclic [6,5,5]-fused systems, spirocyclopenta[a]indene derivatives
constitute core scaffolds, that widely distributed in numerous compounds such as
dendrimer core5 and organic electroluminescence device materials (Scheme 1).6 Thus, it is
a highly desirable work using a strategic cascade reaction to rapidly construct tricyclic
[6,5,5]-fused system and spiroindene motif since they can introduce molecular complexity
through a simple chemical operation. In the past several years, tandem or cascade reactions
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to afford polycyclic scaffolds have been extensively explored.7 However, simultaneously
affording tricyclic [6,5,5]-fused systems and spiroindene scaffolds in a one-pot manner
was less exploited and could be a challenging task at the present stage.8
7
8
9
Scheme 1 Representative examples containing spirocyclopenta[a]indene skeleton.
HO
OMe
Ph
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MeO
H
N
O
Ph
Ph
N
MeO
Ph
MeO
Dendrimer Core
Organic Electroluminescence Device
Materials
In 2012, Liang9 and co-workers reported an efficient cascade cyclization approach for
the synthesis of substituted spiro[indene-1,10-isobenzofuran] derivatives in good yields
under mild reaction conditions from simple propargylic alcohols in the presence of I2
(Scheme 2, eq 1). Moreover, our group recently developed a novel protocol for the
synthesis of all-carbon spirobi(indene) scaffold from a class of propargyl alcohol-tethered
alkylidenecyclopropanes in good to excellent yields upon treating with I2 also under mild
reaction conditions (Scheme 2, eq 2).10 On the other hand, it has been reported that
methylenecyclobutanes (MCBs), as another class of strained small rings bearing an
exo-methylene moiety, could be also used as a precursor for the production of
2-phenylcyclopentan-1-one and (1-phenylcyclobutyl)methanone derivatives due to its high
reactivity.11 As part of our continuous efforts to develop new cascade reactions based on
strained small rings with easily available reactants, we attempted to use propargyl
alcohol-tethered alkylidenecyclobutanes as substrates for the rapid construction of ring
expanded spiroindene frameworks in one step in the presence of I2 (Scheme 1, this work).
In this paper, we wish to disclose our findings along with the isolation of the key
intermediate.
Scheme 2 Previous work9,10 and this work.
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a) Previous work
O
O
5
6
7
OR
OH
O
I2
1)
I
DCM, rt
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R = alkyl
R2
R2
I
R1
R1
I2 (2.0 equiv)
DCE, 80 oC
2)
R3
R3
I
HO
R4
R4
R1 = aryl, R2 = aryl, Me; R3 = aryl, R4 = aryl
55-98% yields
b) This work
R2
R2
R2
R1
or
R1
DCE
80 oC
R1
I2
+
I
R3
HO
R3
R3
R4
R4
R1
()
()
R4
R2
I
R3
R4
isolated key intermediate
RESULTS AND DISCUSSION
Initially, propargyl alcohol-tethered alkylidenecyclobutane 1a (0.2 mmol) was used as a
model substrate in the reaction with iodine (2.0 equiv) to seek out the optimal reaction conditions.
As shown in Table 1, the desired cyclized product 2a was obtained in 48% yield as an
atropisomeric mixture (dr = 2.2:1) at room temperature in 1,2-dichloroethane (DCE) (Table 1,
entry 1). The examination of reaction temperature revealed that carrying out this cascade
cyclization at 60 oC gave the best result, affording 2a in 86% yield (dr = 3:1) and this reaction was
not sensitive to visible light irradiation (Table 1, entries 2-7). Decreasing or increasing the loading
amount of I2, no improvement could be realized, giving 2a in 40% (dr = 2.2:1), 77% (dr = 2.1:1),
and 31% (dr = 1.8:1) yields, respectively (Table 1, entries 8-10). The investigation on solvent
effects suggested that DCE was the solvent of choice (Table 1, entries 11-15). Using
fluorobenzene and (trifluoromethyl)benzene as solvents, the reactions became sluggish, affording
2a in trace (Table 1, entries 14 and 15). The major atropisomer’s configuration of 2a has been
determined by X-ray diffraction. The ORTEP drawing is shown in Table 1 and the CIF data are
presented in the Supporting Information.
Table 1 Optimization of the reaction conditions for the synthesis of 2a.
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I2, solvent
temp
I
OH
9
1a
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2a
entrya
1
solvent
temp (oC)
rt
I2 (equiv)
yield (%)c
48 (2.2:1)
55 (2.4:1)
60 (2.4:1)
86 (3:1)d
86 (3:1)
DCE
DCE
2
2
2
2
2
2
2
1
3
5
2
2
2
2
2
2
40
3
DCE
50
4
DCE
60
5b
6
DCE
60
DCE
70
63 (2.8:1)
40 (2.9:1)
40 (2.2:1)
77 (2.1:1)
31 (1.8:1)
72 (2.4:1)
70 (2.3:1)
33 (2.2:1)
trace
7
DCE
80
8
DCE
60
9
DCE
60
10
11
12
13
14
15
DCE
60
DCM
THF
60
60
toluene
PhF
60
60
PhCF3
60
trace
a
b
Reaction was run under the following conditions: a solution of 1a (0.2 mmol) in dry solvent (2.0 mL) for 4 h.
Reaction was run under the following conditions: a solution of 1a (0.2 mmol) in DCE (2.0 mL) under dark
condition. c NMR yield using 1,3,5-trimethoxybenzene as an internal standard. d Isolated yield.
With the optimized reaction conditions in hand, we next turned our attention towards the
substrate scope, and the results are shown in Scheme 3. Substrates 1b-1n, bearing a variety of
substituted aromatic rings, were tolerated, giving the desired products 2b-2n in good to high yields
ranging from 60%-95% regardless of whether they are electron-rich or -poor ones. For substrate 1j
bearing a trifluoromethyl group, the corresponding product 2j was given in 79% yield after 24
hours. In the cases of substrates 1k and 1l, in which the propargyl alcohol moiety containing two
different aromatic rings, the corresponding products 2k and 2l were obtained in 93% and 77%
yields, respectively as a pair of regioisomers combined with their corresponding atropisomers. For
substrate 1o, in which the propargyl alcohol moiety had an aliphatic methyl group, the reaction
also proceeded smoothly, delivering the corresponding product 2o in 84% yield (dr = 4.0:1). For
substrates 1p and 1q containing a 9H-fluoren-9-ol unit, the reactions were also compatible,
affording the desired products 2p and 2q in 74% yield and 69% yield. The use of 1s as substrate,
in which R2 = Me, products 2s and 3s were both obtained, and product 3s was derived from the
further reaction of 2s under the reaction conditions (see Table 2). In the case of substrate 1r (R1 =
CF3, R2 = Me) and 1t (R1 = Ph, R2 = Me), the corresponding products 2r and 2t were obtained in
65% and 80% yields as a pair of diastereoisomers. However, the corresponding products 3r and 3t
could not be formed perhaps due to the strongly electron-withdrawing property of CF3 group and
steric hindrance of phenyl group, which could impair the Friedel-Crafts-type cyclization for the
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formation of 3r and 3t, respectively. Unfortunately, using 1u as substrate did not give the desired
product after examining several reaction conditions, presumably due to the electronic effect.
6
7
8
Scheme 3 Substrate scope for the synthesis of 2.a,b
R1
9
R2
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60
R2
R1
DCE
60 oC, 4 h
R3
I
+
I2
1
HO
R3
R4
2
R4
R1
R2
1
2
2b
2c
2d
2e
: R = 4-Cl, 95% (dr = 3.0:1)
2g
2h
: R = 3-ClC6H4, 76% (dr = 2.9:1)
I
1
2
: R = 4-CF3, 70% (dr = 2.8:1)
: R = 4-ClC6H4, 90% (dr = 2.9:1)
I
1
2
: R = 5-Cl, 60% (dr = 2.7:1)
2i
: R = 4-BrC6H4, 75% (dr = 3.1:1)
: R2 = 4-CF3C6H4, 79% (dr = 3.6:1)
1
2jc
: R = 5-Br, 85% (dr = 2.4:1)
1
2f
: R = 5-Me, 95% (dr = 3.2:1)
I
3
4
3
4
2k
: R = 4-Me R = H or R = H, R = 4-Me (1:1), 93% (dr = 3.8:1) (dr = 3.8:1)
3
4
3
4
2l
: R = 4-OMe, R = H or R = H, R = 4-OMe (1:0.9), 77% (dr = 2.5:1) (dr = 2.5:1)
R3
R4
R5
I
I
I
2'
1'
3'
4'
R3
R4
: R = 4-Cl, R = 4'-Cl, 88% (dr = 4.0:1)
5
3
4
2o
2p
2q
: 84% (dr = 4.0:1)
R6
: R = Me, 74% (dr = 2.9:1)
2m
2n
5
3
4
: R = Ph, 69% (dr = 12.5:1)
: R = 4-Me, R = 4'-Me, 89% (dr = 4.4:1)
F3C
I
I
I
MeO
OMe
2u
: complex
2rd
2se
: 65% (dr = 1.5:1)
: R6 = Br, 45% (dr = 1.3:1)
6
2t
: R = Ph, 80% (dr = 1.5:1)
a Reaction was run under the following conditions: a solution of 1 (0.2 mmol), I2 (0.4 mmol) in DCE (2.0 mL) at
60 oC for 4 h. b Isolated yield. c A solution of 1j (0.2 mmol), I2 (0.4 mmol) in DCE (2.0 mL) at 60 oC for 24 h. d
solution of 1r (0.2 mmol), I2 (0.4 mmol) in DCE (2.0 mL) at 80 oC for 4 h. e 3s was also obtained in 41% yield.
A
Since different reaction outcome was observed in the case of substrate 1s, we used substrate
1v (0.2 mmol), in which R2 = Me, to further optimize the reaction conditions and the results are
o
outlined in Table 2. Upon examination of the solvent effect at 60 C, we found that product 2v
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could be formed in 59% yield in DCE (2.0 mL) (Table 2, entries 1-5). Using THF as the solvent,
the reaction was sluggish for substrate 1v (Table 1, entry 12 vs Table 2, entry 4). However, a
product mixture of spirocyclopenta[a]indene derivatives 3v and 4v was given in 70% and 7%
7
8
9
o
yields, respectively if the reaction was carried out at 80 C in DCE (2.0 mL) (Table 2, entry 6).
o
Lowering the reaction temperature to 40 C or room temperature, 2v was obtained as the single
product in 48% and 45% yields, respectively (Table 2, entries 7 and 8), suggesting that 3v and 4v
were derived from the further transformation of 2v at higher reaction temperature. Decreasing the
loading amount of I2 to 1.0 or 1.5 equiv and carrying out the reaction at 80 oC afforded 2v in 34%
yield or 48% yield under otherwise identical conditions (Table 2, entries 9 and 10). Increasing the
loading amount of I2 to 5 equiv gave 3v in 70% yield along with 4v in 6% yield (Table 2, entry
11). Prolonging the reaction time to 24 hours, the hydrodeiodinated product 4v was obtained in
67% yield even in the presence of 2.0 equiv of I2, indicating that 4v might be derived from 3v
(Table 2, entry 12). When the reaction was performed in 4.0 mL of DCE, 2v was afforded as the
sole product in 64% yield in the diluted reaction solution (Table 2, entry 13).
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Table 2 Optimization of the reaction conditions for the synthesis of 3v and 4v.
OH
I
I
I2, solvent
temp
+
+
1v
2v
3v
4v
()
()
entrya
solvent
temp (oC)
I2
time (h)
yield (%)c
(equiv)
2v
59
11
-
3v
-
4v
-
1
2
DCE
toluene
MeCN
THF
60
60
60
60
60
80
40
rt
2
2
4
4
-
-
3
2
4
-
-
4
2
4
19
-
-
-
5
CH3NO2
DCE
2
4
-
-
6
2
4
-
70
-
7
-
7
DCE
2
4
48
45
34
48
-
8
DCE
2
4
-
-
9
DCE
80
80
80
80
80
1
4
-
-
10
11
12
13b
DCE
1.5
5
4
-
-
DCE
4
70
-
6
67
-
DCE
2
24
-
DCE
2
4
64
-
a Reaction was run under the following conditions: a solution of 1v (0.2 mmol) in dry solvent (2.0 mL). b Reaction
c
was run under the following conditions: a solution of 1v (0.2 mmol) in dry solvent (4.0 mL). NMR yield using
1,3,5-trimethoxybenzene as an internal standard.
With these optimal reaction conditions in hand, we next explored the scope of this
iodine-initiated cascade ring expansion and cyclization reaction. As shown in Scheme 4, in the
cases of substrates 1w and 1x bearing a methoxy or a chloro substituent on the benzene ring, the
corresponding products 3w and 3x were produced in 74% and 58% yields, respectively along with
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trace of deiodinated products 4w and 4x. For substrates 1y-1aa, in which R2 = ethyl, n-hexyl, or
phenylpropyl group, the reactions proceeded smoothly, delivering the corresponding products
3y-3aa in 32% to 83% yields along with deiodinated products 4y-4aa in 16% to 28% yields.
Interestingly, in the case of substrate 1aa, another polycyclic iodinated product 5aa derived from
the further cyclization of 3aa was also obtained in 41% yield and its structure was confirmed by
X-ray diffraction (Scheme 4). As for substrate 1ab having an isopentyl group, product 4ab was
obtained in 42% yield along with other complex. For substrate 1ac, in which the propargyl alcohol
moiety had two different aromatic rings, the corresponding products 3ac and 3ac’ were obtained
as a pair of regioisomers both in 43% yields. For substrates 1ad and 1ae, in which the propargyl
alcohol moiety had electron-rich aromatic rings (4-MeC6H4) and electron-deficient aromatic rings
(4-ClC6H4), the desired products 3ad and 3ae were given in 6% and 46% yields, respectively
along with 4ad in 89% yield and 4ae in trace, indicating that hydrodeiodination process may more
easily occur in electron-rich one. The use of 1af as substrate, in which the propargyl alcohol
moiety had a methyl group, the desired product 3af was obtained in 69% yield. We failed to get
the desired product 3ag from substrate 1ag similar as that of 1u due to the electronic effect. Using
substrates 1y, 1ae and 1af, the corresponding products 4y, 4ae and 4af could be obtained in 66%,
63%, and 59% yields, respectively after prolonging the reaction time to 24 hours under the
optimized conditions.
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Scheme 4 Substrate scope for the synthesis of 3 and 4.a,b
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R2
R2
5
6
7
R1
R1
DCE
80 oC, 4 h
X
+
I2
R3
8
9
1
R3
HO
R4
3
4
(:: X = I
(:: X = H
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R4
6
1
5
1
3v
4v
: R = H, 70% (X = I); : 7% (X = H)
R1
4
1
3w
4w
: trace (X = H)
: R = 4-OMe, 74% (X = I);
X
2
3
1
3x
4x
: R = 5-Cl, 58% (X = I); : trace (X = H)
R2
3v
x-ray crystal structure of
2
3y
4y
: R = Et, 63% (X = I); : 28% (X = H)
X
c
4y
After 24 h,
was obtained in 66% yield
2
3z
4z
: R = n-hexyl, 83% (X = I); : 16% (X = H)
2
3aa
4aa
: R = phenylpropyl, 32% (X = I);
: 16% (X = H)
2
2
3ab
4ab
: R = isopentyl, trace; R =
: 42% (X = H)
3
4
3
4
3ac
3ac
: R = 4-OMe, R = H, 43% (X = I);
': R = H, R = 4-OMe, 43% (X = I)
3
4
X
3ad
3ae
4ad
: 89% (X = H)
: R = 4-Me, R = 4-Me, 6% (X = I);
2
3
3
4
4ae
: R = 4-Cl, R = 4-Cl, 46% (X = I);
: trace (X = H)
2'
1'
4
c
3'
4'
1
4ae
After 24 h,
was obtained in 63% yield
R3
5
6
R4
Ph
I
I
X
MeO
OMe
3ag
: complex
3af
4af
: 69% (X = I)
: trace (X = H)
4af
5aa
: 41%
5aa
x-ray crystal structure of
c
After 24 h,
was obtained in 59% yield
a Reaction was run under the following conditions: a solution of 1 (0.2 mmol), I2 (0.4 mmol) in DCE (2.0 mL) at
80 oC for 4 h. b Isolated yield. c Reaction was run under the following conditions: a solution of 1 (0.2 mmol), I2
(0.4 mmol) in DCE (2.0 mL) at 80 oC for 24 h.
To investigate the reaction mechanism on the formation of spirocyclopenta[a]indene
framework, several deuterium labeling and control experiments were conducted and the results are
o
summarized in Scheme 5. Upon treatment of 1v with I2 (2.0 equiv) at 80 C in DCE containing
D2O (5.0 equiv) for 2 h, the deuterium incorporation was not observed in product 2v at all.
However, prolonging the reaction time to 4 h, 1v was completely consumed and 62% deuterium
incorporation was identified in product 3v, suggesting a protonation by exogenous proton source
o
(Scheme 5, eq a). Moreover, treating 2a or 2v with HI (2.0 equiv) at 80 C successfully afforded
the corresponding product 4a or 4v in 68% and 93% yields, respectively and 2a could be also
converted to 4a in 41% yield in the presence of I2 (Scheme 5, eq b). In addition, when 3v was
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treated with HI (2.0 equiv) at 80 oC in DCE, 4v was afforded in 85% yield, which was intact upon
further treatment with I2 (2.0 equiv), indicating that the transformation of 3v to 4v was irreversible
(Scheme 5, eq c). For the formation of 4v, several control experiments were performed. A
well-known radical scavenger, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) (2.0 equiv), was
added into reaction solution upon treating 3v with HI (2.0 equiv) or with I2 (2.0 equiv) for 24
hours and we found that no reactions occurred, suggesting that the deiodination process might go
through a radical pathway (Scheme 5, eq c). Furthermore, carrying out the reaction of 3v with I2 in
anhydrous DCE and untreated DCE for 24 hours, 4v was afforded in 8% and 27% yields,
indicating that H2O as a proton source was indeed required in this transformation (Scheme 5, eq c).
Furthermore, substrates 1a and 1v could be directly transformed into products 4a and 4v in 60%
and 70% yields respectively as a single diastereomer in the presence of HI (2.0 equiv) (Scheme 5,
eq d). All these results suggested that both 2a or 2v and 3v could be the intermediates in this
reaction.
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Scheme 5 Deuterium labeling and control experiments.
a)
DCE, D2O (5 equiv)
2v
(64% yield)
1v
+
I2
2 h, 80 oC
without deuterium incorporation
DCE, D2O (5 equiv)
4 h, 80 oC
H/D
I
1v
+
I2
3v
() (64% yield)
D content = 62%
b)
DCE
80 oC, 4 h
4v
4a
2v
2a
HI
I2
(
 (93% yield)
+
DCE
80 oC, 4 h
2a + HI
DCE
80 oC, 4 h
(
 (41% yield)
+
4a
( (68% yield)
c)
DCE
80 oC, 24 h
DCE
80 oC, 4 h
4v
3v
+
+ I2
3v
(not detected)
HI
4v
( (85% yield)
TEMPO (2 equiv)
DCE, 80 oC, 24 h
TEMPO (2 equiv)
DCE, 80 oC, 24 h
4v
(not detected)
4v
3v + I2
3v + I2
(not detected)
3v +
HI
DCE (untreated)
80 oC, 24 h
DCE (anhydrous)
80 oC, 24 h
4v
( (8% yield)
4v
( (27% yield)
3v + I2
d)
DCE
80 oC, 4 h
DCE
80 oC, 4 h
1a
+ HI
4a
( (60% yield)
4v
1v
( (70% yield)
+ HI
To verify the atropisomeric character of 2a, we treated 2a with n-BuLi in THF at -80 oC and
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quenched the reaction with H2O sequentially, affording 6a in 95% yield as a sole product because
of losing the axial chirality (Scheme 6, eq a). Its structure has been also determined by X-ray
diffraction. The gram-scale synthesis of 2a (0.857 g) in 80% yield as well as 3v (1.185 g) in 63%
yield and 4v (0.072 g) in 6% yield were simply achieved to demonstrate the practical utility of this
cascade ring expansion and cyclization reaction (Scheme 6, eq b).
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Scheme 6 Deiodination and large-scale synthesis.
a)
n-BuLi
THF, -80 oC
H2O
rt
2a
6a
(95% yield)
b)
DCE, 60 oC
4 h
1a
(2 mmol, 0.825 g)
+
2a
I2
(0.857 g, 80% yield)
DCE, 80 oC
4 h
1v
(4 mmol, 1.400 g)
3v
4v
(0.072 g, 6% yield)
(1.185 g, 63% yield) +
+
I2
Scheme 7 A plausible reaction mechanism.
H
I
or
H
O
I
I
Ph
Ph
I- (I-)
I2
- HOI
1
or -HOH
or HI
A
intramolecular enyne cyclization
+H+
I
H
2
I
C
B
-H+
.
- I
heat or hv
I
H
I
.
- I
4
D
3
C-I bond homolysis
On the basis of the above control experiments, a plausible reaction mechanism for this ring
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expansion and cyclization process for the formation of spirocyclopenta[a]indene derivatives was
proposed in Scheme 7. The I2 or HI activates the hydroxyl group12 in 1 to afford intermediate A
through an intramolecular enyne cyclization, which undergoes a nucleophilic attack of I- to the
allene moiety, followed by a ring expansion of cyclobutane, affording the corresponding product 2.
Product 2 can be continuously converted to intermediate B upon protonation. Then, an
intramolecular Friedel-Crafts-type cyclization can take place to afford intermediate C, which
releases a proton to deliver the desired product 3. Moreover, the homolysis of C-I bond can take
place with the help of heat or light to give the radical intermediate D, which abstract a hydrogen
atom from HI or the solvent to afford the final product 4.13
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CONCLUSION
In summary, we have developed a novel protocol for the rapid construction of
spirocyclopenta[a]indene scaffolds through the iodination of a class of well designed propargyl
alcohol-tethered alkylidenecyclobutanes under mild conditions with a broad substrate scope. The
reaction proceeded through a cascade iodine-initiated enyne cyclization, ring expansion, and an
intramolecular Friedel-Crafts-type cyclization to give the spiropolycyclic products in moderate to
good yields. A plausible reaction mechanism has been proposed on the basis of deuterium labeling
and control experiments. The further explorations on the synthesis of useful
spirocyclopenta[a]indene compounds are underway.
EXPERIMENT SECTION
1
General information. H NMR spectra were recorded on a Varian Mercury-400 and 600
spectrometer for solution in CDCl3 with tetramethylsilane (TMS) as an internal standard;
coupling constants J are given in Hz. 13C NMR spectra were recorded on a Varian
Mercury-400 and 600 spectrophotometers (100 or 150 MHz) with complete proton
decoupling spectrophotometers (CDCl3: 77.0 ppm). Mass and HRMS spectra were
recorded by EI, DART or ESI method. Organic solvents used were dried by standard
methods when necessary. Infrared spectra were recorded on a Perkin-Elmer PE-983
spectrometer with absorption in cm-1. Melting points were determined on a digital melting
point apparatus and temperatures were uncorrected. The reactions were carried out in an oil
bath. Commercially obtained reagents were used without further purification. All these
reactions were monitored by TLC with silica gel coated plates. Flash column
chromatography was carried out using silica gel at increased pressure.
Compounds S2-S5 were prepared according to the previous literature.14
General procedure for the preparation of compound 1b: To a stirred solution of commercially
available 2-amino-4-chlorobenzoic acid S1b (25 g, 1.0 equiv) in anhydrous THF (150 mL, 0.975
mol/L) was added 1,1′-carbonyldiimidazole (23.7 g, 1.0 equiv) at 0 °C under argon atmosphere.
The reaction mixture was allowed to warm to room temperature and stirred for 2 h, then a
suspension of N,O-dimethylhydroxylamine hydrochloride (14.2 g, 1.0 equiv) and Et3N (15.6 g,
1.0 equiv) in THF (100 mL, 0.975 mol/L) was added, and the reaction mixture was stirred
overnight. The residue was poured into H2O (200 mL). The mixture was extracted with ethyl
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acetate (3 × 50 mL). The combined organic layers were washed with brine (1 × 100 mL), dried
over anhydrous Na2SO4, filtered, and concentrated in vacuo. The residue was purified by flash
6
column
chromatography
(hexane/ethyl
acetate
=
50:50)
to
yield
7
8
9
2-amino-4-chloro-N-methoxybenzamide S2b as a colorless solid in 82% yield (24.9 g). To a
solution of 2-amino-4-chloro-N-methoxybenzamide S2b (18.1 g, 1.0 equiv.) in 200 mL of freshly
distilled anhydrous THF (0.58 mol/L) was added bromobenzene S3 (18.1 g, 1.0 equiv.) and
n-butyllithium (232 mmol, 2.0 equiv.) by dropwise at -78℃. The reaction mixture was capped
under argon atmosphere. The mixture was poured into 5% HCl in ethanol at -0 ℃ and the mixture
was partitioned between brine and a 1:1 mixture of ether and methylene chloride. The organic
extract was dried with Na2SO4 and evaporated in vacuo. The residue was purified by a silica gel
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flash chromatography (petroleum ether
/
ethyl acetate
=
30
/
1) to afford
(2-amino-4-chlorophenyl)(phenyl)methanone S4b as yellow solid in 34% yield (9.154 g). To a
500 mL flask charged with (2-amino-4-chlorophenyl)(phenyl)methanone S4b (9.154 g, 1.0
equiv) and TsOH (22.7 g, 3.0 equiv) in MeCN (200 mL, 0.198 mol/mL) was added NaNO2 (5.469
g, 2.0 equiv) and KI (16.4g, 2.5 equiv) dissolved in H2O (100 mL) dropwise at room temperature
and the resulting solution was stirred at room temperature for another 2 h. Upon completion,
saturated aqueous sodium sulfite was added to the solution to quench the reaction until the
reaction mixture turned to be yellow. After removal of the most of MeCN solvent under reduced
pressure, the mixture was extracted with CH2Cl2 (3 x 50 mL). The combined organic layer was
dried over Na2SO4 and concentrated. The residue was purified by a silica gel flash
chromatography (petroleum ether
/
ethyl acetate
=
50
/
1) to afford
(4-chloro-2-iodophenyl)(phenyl)methanone S5b as colorless oil in 61% yield (8.310g). A
solution of (4-bromobutyl)triphenylphosphonium bromide (13.937 g, 1.2 equiv) and t-BuOK
(6.72g, 2.5 equiv) in THF (60 mL) was stirred at 40 oC in oil bath under Ar for 10 min. Afterwards
compound (4-chloro-2-iodophenyl)(phenyl)methanone S5b (8.310 g, 1.0 equiv) in THF (50 mL,
0.4 mol/L) was added and the reaction solution was stirred at 40 o C in oil bath for another 10 min.
Upon completion, the reaction was cooled to room temperature and the mixture was filtered
through a celite. The filtrate was concentrated under reduced pressure and the residue was purified
by
4-chloro-1-(cyclobutylidene(phenyl)methyl)-2-iodobenzene S6b as colorless oil in 19% (1.751
g). To stirred solution of iodine-tethered
silica
gel
flash
chromatography
(eluent:
petroleum
ether)
to
afford
a
4-chloro-1-(cyclobutylidene(phenyl)methyl)-2-iodobenzene S6b (1.751 g, 1.1 equiv) and
1,1-diphenylprop-2-yn-1-ol S7 (0.958 g, 1.0 equiv) in i-Pr2NH (50 mL, 0.092 mol/L) was added
PdCl2(PPh3)2 (65 mg, 2 mol%) and CuI (17 mg, 2 mol%) in Ar atmosphere. The resulted mixture
was stirred at 80 oC in oil bath for 8 h. After the separation of solid by filtration and the removal of
solvent under reduced pressure, the residue was purified by column chromatography on silica gel
(petroleum ether / ethyl acetate = 10 / 1) to afford the corresponding compound
3-(5-chloro-2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol 1b as a
white solid in 98% yield (2.354 g).
General procedure for the preparation of compound 1y: To a solution of 2-aminobenzonitrile
S8y (4.72g, 1.0 equiv) in 50 mL of freshly distilled anhydrous THF (0.4 mol/L) was added EtMgBr
o
(3.0 equiv.) dropwise at 0 C. The reaction mixture was capped under argon atmosphere and
warmed up to room temperature. After the reaction completion monitored by TLC analysis, the
mixture was poured into 5% NH4Cl in water at room tempeture., and the mixture was partitioned
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between brine and a 1:1 mixture of ether and methylene chloride. The organic extract was dried
over anhydrous Na2SO4 and evaporated in vacuum. The residue was purified by a silica gel flash
6
chromatography (petroleum ether / ethyl acetate = 30 / 1) to afford compound
7
8
9
1-(2-aminophenyl)propan-1-one S9y as yellow solid in 64 % yield (3.813g). To a 250 mL flask
charged with 1-(2-aminophenyl)propan-1-one S9y (3.813 g, 1.0 equiv) and TsOH (14.663 g, 3.0
equiv) in MeCN (100 mL, 0.256 mol/mL) was added NaNO2 (3.588 g, 2.0 equiv) and KI (10.79g,
2.5 equiv) dissolved in H2O (50 mL) dropwise at room temperature and the resulting solution was
stirred at room temperature for another 2 h. Upon completion, saturated aqueous sodium sulfite
was added to the solution to quench the reaction until the reaction mixture turned to be yellow.
After removal of the most of MeCN solvent under reduced pressure, the mixture was extracted
with CH2Cl2 (3 x 50 mL). The combined organic layer was dried over Na2SO4 and concentrated.
The residue was purified by a silica gel flash chromatography (petroleum ether / ethyl acetate = 50
/ 1) to afford 1-(2-iodophenyl)propan-1-one S10y as a white solid in 81% yield (5.385g). A
solution of (4-bromobutyl)triphenylphosphonium bromide (12.046 g, 1.2 equiv) and t-BuOK
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o
(5.645 g, 2.4 equiv) in THF (50 mL) was stirred at 40 C in oil bath under Ar for 10 min.
Afterwards compound 1-(2-iodophenyl)propan-1-one S10y (5.385 g, 1.0 equiv) in THF (50 mL,
o
0.42 mol/L) was added and the reaction solution was stirred at 40 C in oil bath for another 2 h.
Upon completion, the reaction was cooled to room temperature and the mixture was filtered
through a celite. The filtrate was concentrated under reduced pressure and the residue was purified
by
silica
gel
flash
chromatography
(eluent:
petroleum
ether)
to
afford
1-(1-cyclobutylidenepropyl)-2-iodobenzene S11 as colorless oil in 34% (2.013 g). To a stirred
solution of iodine-tethered 1-(1-cyclobutylidenepropyl)-2-iodobenzene S11y (2.013 g, 1.1 equiv)
and 1,1-diphenylprop-2-yn-1-ol S7 (1.456 g, 1.0 equiv) in i-Pr2NH (50 mL, 0.14 mol/L) was
added PdCl2(PPh3)2 (98 mg, 2 mol%) and CuI (27 mg, 2 mol%) in Ar atmosphere. The resulted
o
mixture was stirred at 80 C in oil bath for 8 h. After the separation of solid by filtration and the
removal of solvent under reduced pressure, the residue was purified by column chromatography
on silica gel (petroleum ether / ethyl acetate = 10 / 1) to afford the corresponding compound
3-(2-(1-cyclobutylidenepropyl)phenyl)-1,1-diphenylprop-2-yn-1-ol 1y as a white solid in 94%
yield (2.495 g).
3-(2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1a). Yield: 57%,
630 mg; A light yellow solid; Mp: 102-104 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3,
TMS) δ 1.96 (m, 2H), 2.60-2.64 (m, 3H), 3.04 (t, J = 7.2 Hz, 2H), 7.07-7.10 (m, 2H), 7.10-7.16
(m, 1H), 7.16-7.25 (m, 10H), 7.28-7.34 (m, 1H), 7.42-7.47 (m, 4H), 7.51 (d, J = 7.6 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.3, 31.7, 32.8, 74.7, 86.6, 93.8, 122.5, 125.87, 125.93,
126.7, 127.4, 128.0, 128.7, 130.2, 131.6, 132.3, 139.7, 142.7, 143.0, 145.0; IR (neat):  3551,
3057, 2988, 2955, 1652, 1592, 1447, 1158, 1045, 772, 698 cm-1; HRMS (DART-FTICR) Calcd.
for C32H27O [M+H]+: 427.2056, found: 427.2056.
3-(5-chloro-2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol
(1b).
o
1
Yield: 98%, 2354 mg; A light yellow solid; Mp: 133-135 C; Eluent: PE/EA = 10/1. H NMR
(400 MHz, CDCl3, TMS) δ 1.88-1.98 (m, 2H), 2.59 (t, J = 7.2 Hz, 2H), 2.63 (s, 1H), 3.00 (t, J =
7.2 Hz, 2H), 7.05-7.12 (m, 4H), 7.14-7.22 (m, 8H), 7.24-7.28 (m, 1H), 7.39-7.43 (m, 4H),
7.48-7.50 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.2, 31.6, 32.8, 74.6, 85.2, 95.0,
124.2, 125.8, 126.0, 127.3, 127.4, 128.02, 128.04, 128.9, 130.5, 131.5, 132.0, 132.3, 139.2, 141.4,
143.2, 144.6; IR (neat):  3552, 3089, 3023, 2853, 2900, 1587, 1491, 1472, 1164, 982, 766, 693
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cm-1; HRMS (DART-FTICR) Calcd. for C32H24Cl [M-OH]+: 443.1561, found: 443.1558.
3-(2-(cyclobutylidene(phenyl)methyl)-5-(trifluoromethyl)phenyl)-1,1-diphenylprop-2-yn-1-
o
1
ol (1c). Yield: 75%, 446 mg; White needles; Mp: 149-151 C; Eluent: PE/EA = 10/1. H NMR
(400 MHz, CDCl3, TMS) δ 1.92-2.02 (m, 2H), 2.57-2.63 (m, 2H), 2.65 (s, 1H), 3.00-3.07 (m, 2H),
7.02-7.09 (m, 2H), 7.11-7.27 (m, 9H), 7.31–7.36 (m, 1H), 7.38-7.48 (m, 4H), 7.52–7.57 (m, 1H),
7.80 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.3, 31.6, 32.8, 74.7, 85.1, 95.4, 123.5,
123.8 (q, J = 272.2 Hz), 125.2 (q, J = 3.4 Hz), 125.9, 126.2, 127.3, 127.5, 128.1, 128.2, 129.2 (q, J
= 32.3 Hz), 129.3 (q, J = 3.7 Hz), 130.7, 130.9, 138.9, 143.7, 144.6, 146.7; 19F NMR (376 MHz,
CDCl3) δ -62.44; IR (neat):  3552, 3047, 2989, 2961, 2908, 1190, 1451, 1328, 1167, 1114, 1070,
982, 767, 693 cm-1; HRMS (ESI-TOF) Calcd. for C33H24F3 [M-OH]+: 477.1825, found: 477.1829.
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3-(4-chloro-2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol
(1d).
Yield: 73%, 543 mg; A light yellow solid; Mp: 119-121 oC; Eluent: PE/EA = 10/1. 1H NMR (400
MHz, CDCl3, TMS) δ 1.93-2.03 (m, 2H), 2.56 (s, 1H), 2.64 (t, J = 7.2 Hz, 2H), 3.02 (t, J = 7.2 Hz,
2H), 7.08 (d, J = 7.6 Hz, 2H), 7.15-7.27 (m, 11H), 7.40–7.46 (m, 5H); 13C{1H} NMR (100 MHz,
CDCl3, TMS) δ 17.3, 31.6, 32.8, 74.7, 85.5, 94.7, 121.2, 125.9, 126.1, 127.0, 127.3, 127.5, 128.09,
128.13, 130.3, 130.6, 133.5, 134.5, 139.1, 143.6, 144.7, 144.8; IR (neat):  3576, 3086, 3029,
2906, 2225, 1596, 1488, 1449, 1162, 1042, 979, 759 cm-1; HRMS (DART-FTICR) Calcd. for
C32H24Cl [M-OH]+: 443.1561, found: 443.1557.
3-(4-bromo-2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol
(1e).
Yield: 84%, 1691 mg; A white solid; Mp: 128-130 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz,
CDCl3, TMS) δ 1.92-2.02 (m, 2H), 2.58 (s, 1H), 2.63 (t, J = 7.2 Hz, 2H), 3.02 (t, J = 7.2 Hz, 2H),
7.07 (d, J = 7.6 Hz, 2H), 7.14-7.27 (m, 9H), 7.36–7.45 (m, 7H); 13C{1H} NMR (100 MHz, CDCl3,
TMS) δ 17.3, 31.6, 32.8, 74.7, 85.6, 94.9, 121.6, 122.7, 125.9, 126.1, 127.3, 127.5, 128.06, 128.11,
129.9, 130.6, 133.2, 133.6, 139.1, 143.6, 144.7, 144.9; IR (neat):  3560, 3097, 3057, 3021, 2947,
1600, 1576, 1494, 1171, 982, 822, 745, 690 cm-1; HRMS (DART-FTICR) Calcd. for C32H24OBr
[M-H]+: 503.1005, found: 503.1001.
3-(2-(cyclobutylidene(phenyl)methyl)-4-methylphenyl)-1,1-diphenylprop-2-yn-1-ol
(1f).
Yield: 87%, 653 mg; A white solid; Mp: 112-114 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz,
CDCl3, TMS) δ 1.91-2.01 (m, 2H), 2.35 (s, 3H), 2.54 (s, 1H), 2.61 (t, J = 7.2 Hz, 2H), 3.03 (t, J =
7.2 Hz, 2H), 7.02-7.12 (m, 4H), 7.16-7.26 (m, 9H), 7.40-7.48 (m, 5H); 13C{1H} NMR (100 MHz,
CDCl3, TMS) δ 17.3, 21.4, 31.7, 32.8, 74.7, 86.8, 93.0, 119.5, 125.8, 126.0, 127.3, 127.4, 127.5,
127.99, 128.02, 130.9, 131.6, 132.2, 138.8, 139.8, 142.5, 143.0, 145.1; IR (neat):  3539, 3086,
3068, 2981, 2947, 2230, 1597, 1489, 1448, 1339, 1181, 1003, 825, 781, 691 cm-1; HRMS
(DART-FTICR) Calcd. for C33H27 [M-OH]+: 423.2107, found: 423.2104.
3-(2-((3-chlorophenyl)(cyclobutylidene)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol
(1g).
Yield: 85%, 1759 mg; A white solid; Mp: 105-107 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz,
CDCl3, TMS) δ 1.89-1.98 (m, 2H), 2.59 (t, J = 7.2 Hz, 2H), 2.70 (s, 1H), 2.99 (t, J = 7.2 Hz, 2H),
6.93–6.98 (m, 1H), 7.08-7.11 (m, 3H), 7.15-7.24 (m, 8H), 7.27-7.33 (m, 1H), 7.42-7.47 (m, 4H),
7.51 (d, J = 7.6 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.2, 31.7, 32.7, 74.7, 86.3,
94.0, 122.5, 125.4, 125.9, 126.9, 127.1, 127.4, 128.0, 128.8, 129.2, 130.1, 130.5, 132.4, 133.9,
141.4, 142.2, 144.5, 144.8; IR (neat):  3548, 3060, 2958, 2913, 1641, 1587, 1476, 1446, 1158,
1046, 1030, 872, 771, 712 cm-1; HRMS (DART-FTICR) Calcd. for C32H24OCl [M-H]+: 459.1510,
found: 459.1509.
3-(2-((4-chlorophenyl)(cyclobutylidene)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol
(1h).
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Yield: 72%, 2091 mg; A white solid; Mp: 107-109 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz,
CDCl3, TMS) δ 1.91-2.01 (m, 2H), 2.60 (t, J = 7.2 Hz, 2H), 2.68 (s, 1H), 2.99 (t, J = 7.2 Hz, 2H),
6.97-7.25 (m, 12H), 7.29-7.34 (m, 1H), 7.40-7.44 (m, 4H), 7.51 (d, J = 7.6 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3, TMS) δ 17.3, 31.7, 32.8, 74.7, 86.3, 94.0, 122.5, 125.9, 126.9, 127.5,
128.0, 128.1, 128.5, 128.8, 130.1, 130.6, 131.5, 132.4, 138.0, 143.4, 144.8; IR (neat):  3524,
3057, 2987, 2908, 2220, 1654, 1600, 1488, 1449, 1162, 1046, 1009, 752, 698 cm-1; HRMS
(DART-FTICR) Calcd. for C32H24OCl [M-H]+: 459.1510, found: 459.1513.
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3-(2-((4-bromophenyl)(cyclobutylidene)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol
(1i).
Yield: 71%, 2119 mg; A white solid; Mp: 130-132 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz,
CDCl3, TMS) δ 1.91-2.00 (m, 2H), 2.59 (t, J = 7.2 Hz, 2H), 2.68 (s, 1H), 2.98 (t, J = 7.2 Hz, 2H),
6.93 (d, J = 8.4 Hz, 2H), 7.15-7.25 (m, 8H), 7.28-7.33 (m, 3H), 7.39-7.44 (m, 4H), 7.51 (d, J = 7.2
Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.3, 31.7, 32.8, 74.7, 86.3, 94.0, 119.7, 122.5,
125.9, 126.9, 127.5, 128.0, 128.8, 128.9, 130.1, 130.7, 131.0, 132.4, 138.4, 142.4, 143.6, 144.8; IR
(neat):  3516, 3015, 2992, 2932, 2215, 1654, 1486, 1449, 1393, 1161, 1046, 1001, 823, 752, 698
cm-1; HRMS (DART-FTICR) Calcd. for C32H24Br [M-OH]+: 487.1056, found: 487.1059.
3-(2-(cyclobutylidene(4-(trifluoromethyl)phenyl)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol
(1j). Yield: 69%, 1860 mg; A white solid; Mp: 105-107 oC; Eluent: PE/EA = 10/1. 1H NMR (400
MHz, CDCl3, TMS) δ 1.95-2.05 (m, 2H), 2.60-2.67 (m, 3H), 3.03 (t, J = 7.2 Hz, 2H), 7.15 (d, J =
8.4 Hz, 2H), 7.18-7.31 (m, 8H), 7.34-7.47 (m, 7H), 7.56 (d, J = 7.6 Hz, 1H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 17.3, 31.8, 32.9, 74.7, 86.3, 94.1, 122.6, 124.9 (q, J = 3.7 Hz), 125.7, 127.0
(q, J = 270.1 Hz), 127.1, 127.4, 127.59, 127.64 (q, J = 32.2 Hz), 128.1, 128.9, 130.1, 130.8, 132.5,
142.2, 143.0, 144.8, 145.7; 19F NMR (376 MHz, CDCl3) δ -62.21; IR (neat):  3518, 3060, 3000,
2900, 1609, 1488, 1451, 1321, 1116, 1046, 762, 751, 703 cm-1; HRMS (DART-FTICR) Calcd. for
C33H24F3 [M-OH]+: 477.1825, found: 477.1829.
3-(2-(cyclobutylidene(phenyl)methyl)phenyl)-1-phenyl-1-(p-tolyl)prop-2-yn-1-ol (1k). Yield:
75%, 2150 mg; A white solid; Mp: 99-101 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3,
TMS) δ 1.90-2.00 (m, 2H), 2.26 (s, 3H), 2.55 (s, 1H), 2.62 (t, J = 8.8 Hz, 2H), 3.04 (t, J = 7.2 Hz,
2H), 6.99 (d, J = 8.0 Hz, 2H), 7.08-7.13 (m, 3H), 7.14-7.23 (m, 7H), 7.27-7.35 (m, 3H), 7.41-7.52
(m, 3H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.3, 21.0, 31.7, 32.8, 74.5, 86.4, 94.0, 122.6,
125.8, 125.87, 125.89, 126.6, 127.3, 127.4, 128.0, 128.6, 128.7, 130.2, 131.6, 132.3, 137.0, 139.7,
142.2, 142.6, 143.0, 145.1; IR (neat):  3563, 3057, 3023, 2940, 2908, 1649, 1592, 1445, 1163,
1031, 796, 717, 691 cm-1; HRMS (EI-TOF) Calcd. for C33H28O [M]+: 440.2140, found: 440.2143.
3-(2-(cyclobutylidene(phenyl)methyl)phenyl)-1-(4-methoxyphenyl)-1-phenylprop-2-yn-1-ol
o
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(1l). Yield: 93%, 1691 mg; A white solid; Mp: 135-137 C; Eluent: PE/EA = 8/1. H NMR (400
MHz, CDCl3, TMS) δ 1.90-2.00 (m, 2H), 2.62 (t, J = 7.6 Hz, 2H), 2.68 (s, 1H), 3.04 (t, J = 7.6 Hz,
2H), 3.69 (s, 3H), 6.69 (d, J = 8.0 Hz, 2H), 7.07-7.22 (m, 10H), 7.23-7.36 (m, 3H), 7.42-7.45 (m,
2H), 7.50 (d, J = 8.0 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.3, 31.6, 32.8, 55.1,
74.3, 86.7, 94.0, 113.2, 122.6, 125.82, 125.84, 126.6, 127.2, 127.27, 127.34, 127.9, 128.0, 128.6,
130.2, 131.6, 132.3, 137.3, 139.7, 142.6, 143.0, 145.2, 158.7; IR (neat):  3456, 3052, 2963, 2929,
2905, 1605, 1506, 1494, 1242, 1027, 990, 789, 701, 690 cm-1; HRMS (ESI-TOF) Calcd. for
C33H27O [M-OH]+: 439.2056, found: 439.2058.
1,1-bis(4-chlorophenyl)-3-(2-(cyclobutylidene(phenyl)methyl)phenyl)prop-2-yn-1-ol (1m).
o
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Yield: 86%, 2131 mg; A light yellow solid; Mp: 148-150 C; Eluent: PE/EA = 10/1. H NMR
(400 MHz, CDCl3, TMS) δ 1.94-2.03 (m, 2H), 2.58 (s, 1H), 2.61 (t, J = 7.2 Hz, 2H), 3.06 (t, J =
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6.4 Hz, 2H), 7.06-7.10 (m, 2H), 7.13-7.19 (m, 5H), 7.20-7.28 (m, 4H), 7.29-7.37 (m, 5H), 7.50 (d,
J = 8.0 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.4, 31.7, 33.0, 73.8, 87.3, 92.8,
122.0, 126.0, 126.8, 127.28, 127.33, 128.1, 128.2, 129.0, 130.4, 131.6, 132.3, 133.5, 139.6, 142.8,
143.0, 143.2; IR (neat):  3535, 3084, 3060, 2987, 2903, 2228, 1592, 1486, 1439, 1170, 1085,
1034, 841, 769, 713 cm-1; HRMS (DART-FTICR) Calcd. for C32H25OCl2 [M+H]+: 495.1277,
found: 495.1276.
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3-(2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-di-p-tolylprop-2-yn-1-ol (1n). Yield: 73%,
1659 mg; A white solid; Mp: 99-101 oC; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3, TMS)
δ 1.94-2.03 (m, 2H), 2.28 (s, 6H), 2.47 (s, 1H), 2.63 (t, J = 7.6 Hz, 2H), 3.06 (t, J = 7.2 Hz, 2H),
7.01 (d, J = 8.0 Hz, 4H), 7.08-7.18 (m, 3H), 7.20-7.36 (m, 9H), 7.51 (d, J = 7.6 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3, TMS) δ 17.3, 21.0, 31.7, 32.8, 74.5, 86.3, 94.2, 122.7, 125.9, 126.6,
127.4, 128.0, 128.6, 128.7, 130.2, 131.7, 132.4, 137.0, 139.8, 142.4, 142.6, 143.1; IR (neat): 
3521, 3063, 3021, 2961, 1654, 1594, 1507, 1439, 1177, 1020, 779, 758, 693 cm-1; HRMS
(ESI-TOF) Calcd. for C34H29 [M-OH]+: 437.2264, found: 437.2266.
4-(2-(cyclobutylidene(phenyl)methyl)phenyl)-2-phenylbut-3-yn-2-ol (1o). Yield: 64%, 698
o
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mg; A white solid; Mp: 82-84 C; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ
1.64 (s, 3H), 1.95-2.05 (m, 2H), 2.13 (s, 1H), 2.67 (t, J = 7.6 Hz, 2H), 3.05 (t, J = 8.0 Hz, 2H),
7.08-7.16 (m, 3H), 7.20-7.27 (m, 7H), 7.30-7.35 (m, 1H), 7.47-7.52 (m, 3H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 17.3, 31.6, 32.8, 33.0, 70.2, 84.4, 94.8, 122.6, 125.0, 125.8, 126.7, 127.4,
127.5, 127.9, 128.1, 128.5, 130.3, 131.7, 132.3, 139.9, 142.5, 143.0, 145.6; IR (neat):  3285,
3055, 2979, 2947, 1597, 1493, 1443, 1088, 943, 761, 691 cm-1; HRMS (EI-TOF) Calcd. for
C27H24O [M]+: 364.1827, found: 364.1819.
9-((2-(1-cyclobutylideneethyl)phenyl)ethynyl)-9H-fluoren-9-ol (1p). Yield: 61%, 1101 mg; A
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yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ 1.64-1.74 (m, 5H),
2.32 (t, J = 7.2 Hz, 2H), 2.55 (t, J = 7.6 Hz, 2H), 2.73 (s, 1H), 7.03-7.10 (m, 2H), 7.16-7.22 (m,
1H), 7.29-7.42 (m, 5H), 7.59 (d, J = 6.8 Hz, 2H), 7.72 (d, J = 7.6 Hz, 2H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 15.9, 17.9, 29.7, 30.1, 75.2, 82.9, 90.8, 120.1, 120.6, 124.3, 125.81, 125.85,
128.2, 128.3, 128.4, 129.5, 132.6, 138.3, 138.9, 145.4, 147.3; IR (neat):  3390, 3060, 2945, 2995,
1605, 1449, 1188, 1098, 767, 746, 730 cm-1; HRMS (DART-FTICR) Calcd. for C27H23O [M+H]+:
363.1743, found: 363.1742.
9-((2-(cyclobutylidene(phenyl)methyl)phenyl)ethynyl)-9H-fluoren-9-ol (1q). Yield: 82%,
1034 mg; A yellow liquid; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3, TMS) δ 1.73-1.82
(m, 2H), 2.44-2.50 (m, 3H), 2.83 (t, J = 7.2 Hz, 2H), 7.01 (d, J = 7.2 Hz, 2H), 7.07-7.27 (m, 8H),
7.31 (t, J = 7.6 Hz, 2H), 7.40-7.45 (m, 3H), 7.54 (d, J = 7.2 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3, TMS) δ 17.1, 31.4, 32.5, 74.8, 82.6, 91.2, 119.9, 122.3, 124.2, 125.7, 126.5, 127.4, 127.8,
128.3, 128.5, 129.3, 130.0, 131.2, 132.3, 138.9, 139.7, 142.6, 143.3, 147.0; IR (neat):  3394,
3057, 3015, 2903, 2220, 1493, 1449, 1343, 1187, 1048, 765, 747, 695 cm-1; HRMS (EI-TOF)
Calcd. for C32H24O [M]+: 424.1827, found: 424.1833.
3-(2-(1-cyclobutylideneethyl)-5-(trifluoromethyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1r).
Yield: 69%, 1139mg; A yellow liquid; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3, TMS)
δ 1.75-1.95 (m, 5H), 2.30-2.60 (m, 2H), 2.68-2.72 (m, 2H), 3.02 (s, 1H), 7.20-7.27 (m, 3H),
7.29-7.35 (m, 4H), 7.48 (d, J = 8.0 Hz, 1H), 7.61-7.67 (m, 4H), 7.74 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 16.1, 18.0, 29.8, 30.1, 74.9, 85.6, 94.8, 121.7, 123.8 (q, J = 270.7 Hz),
125.0 (q, J = 3.6 Hz), 125.4, 126.1, 127.7, 128.2, 128.6, (q, J = 32.3 Hz), 129.0, 129.4 (q, J = 3.7
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Hz), 139.8, 144.8, 148.7; IR (neat):  3432, 3060, 3021, 2911, 1578, 1468, 1448, 1164, 1041,
1002, 748, 696 cm-1; HRMS (DART-FTICR) Calcd. for C28H22F3 [M-OH]+: 415.1668, found:
415.1671.
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3-(4-bromo-2-(1-cyclobutylideneethyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1s). Yield: 71%,
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1095mg; A yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ 1.80-1.89
(m, 5H), 2.48 (t, J = 7.2 Hz, 2H), 2.69 (t, J = 7.2 Hz, 2H), 2.87 (s, 1H), 7.23-7.36 (m, 9H), 7.64 (d,
J = 7.6 Hz, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 16.1, 18.1, 29.8, 30.2, 74.9, 86.1, 94.3,
119.9, 122.5, 125.3, 126.1, 127.7, 128.2, 129.3, 131.4, 133.8, 139.5, 144.9, 147.0; IR (neat): 
3432, 3060, 3021, 2911, 1578, 1468, 1448, 1164, 1041, 1002, 748, 696 cm-1; HRMS
(DART-FTICR) Calcd. for C27H24OBr [M+H]+: 443.1005, found: 443.1001.
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3-(3-(1-cyclobutylideneethyl)-[1,1'-biphenyl]-4-yl)-1,1-diphenylprop-2-yn-1-ol (1t). Yield:
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69%, 2120 mg; A yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ
1.82-1.92 (m, 5H), 2.54 (t, J = 7.2 Hz, 2H), 2.74 (t, J = 7.2 Hz, 2H), 2.87 (s, 1H), 7.24-7.30 (m,
2H), 7.31-7.37 (m, 5H), 7.38-7.45 (m, 4H), 7.52-7.60 (m, 3H), 7.67-7.71 (m, 4H); 13C{1H} NMR
(100 MHz, CDCl3, TMS) δ 16.2, 18.4, 29.8, 30.3, 75.0, 87.1, 93.9, 119.8, 124.8, 126.1, 126.4,
127.0, 127.1, 127.56, 127.63, 128.2, 128.8, 133.0, 138.5, 140.4, 141.2, 145.2, 145.6; IR (neat): 
3403, 3055, 3023, 2906, 2220, 1597, 1468, 1448, 1176, 1039, 762, 723, 695 cm-1; HRMS
(DART-FTICR) Calcd. for C33H29O [M+H]+: 441.2213, found: 441.2209.
3-(2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol (1u).
Yield: 83%, 2019 mg; A White solid; Mp: 137-139 oC; Eluent: PE/EA = 6/1. 1H NMR (400 MHz,
CDCl3, TMS) δ 1.92-2.01 (m, 2H), 2.56 (s, 1H), 2.62 (t, J = 7.2 Hz, 2H), 3.04 (t, J = 6.8 Hz, 2H),
3.73 (s, 6H), 6.69-6.73 (m, 4H), 7.08-7.16 (m, 3H), 7.19-7.25 (m, 4H), 7.29-7.36 (m, 5H),
7.49-7.52 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 17.3, 31.7, 32.9, 55.2, 74.0, 86.2,
94.2, 113.3, 122.7, 125.8, 126.6, 127.3, 127.4, 128.0, 128.6, 130.2, 131.6, 132.3, 137.6, 139.7,
142.7, 143.0, 158.7; IR (neat):  3459, 2983, 2946, 2890, 1607, 1506, 1236, 1171, 1056, 767, 693
cm-1; HRMS (EI-TOF) Calcd. for C34H30O3 [M]+: 486.2195, found: 486.2191.
3-(2-(1-cyclobutylideneethyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1v). Yield: 48%, 412 mg;
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A light yellow solid; Mp: 66-68 C; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ
1.80-1.88 (m, 5H), 2.48 (t, J = 7.2 Hz, 2H), 2.71 (t, J = 7.6 Hz, 2H), 2.87 (s, 1H), 7.11-7.17 (m,
2H), 7.22-7.28 (m, 3H), 7.30-7.36 (m, 4H), 7.47 (d, J = 8.0 Hz, 1H), 7.67 (d, J = 8.0 Hz, 4H);
13C{1H} NMR (100 MHz, CDCl3, TMS) δ 16.1, 18.3, 29.8, 30.2, 74.9, 87.2, 93.3, 120.9, 126.08,
126.12, 126.4, 127.6, 128.2, 128.4, 128.5, 132.5, 138.2, 145.1, 145.2; IR (neat):  3517, 3060,
3018, 2908, 2843, 2233, 1597, 1449, 1168, 1026, 990, 746, 699 cm-1; HRMS (DART-FTICR)
Calcd. for C27H23 [M-OH]+: 347.1794, found: 347.1792.
3-(2-(1-cyclobutylideneethyl)-5-methoxyphenyl)-1,1-diphenylprop-2-yn-1-ol (1w). Yield:
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85%, 1607 mg; A yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ
1.60-1.75 (m, 5H), 2.30-2.38 (m, 2H), 2.52-2.61 (m, 2H), 3.15 (s, 1H), 3.47 (s, 3H), 6.66 (d, J =
8.0 Hz, 1H), 6.82-6.90 (m, 2H), 7.03-7.18 (m, 6H), 7.50-7.57 (m, 4H); 13C{1H} NMR (100 MHz,
CDCl3, TMS) δ 16.0, 18.4, 29.7, 30.1, 55.1, 74.7, 86.9, 93.1, 115.3, 116.5, 121.5, 125.9, 126.0,
127.5, 128.0, 129.3, 137.7, 137.9, 145.1, 157.3; IR (neat):  3451, 3059, 2940, 2830, 2225, 1599,
1489, 1286, 1209, 1024, 853, 770, 697 cm-1; HRMS (DART-FTICR) Calcd. for C28H25O2 [M-H]+:
393.1849, found: 393.1844.
3-(4-chloro-2-(1-cyclobutylideneethyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1x). Yield: 66%,
1
917 mg; A yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ 1.79-1.88
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(m, 5H), 2.47 (t, J = 7.2 Hz, 2H), 2.68 (t, J = 7.6 Hz, 2H), 2.92 (s, 1H), 7.08-7.13 (m, 2H),
7.22-7.38 (m, 7H), 7.61-7.66 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 16.1, 18.1, 29.7,
30.1, 74.9, 86.0, 94.2, 119.5, 125.3, 126.1, 126.3, 127.6, 128.2, 128.5, 133.6, 134.2, 139.4, 144.9,
146.8; IR (neat):  3557, 2979, 2911, 2851, 2222, 1584, 1488, 1448, 1161, 1031, 749 cm-1; HRMS
(DART-FTICR) Calcd. for C27H24OCl [M+H]+: 399.1510, found: 399.1505.
3-(2-(1-cyclobutylidenepropyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1y). Yield: 94%, 2495
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mg; A White solid; Mp: 85-87 C; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ
0.85 (t, J = 7.6 Hz, 3H), 1.78-1.87 (m, 2H), 2.28 (q, J = 7.6 Hz, 2H), 2.45 (t, J = 7.6 Hz, 2H), 2.72
(t, J = 7.6 Hz, 2H), 2.98 (s, 1H), 7.07-7.16 (m, 3H), 7.23 (t, J = 7.2 Hz, 2H), 7.31 (t, J = 7.6 Hz,
4H), 7.46 (d, J = 7.6 Hz, 1H), 7.67 (d, J = 8.0 Hz, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ
12.7, 16.3, 25.7, 29.5, 30.1, 74.8, 87.3, 93.0, 121.6, 126.0, 126.1, 127.5, 128.1, 128.2, 128.9, 132.4,
132.6, 137.5, 143.6, 145.2; IR (neat):  3550, 3086, 3057, 2932, 1594, 1449, 1156, 1000, 769, 703,
693 cm-1; HRMS (DART-FTICR) Calcd. for C28H27O [M+H]+: 379.2056, found: 379.2056.
3-(2-(1-cyclobutylideneheptyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1z). Yield: 85%, 2590 mg;
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A light yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ 0.79-0.85 (m,
3H), 1.12-1.26 (m, 8H), 1.78-1.88 (m, 2H), 2.22-2.28 (m, 2H), 2.46 (t, J = 7.6 Hz, 2H), 2.72 (t, J =
7.6 Hz, 2H), 2.73 (s, 1H), 7.07-7.16 (m, 2H), 7.21-7.28 (m, 3H), 7.32 (t, J = 7.6 Hz, 4H), 7.47 (d,
J = 7.6 Hz, 1H), 7.67 (d, J = 7.2 Hz, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 14.1, 16.3,
22.6, 28.0, 29.2, 29.7, 30.2, 31.7, 32.5, 74.9, 87.4, 93.1, 121.4, 126.0, 126.1, 127.6, 128.1, 128.2,
128.9, 131.3, 132.5, 138.2, 143.9, 145.2; IR (neat):  3453, 3055, 2958, 2853, 2228, 1600, 1448,
1030, 754, 696 cm-1; HRMS (DART-FTICR) Calcd. for C32H35O [M+H]+: 435.2682, found:
435.2683.
3-(2-(1-cyclobutylidene-4-phenylbutyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1aa). Yield: 89%,
1
2991 mg; A light yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3, TMS) δ
1.50-1.60 (m, 2H), 1.76-1.87 (m, 2H), 2.31 (t, J = 6.8 Hz, 2H), 2.42-2.54 (m, 4H), 2.68 (t, J = 7.2
Hz, 2H), 2.80 (s, 1H), 7.02 (d, J = 7.2 Hz, 2H), 7.07-7.30 (m, 12H), 7.47 (d, J = 7.6 Hz, 1H), 7.63
(d, J = 7.6 Hz, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 16.3, 29.67, 29.75, 30.3, 32.1, 35.6,
74.8, 87.3, 93.2, 121.5, 125.5, 126.1, 127.5, 128.1, 128.28, 128.32, 128.8, 130.7, 132.7, 138.9,
142.5, 143.6, 145.1; IR (neat):  3565, 3060, 2981, 2929, 1597, 1489, 1449, 1159, 1030, 748 cm-1;
HRMS (DART-FTICR) Calcd. for C35H33O [M+H]+: 469.2526, found: 469.2520.
3-(2-(1-cyclobutylidene-4-methylpentyl)phenyl)-1,1-diphenylprop-2-yn-1-ol (1ab). Yield:
94%, 788 mg; A light yellow liquid; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3, TMS) δ
0.78 (d, J = 6.8 Hz, 6H), 1.09-1.17 (m, 2H), 1.44-1.51 (m, 1H), 1.76-1.86 (m, 2H), 2.27 (t, J = 7.6
Hz, 2H), 2.46 (t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.94 (s, 1H), 7.07-7.14 (m, 2H),
7.20-7.26 (m, 3H), 7.30 (t, J = 7.6 Hz, 4H), 7.45 (d, J = 7.6 Hz, 1H), 7.66 (d, J = 7.2 Hz, 4H);
13C{1H} NMR (100 MHz, CDCl3, TMS) δ 16.3, 22.5, 27.6, 29.7, 30.2, 30.4, 37.0, 74.9, 87.4, 93.1,
121.5, 126.0, 126.1, 127.5, 128.1, 128.2, 128.8, 131.3, 132.5, 138.1, 143.8, 145.2; IR (neat): 
3549, 3021, 2951, 2927, 2220, 1597, 1466, 1414, 1161, 1030, 754, 697 cm-1; HRMS
(DART-FTICR) Calcd. for C31H33O [M+H]+: 421.2526, found: 421.2521.
3-(2-(1-cyclobutylideneethyl)phenyl)-1-(4-methoxyphenyl)-1-phenylprop-2-yn-1-ol
(1ac).
1
Yield: 77%, 1213 mg; A light yellow liquid; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3,
TMS) δ 1.80-1.89 (m, 5H), 2.48 (t, J = 7.2 Hz, 2H), 2.71 (t, J = 8.0 Hz, 2H), 2.92 (s, 1H), 3.77 (s,
3H), 6.83-6.87 (m, 2H), 7.11-7.17 (m, 2H), 7.21-7.28 (m, 2H), 7.30-7.35 (m, 2H), 7.44-7.48 (m,
1H), 7.55-7.59 (m, 2H), 7.63-7.68 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 16.1, 18.3,
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29.8, 30.2, 55.2, 74.6, 86.9, 93.5, 113.4, 120.9, 126.1, 126.4, 127.5, 128.1, 128.36, 128.41, 132.5,
137.5, 138.2, 145.1, 145.4, 159.0; IR (neat):  3447, 3052, 2909, 2840, 1607, 1507, 1246, 1031,
794, 732, 697 cm-1; HRMS (EI-TOF) Calcd. for C28H26O2 [M]+: 394.1933, found: 394.1940.
3-(2-(1-cyclobutylideneethyl)phenyl)-1,1-di-p-tolylprop-2-yn-1-ol (1ad). Yield: 92%, 1302
mg; A light yellow liquid; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3, TMS) δ 1.81-1.90
(m, 5H), 2.31 (s, 6H), 2.48 (t, J = 8.4 Hz, 2H), 2.73 (t, J = 8.4 Hz, 2H), 2.82 (s, 1H), 7.10-7.15 (m,
6H), 7.21-7.27 (m, 1H), 7.43-7.47 (m, 1H), 7.52-7.56 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3,
TMS) δ 16.1, 18.3, 21.0, 29.8, 30.2, 74.7, 86.8, 93.6, 121.0, 126.0, 126.5, 128.32, 128.34, 128.8,
132.5, 137.1, 138.2, 142.5, 145.1; IR (neat):  3447, 3052, 2976, 2953, 2917, 2217, 1607, 1508,
1319, 1178, 1056, 1041, 817, 781, 757 cm-1; HRMS (EI-TOF) Calcd. for C29H28O [M]+: 392.2140,
found: 392.2139.
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1,1-bis(4-chlorophenyl)-3-(2-(1-cyclobutylideneethyl)phenyl)prop-2-yn-1-ol (1ae). Yield:
95%, 1649 mg; A light yellow liquid; Eluent: PE/EA = 10/1. 1H NMR (400 MHz, CDCl3, TMS) δ
1.80-1.90 (m, 5H), 2.46 (t, J = 7.2 Hz, 2H), 2.70 (t, J = 7.6 Hz, 2H), 3.01 (s, 1H), 7.12-7.18 (m,
2H), 7.27-7.31 (m, 5H), 7.44 (d, J = 7.6 Hz, 1H), 7.56 (d, J = 8.4 Hz, 4H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 16.1, 18.3, 29.8, 30.1, 55.2, 74.2, 86.6, 93.8, 113.4, 121.0, 126.0, 126.4,
127.4, 128.3, 132.4, 137.7, 138.1, 145.0, 158.9; IR (neat):  3398, 2972, 2910, 2225, 1589, 1486,
1400, 1090, 1014, 814, 757, 723 cm-1; HRMS (ESI-TOF) Calcd. for C27H21Cl2 [M-OH]+:
415.1015, found: 415.1007.
4-(2-(1-cyclobutylideneethyl)phenyl)-2-phenylbut-3-yn-2-ol (1af). Yield: 97%, 1091 mg; A
o
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white solid; Mp: 79-81 C; Eluent: PE/EA = 10/1. H NMR (400 MHz, CDCl3) δ 1.84-1.87 (m,
4H), 1.87-1.92 (m, 3H), 2.52 (t, J = 6.8 Hz, 2H), 2.74 (t, J = 8.0 Hz, 2H), 7.10-7.15 (m, 2H),
7.21-7.30 (m, 2H), 7.32-7.38 (m, 2H), 7.42-7.46 (m, 1H), 7.71-7.75 (m, 2H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 16.1, 18.1, 29.8, 30.2, 33.2, 70.4, 84.8, 94.2, 120.9, 125.0, 126.0, 126.4,
127.6, 128.18, 128.24, 128.3, 132.4, 138.1, 145.0, 145.8; IR (neat):  3385, 3055, 2978, 2910,
1600, 1445, 1141, 1070, 938, 756, 697 cm-1; HRMS (EI-TOF) Calcd. for C22H22O [M]+: 302.1671,
found: 302.1663.
3-(2-(1-cyclobutylideneethyl)phenyl)-1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol (1ag). Yield:
1
84%, 1424; A light yellow liquid; Eluent: PE/EA = 6/1. H NMR (400 MHz, CDCl3, TMS) δ
1.80-1.89 (m, 5H), 2.47 (t, J = 7.2 Hz, 2H), 2.71 (t, J = 7.2 Hz, 2H), 3.02 (s, 1H), 3.75 (s, 6H),
6.82-6.86 (m, 4H), 7.09-7.15 (m, 2H), 7.21-7.26 (m, 1H), 7.42-7.46 (m, 1H), 7.53-7.58 (m, 4H);
13C{1H} NMR (100 MHz, CDCl3, TMS) δ 16.1, 18.3, 29.8, 30.1, 55.2, 74.2, 86.6, 93.8, 113.4,
121.0, 126.0, 126.4, 127.4, 128.3, 132.4, 137.7, 138.1, 145.0, 158.9; IR (neat):  3450, 3057, 2947,
2908, 2835, 1607, 1507, 1247, 1171, 1033, 829, 759 cm-1; HRMS (DART-FTICR) Calcd. for
C29H27O2 [M-OH]+: 407.2006, found: 407.2009.
General procedure for the synthesis of compound 2b: To a stirred solution of compound
3-(5-chloro-2-(cyclobutylidene(phenyl)methyl)phenyl)-1,1-diphenylprop-2-yn-1-ol 1b (92 mg,
1.0 equiv) in DCE (2 mL) was added I2 (101 mg, 2.0 equiv). The resulted mixture was stirred at
60 oC for 4 h. After quenching the remaining I2 by Na2SO3 solution and removing solvent under
reduced pressure, the residue was purified by a column chromatography on silica gel (petroleum
ether
/
ethyl acetate
=
200
/
1) to afford the corresponding product
6-chloro-8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene 2b
in 95% yield (108 mg).
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8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2a) (major).
Yield: 65%, 69 mg, 3.0:1 dr (determined by 1H NMR); A white solid; Mp＞200oC; Eluent: PE/EA
= 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 1.32-1.42 (m, 1H), 1.74-2.00 (m, 2H), 2.07-2.21 (m,
1H), 2.34-2.47 (m, 2H), 6.61-6.65 (m, 2H), 7.00-7.09 (m, 4H), 7.15-7.28 (m, 7H), 7.32-7.44 (m,
5H), 7.48-7.54 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.7, 28.6, 32.5, 66.0, 94.0,
121.6, 123.5, 124.9, 126.0, 126.4, 126.7, 127.0, 127.6, 127.9, 128.2, 128.3, 128.4, 128.7, 129.6,
138.2, 141.9, 142.2, 144.1, 145.3, 150.6, 153.5, 160.4; IR (neat): 3060, 3015, 2959, 2921, 2835,
1600, 1579, 1458, 1441, 1124, 761, 694 cm-1; HRMS (DART-FTICR) Calcd. for C32H26I [M+H]+:
537.1074, found: 537.1072.
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8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2a) (minor).
Yield: 21%, 23 mg, 3.0:1 dr (determined by 1H NMR); A white solid; Mp＞200oC; Eluent: PE/EA
= 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 0.79-0.88 (m, 1H), 1.32-1.42 (m, 1H), 1.74-2.00 (m,
2H), 2.07-2.21 (m, 1H), 2.34-2.47 (m, 1H), 7.00-7.09 (m, 6H), 7.15-7.28 (m, 7H), 7.32-7.44 (m,
5H), 7.48-7.54 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.3, 28.5, 30.6, 65.4, 93.7,
120.7, 123.6, 125.8, 126.6, 126.9, 127.5, 127.8, 128.7, 129.7, 138.0, 140.5, 142.0, 145.5, 145.7,
10.6, 157.8.
6-chloro-8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2b) (major). Yield: 71%, 81 mg, 3.0:1 dr (determined by 1H NMR); A white solid; Mp; 179-181
oC; Eluent: PE/EA = 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 1.30-1.42 (m, 1H), 1.75-2.02 (m,
2H), 2.07-2.23 (m, 1H), 2.34-2.48 (m, 2H), 6.59 (d, J = 7.2 Hz, 2H), 6.97-7.15 (m, 5H), 7.16-7.28
(m, 5H), 7.33-7.49 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.8, 28.5, 32.4, 65.6, 92.7,
121.6, 124.5, 124.7, 125.8, 126.6, 127.1, 128.2, 128.4, 128.5, 128.6, 129.5, 132.7, 137.5, 141.6,
141.7, 145.1, 145.9, 148.8, 154.2, 162.3. IR (neat):  2995, 2970, 2942, 2900, 1596, 1451, 1072,
792, 696 cm-1; HRMS (DART-FTICR) Calcd. for C32H25ClI [M+H]+: 571.0684, found: 571.0687.
6-chloro-8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2b) (minor). Yield: 24%, 27 mg, 3.0:1 dr (determined by 1H NMR); A white solid; Mp; 179-181
oC; Eluent: PE/EA = 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 0.75-0.90 (m, 1H), 1.30-1.42 (m,
1H), 1.75-2.02 (m, 2H), 2.07-2.23 (m, 1H), 2.34-2.48 (m, 1H), 6.97-7.15 (m, 6H), 7.16-7.28 (m,
6H), 7.33-7.49 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.5, 28.5, 30.6, 65.0, 91.9,
120.8, 125.6, 126.6, 127.7, 128.0, 128.7, 128.8, 129.6, 132.8, 137.3, 140.4, 141.3, 145.2, 147.4,
148.9, 151.2, 159.9.
8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-6-(trifluoromethyl)-1,2,3,3a-tetrahydrocyclopenta[a]i
ndene (2c) (major). Yield: 51%, 62 mg, 2.8:1 dr (determined by 1H NMR); White needles; Mp＞
1
200oC; Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) 1.30-1.44 (m, 1H), 1.75-1.98
(m, 2H), 2.05-2.25 (m, 1H), 2.37-2.50 (m, 2H), 6.61 (d, J = 7.2 Hz, 2H), 6.95-7.15 (m, 3H),
7.19-7.46 (m, 12H), 7.74 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.8, 28.5, 32.4, 66.0,
92.4, 118.2 (q, J = 4.2 Hz), 122.0 (q, J = 3.9 Hz), 124.6 (q, J = 270 Hz), 125.9, 126.8, 127.2, 127.7,
128.0, 128.3, 128.5, 128.60, 128.62, 128.9, 129.2 (q, J = 31.7 Hz), 129.5, 137.6, 141.1, 141.8,
144.7, 145.0, 153.9, 154.4, 162.2.; IR (neat):  3060, 2961, 2919, 2848, 1492, 1445, 1259, 1112,
1090, 1017, 795, 740, 696 cm-1; HRMS (DART-FTICR) Calcd. for C33H25F3I [M+H]+: 605.0948,
found: 605.0942.
8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-6-(trifluoromethyl)-1,2,3,3a-tetrahydrocyclopenta[a]i
ndene (2c) (minor). Yield: 19%, 22 mg, 2.8:1 dr (determined by 1H NMR); White needles; Mp＞
200oC; Eluent: PE/EA = 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 0.82-0.94 (m, 1H), 1.30-1.44
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(m, 1H), 1.75-1.98 (m, 2H), 2.05-2.25 (m, 1H), 2.37-2.50 (m, 1H), 6.95-7.15 (m, 5H), 7.19-7.46
(m, 12H), 7.64 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.6, 28.4, 30.6, 65.5, 91.3,
117.3 (q, J = 4.2 Hz), 125.7, 127.0, 127.8, 128.7, 129.6, 137.6, 140.4, 140.9, 145.2, 145.9, 151.5,
160.3; 19F NMR (376 MHz, CDCl3) δ -61.67.
5-chloro-8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2d) (major). Yield: 44%, 50 mg, 2.7:1 dr (determined by 1H NMR); A white solid; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.34-1.43 (m, 1H), 1.73-1.97 (m,
2H), 2.07-2.12 (m, 1H), 2.33-2.46 (m, 2H), 6.60 (d, J = 7.2 Hz, 2H), 7.03-7.14 (m, 4H), 7.19-7.28
(m, 5H), 7.34-7.45 (m, 7H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.7, 28.4, 32.4, 65.9, 93.0,
122.3, 124.2, 125.9, 126.7, 126.9, 127.1, 128.0, 128.2, 128.4, 128.6, 129.5, 130.8, 137.6, 141.4,
141.8, 142.5, 145.1, 152.1, 154.0, 160.8; IR (neat):  3050, 2979, 2916, 2851, 1594, 1490, 1443,
1123, 1092, 817, 693 cm-1; HRMS (DART-FTICR) Calcd. for C32H25ClI [M+H]+: 571.0684,
found: 571.0677.
5-chloro-8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2d) (minor). Yield: 16%, 18 mg, 2.7:1 dr (determined by 1H NMR); A white solid; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.79-0.88 (m, 1H), 1.34-1.43 (m,
1H), 1.73-1.97 (m, 2H), 2.07-2.12 (m, 1H), 2.33-2.46 (m, 1H), 6.95-6.99 (m, 2H), 7.03-7.14 (m,
4H), 7.19-7.28 (m, 6H), 7.34-7.45 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.4, 28.4,
30.6, 65.3, 92.2, 121.5, 125.7, 127.7, 127.9, 128.7, 128.8, 129.6, 130.7, 137.4, 140.4, 141.2, 144.1,
145.3, 151.0, 152.1, 158.3.
5-bromo-8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2e) (major). Yield: 60%, 74 mg, 2.4:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.30-1.42 (m, 1H), 1.70-2.01 (m,
2H), 2.05-2.23 (m, 1H), 2.33-2.45 (m, 2H), 6.60 (d, J = 7.2 Hz, 2H), 6.95-7.15 (m, 3H), 7.16-7.28
(m, 6H), 7.32-7.43 (m, 7H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.7, 28.5, 32.4, 66.0, 92.9,
118.9, 122.7, 125.9, 126.7, 127.0, 127.1, 128.0, 128.2, 128.4, 128.6, 129.5, 129.8, 137.7, 141.3,
141.8, 143.0, 145.0, 152.4, 154.0, 160.8; IR (neat):  2987, 2953, 2898, 1600, 1445, 1066, 751,
694 cm-1; HRMS (DART-FTICR) Calcd. for C32H25BrI [M+H]+: 615.0179, found: 615.0175.
5-bromo-8-(1-iodo-2,2-diphenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2e) (minor). Yield: 25%, 31 mg, 2.4:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.78-0.91 (m, 1H), 1.30-1.42 (m,
1H), 1.70-2.01 (m, 2H), 2.05-2.23 (m, 1H), 2.33-2.45 (m, 1H), 6.95-7.15 (m, 6H), 7.16-7.28 (m,
6H), 7.32-7.43 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.4, 28.4, 30.5, 65.4, 92.2,
118.9, 121.9, 125.7, 126.7, 127.7, 127.9, 128.6, 128.8, 129.6, 130.0, 137.5, 140.4, 141.0, 144.6,
145.3, 151.1, 152.4, 158.3.
8-(1-iodo-2,2-diphenylvinyl)-5-methyl-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
1
(2f) (major). Yield: 73%, 79 mg, 3.2:1 dr (determined by H NMR); Light yellow needles; Mp;
o
1
159-161 C; Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.30-1.41 (m, 1H),
1.71-1.94 (m, 2H), 2.02-2.20 (m, 1H), 2.28 (s, 3H), 2.32-2.45 (m, 2H), 6.64 (d, J = 7.2 Hz, 2H),
7.01-7.09 (m, 5H), 7.17-7.27 (m, 5H), 7.32-7.43 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3, TMS)
δ 21.5, 22.6, 28.5, 32.6, 65.8, 94.3, 121.2, 124.6, 126.0, 126.3, 126.9, 127.4, 127.8, 128.2, 128.3,
128.4, 128.7, 129.6, 134.5, 138.1, 141.4, 141.9, 142.4, 145.3, 150.7, 153.3, 159.4; IR (neat): 
3055, 3023, 2960, 2919, 2858, 1594, 1589, 1442, 1028, 754, 695 cm-1; HRMS (DART-FTICR)
Calcd. for C33H28I [M+H]+: 551.1230, found: 551.1231.
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8-(1-iodo-2,2-diphenylvinyl)-5-methyl-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
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(2f) (minor). Yield: 22%, 25 mg, 3.2:1 dr (determined by H NMR); Light yellow needles; Mp;
o
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159-161 C; Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.77-0.90 (m, 1H),
1.30-1.41 (m, 1H), 1.71-1.94 (m, 2H), 2.02-2.20 (m, 1H), 2.28 (s, 3H), 2.32-2.45 (m, 1H), 6.99 (s,
1H), 7.01-7.09 (m, 5H), 7.17-7.27 (m, 6H), 7.32-7.43 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3,
TMS) δ 21.2, 28.5, 30.6, 65.1, 93.7, 120.3, 125.8, 126.5, 127.46, 127.55, 127.60, 127.8, 128.6,
128.7, 129.7, 134.5, 137.7, 140.5, 142.2, 143.0, 145.6, 150.2, 150.8, 156.5.
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3a-(3-chlorophenyl)-8-(1-iodo-2,2-diphenylvinyl)-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2g) (major). Yield: 56%, 64 mg, 2.9:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.31-1.45 (m, 1H), 1.70-2.04 (m,
2H), 2.05-2.26 (m, 1H), 2.28-2.46 (m, 2H), 6.47 (d, J = 7.6 Hz, 1H), 6.83-6.86 (m, 1H) 6.92-7.17
(m, 5H), 7.18-7.47 (m, 10H), 7.49-7.56 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.6,
28.6, 32.6, 65.7, 93.6, 121.8, 123.6, 124.3, 125.0, 126.0, 126.8, 127.0, 127.6, 127.9, 128.2, 128.4,
128.6, 129.56, 129.58, 134.3, 138.8, 141.5, 144.0, 144.3, 145.4, 149.9, 153.7, 159.2; IR (neat): 
2995, 2919, 2864, 1590, 1489, 1456, 1072, 740, 696 cm-1; HRMS (DART-FTICR) Calcd. for
C32H25ClI [M+H]+: 571.0684, found: 571.0685.
3a-(3-chlorophenyl)-8-(1-iodo-2,2-diphenylvinyl)-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2g) (minor). Yield: 20%, 22 mg, 2.9:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.78-0.91 (m, 1H), 1.31-1.45 (m,
1H), 1.70-2.04 (m, 2H), 2.05-2.26 (m, 1H), 2.28-2.46 (m, 1H), 6.92-7.17 (m, 5H), 7.18-7.47 (m,
12H), 7.49-7.56 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.5, 28.5, 30.6, 65.1, 92.7,
120.9, 124.1, 125.0, 126.0, 126.9, 127.2, 128.7, 129.7, 130.0, 134.4, 138.5, 140.5, 144.3, 145.4,
145.6, 149.9, 150.7, 156.9.
3a-(4-chlorophenyl)-8-(1-iodo-2,2-diphenylvinyl)-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2h) (major). Yield: 67%, 76 mg, 2.9:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.32-1.43 (m, 1H), 1.70-1.92 (m,
2H), 2.05-2.24 (m, 1H), 2.28-2.45 (m, 2H), 6.54 (d, J = 8.4 Hz, 2H), 6.95-7.14 (m, 4H), 7.15-7.31
(m, 6H), 7.32-7.46 (m, 5H), 7.48-7.55 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.5,
28.5, 32.4, 65.4, 93.5, 121.7, 123.4, 125.0, 126.9, 127.0, 127.4, 127.9, 128.2, 128.4, 128.5, 128.6,
129.5, 132.1, 138.5, 140.8, 142.0, 144.0, 145.1, 150.1, 153.7, 159.8; IR (neat):  3076, 3052, 2963,
2861, 1597, 1488, 1442, 1179, 1047, 789, 699 cm-1; HRMS (DART-FTICR) Calcd. for C32H25ClI
[M+H]+: 571.0684, found: 571.0687.
3a-(4-chlorophenyl)-8-(1-iodo-2,2-diphenylvinyl)-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2h) (minor). Yield: 23%, 26 mg, 2.9:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
1
Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.77-0.90 (m, 1H), 1.32-1.43 (m,
1H), 1.70-1.92 (m, 2H), 2.05-2.24 (m, 1H), 2.28-2.45 (m, 1H), 6.95-7.14 (m, 6H), 7.15-7.31 (m,
7H), 7.32-7.46 (m, 4H), 7.48-7.55 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.2, 28.5,
30.5, 64.8, 92.8, 120.8, 123.5, 127.1, 127.2, 127.58, 127.64, 127.9, 128.7, 128.8, 129.7, 132.3,
138.2, 140.4, 140.5, 145.4, 145.6, 150.2, 150.7, 157.2.
3a-(4-bromophenyl)-8-(1-iodo-2,2-diphenylvinyl)-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2i) (major). Yield: 57%, 70 mg, 3.1:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.31-1.44 (m, 1H), 1.70-2.01 (m,
2H), 2.05-2.24 (m, 1H), 2.28-2.45 (m, 2H), 6.48 (d, J = 8.0 Hz, 2H), 6.96-7.17 (m, 5H), 7.17-7.31
(m, 5H), 7.32-7.44 (m, 5H), 7.46-7.55 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.5,
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28.5, 32.3, 65.5, 93.5, 120.3, 121.7, 123.4, 125.0, 126.9, 127.0, 127.8, 127.9, 128.2, 128.4, 128.6,
129.5, 131.5, 138.6, 141.4, 142.0, 144.0, 145.1, 150.0, 153.7, 159.7; IR (neat):  3073, 3047, 2955,
2911, 2868, 1594, 1484, 1441, 1186, 1105, 738, 699 cm-1; HRMS (DART-FTICR) Calcd. for
C32H23BrI [M+H]+: 613.0022, found: 613.0026.
3a-(4-bromophenyl)-8-(1-iodo-2,2-diphenylvinyl)-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2i) (minor). Yield: 18%, 22 mg, 3.1:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.77-0.90 (m, 1H), 1.31-1.44 (m,
1H), 1.70-2.01 (m, 2H), 2.05-2.24 (m, 1H), 2.28-2.45 (m, 1H), 6.96-7.17 (m, 4H), 7.17-7.31 (m,
8H), 7.32-7.44 (m, 5H), 7.46-7.55 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.2, 28.5,
30.5, 64.9, 92.8, 120.5, 120.8, 123.5, 127.1, 127.58, 127.64, 127.9, 128.7, 129.7, 131.8, 138.3,
140.5, 141.1, 145.4, 145.6, 150.1, 150.7, 157.2.
8-(1-iodo-2,2-diphenylvinyl)-3a-(4-(trifluoromethyl)phenyl)-1,2,3,3a-tetrahydrocyclopenta[
a]indene (2j) (major). Yield: 62%, 74 mg, 3.6:1 dr (determined by 1H NMR); White needles; Mp
＞ 200oC; Eluent: PE/EA = 100/1. H NMR (400 MHz, CDCl3, TMS) δ 1.37-1.49 (m, 1H)
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1.72-1.88 (m, 2H), 1.98-2.24 (m, 1H), 2.41-2.47 (m, 2H), 6.73 (d, J = 8.0 Hz, 2H), 7.00-7.14 (m,
3H), 7.20-7.31 (m, 7H), 7.34-7.42 (m, 5H), 7.49-7.56 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3,
TMS) δ 22.6, 28.6, 32.4, 65.8, 93.2, 121.8, 123.5, 124.2 (q, J = 270. 5 Hz), 125.1, 125.4 (q, J = 3.5
Hz), 126.3, 127.09, 127.10, 128.0, 128.2, 128.4, 128.6, 128.7, (q, J = 32.2 Hz), 129.5, 138.9,
142.0, 144.1, 145.1, 146.6, 149.7, 153.8, 159.4. 19F NMR (376 MHz, CDCl3) δ -62.43; IR (neat):
 3060, 3021, 2989, 2953, 1613, 1442, 1411, 1324, 1119, 1016, 735, 698 cm-1; HRMS
(DART-FTICR) Calcd. for C33H24F3 [M-I]+: 477.1825, found: 477.1825.
8-(1-iodo-2,2-diphenylvinyl)-3a-(4-(trifluoromethyl)phenyl)-1,2,3,3a-tetrahydrocyclopenta[
a]indene (2j) (minor). Yield: 17%, 21 mg, 3.6:1 dr (determined by 1H NMR); White needles; Mp
＞ 200oC; Eluent: PE/EA = 100/1. H NMR (400 MHz, CDCl3, TMS) δ 0.85-0.92 (m, 1H),
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1.37-1.49 (m, 1H) 1.72-1.88 (m, 1H), 1.98-2.24 (m, 2H), 2.41-2.47 (m, 1H), 7.00-7.14 (m, 3H),
7.20-7.31 (m, 7H), 7.34-7.42 (m, 6H), 7.49-7.56 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3, TMS)
δ 21.2, 28.5, 30.5, 65.2, 92.5, 120.9, 123.6, 125.7 (q, J = 3.7 Hz), 126.2, 127.3, 127.7, 127.9,
128.7, 129.6, 138.6, 140.4, 145.3, 145.7, 146.4, 149.8, 150.9, 156.9; 19F NMR (376 MHz, CDCl3)
δ -62.43.
8-(1-iodo-2-phenyl-2-(p-tolyl)vinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2k
1
and 2k’). Yield: 93%, 102 mg (1:1), 3.8:1 dr (determined by H NMR); Yellow needles; Mp;
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141-143 C; Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.8-0.99 (m, 0.34H),
1.32-1.39 (m, 1.40H), 1.76-1.89 (m, 2.75H), 2.13-2.18 (m, 1.55H), 2.30-2.34 (m, 1.37H),
2.36-2.46 (m, 4.43H), 6.62 (d, J = 7.2 Hz, 1H), 6.69 (d, J = 7.2 Hz, 1H), 6.82-6.93 (m, 0.51H),
7.00-7.12 (m, 7.43H), 7.15-7.43 (m, 14.08H), 7.48-7.53 (m, 1.35H); 13C{1H} NMR (100 MHz,
CDCl3, TMS) δ 21.1, 21.2, 21.3, 21.4, 22.7, 28.5, 28.6, 30.6, 30.7, 32.50, 32.54, 65.3, 65.9, 92.6,
92.7, 93.4, 93.5, 120.7, 121.6, 123.5, 124.8, 125.8, 125.9, 126.1, 126.35, 126.40, 126.6, 126.7,
126.8, 126.9, 127.4, 127.5, 127.7, 127.8, 128.1, 128.2, 128.28, 128.36, 128.58, 128.62, 128.66,
128.72, 128.9, 129.0, 129.49, 129.55, 129.59, 129.67, 136.8, 137.4, 137.59, 137.64, 138.05,
138.08, 138.3, 139.1, 140.7, 142.1, 142.22, 142.24, 142.4, 142.6, 144.08, 144.13, 145.4, 150.46,
150.52, 150.6, 153.4, 153.5, 157.7, 160.1, 160.3; IR (neat):  2980, 2958, 2924, 2900, 1597, 1489,
1442, 1259, 1080, 743, 696 cm-1; HRMS (DART-FTICR) Calcd. for C33H26I [M+H]+: 549.1074,
found: 549.1074.
8-(1-iodo-2-(4-methoxyphenyl)-2-phenylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]i
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ndene (2l and 2l’). 77%, 87 mg (1:0.91), 2.5:1 dr (determined by 1H NMR); White needles; Mp:
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189-191 C; Eluent: PE/EA = 80/1. H NMR (400 MHz, CDCl3, TMS) δ 0.80-0.98 (m, 0.83H),
1.34-1.39 (m, 3.03H), 1.74-2.15 (m, 7.52H), 2.38-2.43 (m, 4.39H), 3.62 (s, 0.68H), 3.71 (s, 2.74H),
3.79 (s, 3.00H), 6.53-6.62 (m, 2.36H), 6.70-6.74 (m, 3.75H), 6.90-6.93 (m, 2.93H), 6.99-7.25 (m,
23.54H), 7.31-7.53 (m, 10.75H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.3, 22.6, 28.5, 30.6,
30.8, 32.50, 32.55, 55.0, 55.1, 65.7, 65.9, 91.9, 92.8, 93.2, 112.9, 113.4, 113.6, 120.6, 121.4, 121.5,
123.5, 124.8, 125.7, 125.9, 126.1, 126.3, 126.46, 126.53, 126.7, 126.8, 127.5, 127.7, 128.1, 128.2,
128.3, 128.6, 128.7, 129.6, 129.7, 129.9, 130.0, 131.0, 134.3, 137.5, 137.7, 138.1, 138.4, 140.8,
141.9, 142.20, 142.22, 144.0, 144.1, 145.4, 145.7, 150.0, 150.5, 152.9, 153.6, 157.6, 158.8, 159.0,
159.1, 159.9, 160.2; IR (neat):  2986, 2969, 2900, 1602, 1505, 1455, 1242, 1065, 1027, 832, 740,
694 cm-1; HRMS (DART-FTICR) Calcd. for C33H28OI [M+H]+: 567.1179, found: 567.1179.
8-(2,2-bis(4-chlorophenyl)-1-iodovinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2m) (major). Yield: 70%, 85 mg, 4.0:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.32-1.43 (m, 1H), 1.73-2.00 (m,
2H), 2.10-2.24 (m, 1H), 2.29-2.50 (m, 2H), 6.62-6.67 (m, 2H), 7.01-7.14 (m, 5H), 7.17-7.29 (m,
5H), 7.30-7.42 (m, 4H), 7.43-7.51 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.7, 28.6,
32.6, 66.1, 95.1, 121.5, 123.7, 125.1, 125.9, 126.7, 126.8, 128.5, 128.6, 128.7, 130.0, 131.1, 133.4,
134.1, 138.0, 140.1, 141.9, 142.9, 143.7, 150.5, 151.0, 160.7; IR (neat):  3068, 2981, 2924, 2864,
1587, 1487, 1104, 757, 700 cm-1; HRMS (DART-FTICR) Calcd. for C32H24Cl2I [M+H]+:
605.0294, found: 605.0289.
8-(2,2-bis(4-chlorophenyl)-1-iodovinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
(2m) (minor). Yield: 18%, 21 mg, 4.0:1 dr (determined by 1H NMR); White needles; Mp＞200oC;
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.82-0.92 (m, 1H), 1.32-1.43 (m,
1H), 1.73-2.00 (m, 2H), 2.10-2.24 (m, 1H), 2.29-2.50 (m, 1H), 6.91 (d, J = 8.0 Hz, 1H), 7.01-7.14
(m, 7H), 7.17-7.29 (m, 4H), 7.30-7.42 (m, 4H), 7.43-7.51 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3, TMS) δ 21.4, 28.5, 30.8, 65.5, 94.4, 120.5, 123.8, 125.7, 127.0, 127.9, 128.7, 131.2, 133.7,
134.0, 137.6, 138.6, 141.8, 143.3, 145.2, 148.1, 150.6, 158.3.
8-(1-iodo-2,2-di-p-tolylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2n) (major).
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Yield: 72%, 81 mg, 4.4:1 dr (determined by H NMR); White needles; Mp ＞ 200 C; Eluent:
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PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.32-1.42 (m, 1H), 1.73-2.00 (m, 2H),
2.02-2.16 (m, 1H), 2.31 (s, 3H), 2.37 (s, 3H), 2.38-2.46 (m, 2H), 6.68 (d, J = 7.6 Hz, 2H),
6.97-7.11 (m, 7H), 7.13-7.33 (m, 7H), 7.48-7.54 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS)
δ 21.2, 21.4, 22.6, 28.5, 32.6, 65.9, 92.9, 121.6, 123.5, 124.8, 126.1, 126.4, 126.6, 128.2, 128.6,
128.8, 128.9, 129.5, 136.7, 137.6, 138.4, 139.3, 142.2, 142.5, 144.2, 150.5, 153.4, 160.1; IR (neat):
 2962, 2913, 1738, 1594, 1455, 1047, 1023, 743, 698 cm-1; HRMS (DART-FTICR) Calcd. for
C34H30I [M+H]+: 565.1387, found: 565.1382.
8-(1-iodo-2,2-di-p-tolylvinyl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2n) (minor).
1
o
Yield: 17%, 19 mg, 4.4:1 dr (determined by H NMR); White needles; Mp ＞ 200 C; Eluent:
1
PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.83-0.93 (m, 1H), 1.32-1.42 (m, 1H),
1.73-2.00 (m, 2H), 2.02-2.16 (m, 1H), 2.18 (s, 3H), 2.39 (s, 3H), 2.38-2.46 (m, 1H), 6.80-6.90 (m,
4H), 6.97-7.11 (m, 6H), 7.13-7.33 (m, 6H), 7.48-7.54 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3,
TMS) δ 21.1, 21.3, 28.5, 30.7, 65.3, 92.2, 120.7, 125.8, 126.4, 126.8, 128.2, 128.7, 128.8, 129.6,
137.3, 137.5, 137.9, 138.1, 142.0, 142.8, 145.7, 150.4, 150.6, 157.6.
8-(1-iodo-2-phenylprop-1-en-1-yl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2o)
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(major). Yield: 67%, 64 mg, 4.0:1 dr (determined by H NMR); Light yellow needles; Mp;
o
1
149-151 C; Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.25-1.32 (m, 1H),
1.64-1.85 (m, 2H), 1.99-2.14 (m, 1H), 2.15-2.41 (m, 2H), 2.49 (s, 3H), 6.53-6.58 (m, 2H),
6.96-7.06 (m, 4H), 7.09-7.12 (m, 1H), 7.14-7.23 (m, 6H), 7.38-7.42 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 22.5, 28.6, 30.8, 32.3, 65.8, 92.8, 121.2, 123.3, 124.7, 125.9, 126.3, 126.6,
126.7, 127.2, 128.3, 128.4, 138.0, 142.1, 142.3, 144.4, 147.9, 150.4, 159.8.; IR (neat):  3167,
3049, 3015, 2958, 2864, 1594, 1487, 1456, 1440, 1133, 990, 761, 698 cm-1; HRMS (EI-TOF)
Calcd. for C27H23I [M]+: 474.0845, found: 474.0851.
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8-(1-iodo-2-phenylprop-1-en-1-yl)-3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2o)
1
(minor). Yield: 17%, 16 mg, 4.0:1 dr (determined by H NMR); Light yellow needles; Mp;
o
1
149-151 C; Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.64-0.75 (m, 1H),
1.25-1.32 (m, 1H), 1.64-1.85 (m, 2H), 1.99-2.14 (m, 1H), 2.15-2.41 (m, 1H), 2.50 (s, 3H),
6.53-6.58 (m, 1H), 6.96-7.06 (m, 6H), 7.09-7.12 (m, 1H), 7.14-7.23 (m, 5H), 7.38-7.42 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.2, 30.4, 30.7, 65.1, 92.8, 120.4, 123.4, 125.7, 126.5,
126.8, 127.1, 127.6, 128.6, 138.0, 140.9, 142.0, 144.7, 146.0, 150.5, 157.5.
9-(iodo(3a-methyl-1,2,3,3a-tetrahydrocyclopenta[a]inden-8-yl)methylene)-9H-fluorene (2p)
(major). Yield: 55%, 51 mg, 2.9:1 dr (determined by 1H NMR); Yellow needles; Mp; 113-115 oC;
1
Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.24-1.31 (m, 1H), 1.46 (s, 3H),
1.79-1.87 (m, 1H), 2.08-2.18 (m, 1H), 2.22-2.33 (m, 1H), 2.35-2.51 (m, 2H), 6.91-6.98 (m, 1H),
7.16-7.26 (m, 4H), 7.36-7.49 (m, 3H), 7.58-7.76 (m, 3H), 9.06-9.14 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3, TMS) δ 20.6, 22.0, 28.5, 31.9, 58.5, 93.9, 118.9, 119.5, 121.0, 122.6, 124.9, 125.3,
126.3, 127.0, 127.1, 128.2, 129.4, 137.2, 138.0, 138.6, 139.2, 141.66, 141.69, 142.7, 151.6, 161.6;
IR (neat):  3063, 3039, 2958, 2919, 2856, 1605, 1463, 1444, 1046, 752, 727 cm-1; HRMS
(DART-FTICR) Calcd. for C27H22I [M+H]+: 473.0761, found: 473.0753.
9-(iodo(3a-methyl-1,2,3,3a-tetrahydrocyclopenta[a]inden-8-yl)methylene)-9H-fluorene (2p)
(minor). Yield: 19%, 19 mg, 2.9:1 dr (determined by 1H NMR); Yellow needles; Mp; 113-115 oC;
1
Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.24-1.31 (m, 1H), 1.37 (s, 3H),
1.95-2.02 (m, 1H), 2.08-2.18 (m, 1H), 2.22-2.33 (m, 1H), 2.35-2.51 (m, 2H), 6.82-6.88 (m, 1H),
7.07-7.12 (m, 1H), 7.16-7.26 (m, 1H), 7.36-7.49 (m, 4H), 7.58-7.76 (m, 3H), 7.80-7.91 (m, 1H),
9.06-9.14 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.0, 22.0, 28.0, 31.3, 93.3, 119.5,
120.4, 122.8, 124.5, 124.86, 124.91, 126.4, 127.0, 127.1, 138.0, 139.1, 140.5, 141.6, 144.1, 151.0,
160.1.
9-(iodo(3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]inden-8-yl)methylene)-9H-fluorene (2q)
(major). Yield: 64%, 69 mg, 12.5:1 dr (determined by H NMR); Yellow needles; Mp＞200oC;
1
1
Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.69-1.80 (m, 1H), 2.04-2.20 (m,
2H), 2.25-2.41 (m, 2H), 2.75-2.83 (m, 1H), 6.88 (m, 1H), 7.05-7.17 (m, 2H), 7.18-7.24 (m, 4H),
7.27-7.35 (m, 3H), 7.40-7.52 (m, 4H), 7.64-7.67 (m, 1H), 7.70-7.85 (m, 1H), 9.08-9.19 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.5, 28.7, 31.1, 66.1, 92.1, 119.0, 119.6, 120.4, 124.1,
124.6, 124.9, 125.3, 125.6, 126.5, 126.8, 127.1, 127.2, 128.4, 128.8, 129.5, 138.0, 139.2, 140.8,
141.1, 141.7, 142.8, 143.9, 150.5, 158.6; IR (neat):  3057, 2992, 2950, 2900, 1734, 1455, 1443,
1075, 776, 745, 698 cm-1; HRMS (DART-FTICR) Calcd. for C32H24I [M+H]+: 535.0917, found:
535.0920.
9-(iodo(3a-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]inden-8-yl)methylene)-9H-fluorene (2q)
(minor). Yield: 5%, 5 mg, 12.5:1 dr (determined by H NMR); Yellow needles; Mp ＞ 200oC;
1
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Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.80-0.90 (m, 1H), 1.69-1.80 (m,
1H), 2.04-2.20 (m, 2H), 2.25-2.41 (m, 2H), 6.88 (m, 1H), 7.05-7.17 (m, 1H), 7.18-7.24 (m, 4H),
7.27-7.35 (m, 4H), 7.40-7.52 (m, 4H), 7.64-7.67 (m, 1H), 7.70-7.85 (m, 1H), 9.08-9.19 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3, TMS) δ 22.9, 29.2, 33.6, 66.8, 121.0, 124.0, 125.5, 125.8, 126.4,
127.0, 127.3, 128.5, 128.8, 129.6, 138.0, 140.6, 142.7, 142.9, 150.7, 159.2.
8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-6-(trifluoromethyl)-1,2,3,3a-tetrahydrocyclopenta[a]i
ndene (2r) (major). Yield: 39%, 42 mg, 1.5:1 dr (determined by 1H NMR); Light yellow needles;
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Mp; 165-167 C; Eluent: PE/EA = 200/1. H NMR (600 MHz, CDCl3, TMS) δ 0.95 (s, 3H),
1.59-1.80 (m, 2H), 1.94-2.15 (m, 1H), 2.16-2.37 (m, 3H), 6.87-7.03 (m, 2H), 7.02-7.12 (m, 3H),
7.27-7.45 (m, 7H), 7.77 (s, 1H); 13C{1H} NMR (150 MHz, CDCl3, TMS) δ 20.7, 22.2, 27.9, 31.3,
58.1, 93.1, 118.1 (q, J = 4.1 Hz), 121.4 (q, J = 3.2 Hz), 122.4, 124.7 (q, J = 270.3 Hz), 127.2,
127.7, 128.0, 128.2, 128.9, 129.1 (q, J = 31.8 Hz), 129.7, 133.6, 141.1, 145.3, 145.5, 153.5, 154.8,
164.1. 19F NMR (376 MHz, CDCl3) δ -61.66; IR (neat):  3060, 3023, 2961, 2924, 2861, 1445,
1330, 1165, 1122, 1056, 1006, 830, 760, 696 cm-1; HRMS (DART-FTICR) Calcd. for C28H22F3
[M-I]+: 415.1668, found: 415.1671.
8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-6-(trifluoromethyl)-1,2,3,3a-tetrahydrocyclopenta[a]i
ndene (2r) (minor). Yield: 26%, 28 mg, 1.5:1 dr (determined by 1H NMR); Light yellow needles;
Mp; 165-167 oC; Eluent: PE/EA = 200/1. 1H NMR (600 MHz, CDCl3, TMS) δ 0.64-0.76 (m, 1H),
1.25 (s, 3H), 1.59-1.80 (m, 2H), 1.94-2.15 (m, 1H), 2.16-2.37 (m, 2H), 6.87-7.03 (m, 1H),
7.02-7.12 (m, 3H), 7.27-7.45 (m, 8H), 7.66 (s, 1H); 13C{1H} NMR (150 MHz, CDCl3, TMS) δ
20.8, 21.2, 27.8, 31.2, 57.6, 92.3, 117.2 (q, J = 4.4 Hz), 121.5 (q, J = 3.9 Hz), 124.7 (q, J = 270.8
Hz), 127.58, 127.62, 127.9, 128.2, 128.7, 129.6, 134.6, 140.5, 145.4, 146.2, 151.2, 154.4, 161.8.
19F NMR (376 MHz, CDCl3) δ -61.66.
5-bromo-8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
1
(2s) (major). Yield: 26%, 29 mg, 1.3:1 dr (determined by H NMR); Light yellow needles; Mp;
161-163 oC; Eluent: PE/EA = 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 0.93 (s, 3H), 1.50-1.72
(m, 2H), 1.84-2.08 (m, 1H), 2.13-2.30 (m, 3H), 6.89-6.93 (m, 1H), 6.96-7.12 (m, 4H), 7.32-7.45
(m, 8H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 20.8, 22.1, 27.8, 31.4, 58.1, 93.6, 118.5, 122.7,
125.9, 127.2, 127.6, 127.8, 128.2, 128.8, 129.65, 129.70, 133.7, 141.1, 143.6, 145.5, 153.1, 153.3,
162.8; IR (neat):  2989, 2950, 2919, 2866, 1644, 1473, 1258, 1072, 880, 775, 699 cm-1; HRMS
(DART-FTICR) Calcd. for C27H23BrI [M+H]+: 553.0022, found: 553.0018.
5-bromo-8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
1
(2s) (minor). Yield: 19%, 21 mg, 1.3:1 dr (determined by H NMR); Light yellow needles; Mp;
161-163 oC; Eluent: PE/EA = 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 0.58-0.70 (m, 1H), 1.21
(s, 3H), 1.21-1.23 (m, 1H), 1.50-1.72 (m, 2H), 1.84-2.08 (m, 1H), 2.13-2.30 (m, 1H), 6.96-7.12 (m,
4H), 7.20-7.24 (m, 1H), 7.32-7.45 (m, 8H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 20.7, 21.0,
27.7, 31.2, 57.6, 93.1, 118.6, 121.8, 126.0, 127.5, 128.2, 128.6, 129.6, 129.8, 134.3, 134.5, 140.5,
144.8, 145.5, 150.8, 153.0, 159.9.
8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-5-phenyl-1,2,3,3a-tetrahydrocyclopenta[a]indene
1
(2t) (major). Yield: 48%, 53 mg, 1.5:1 dr (determined by H NMR); White needles; Mp;
1
140-142oC; Eluent: PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.98 (s, 3H), 1.55-1.76
(m, 2H), 1.84-2.35 (m, 4H), 6.94-6.99 (m, 2H), 7.02-7.12 (m, 3H), 7.26-7.49 (m, 9H), 7.52-7.66
(m, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.0, 22.2, 27.9, 31.6, 58.0, 94.6, 121.3, 121.7,
125.6, 126.8, 127.1, 127.5, 127.6, 128.1, 128.6, 129.0, 129.8, 134.0, 137.4, 141.2, 141.7, 144.0,
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145.8, 152.0, 152.7, 162.9; IR (neat):  3055, 3029, 2957, 2858, 1598, 1464, 1439, 1118, 1075,
946, 730, 694 cm-1; HRMS (DART-FTICR) Calcd. for C33H28I [M+H]+: 551.1230, found:
551.1221.
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(2t) (minor). Yield: 32%, 35 mg, 1.5:1 dr (determined by H NMR); White needles; Mp;
140-142oC; Eluent: PE/EA = 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 0.65-0.77 (m, 1H), 1.27
(s, 3H), 1.55-1.76 (m, 2H), 1.84-2.35 (m, 3H), 6.94-6.99 (m, 1H), 7.02-7.12 (m, 4H), 7.26-7.49 (m,
9H), 7.52-7.66 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 21.0, 27.8, 31.4, 57.5, 94.1,
120.7, 121.4, 125.9, 127.0, 127.1, 127.4, 127.7, 128.66, 128.73, 129.7, 134.7, 137.5, 140.5, 141.7,
145.2, 145.6, 150.3, 151.6, 159.7.
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General procedure for the synthesis of 2v; To
a
stirred solution of
3-(2-(1-cyclobutylideneethyl)phenyl)-1,1-diphenylprop-2-yn-1-ol 1v (73 mg, 1.0 equiv) in
DCE (2 mL) was added I2 (101mg, 2 equiv). The resulted mixture was stirred at 60 oC for 2 h.
After quenching the remaining I2 by Na2SO3 solution and removing solvent under reduced
pressure, the residue was purified by a column chromatography on silica gel (petroleum ether /
ethyl
acetate
=
200
/
1)
to
afford
the
corresponding
product
8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-1,2,3,3a-tetrahydrocyclopenta[a]indene 2v in 73%
yield (69 mg).
8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2v) (major).
1
o
Yield: 44%, 42 mg, 1.5:1 dr (determined by H NMR); White needles; Mp; 160-162 C; Eluent:
1
PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 0.94 (s, 3.00H), 1.24-1.30 (m, 1.00H),
1.45-1.74 (m, 2H), 1.86-2.09 (m, 1H) 2.10-2.35 (m, 2H), 6.92-6.98 (m, 2H), 7.02-7.18 (m, 4H),
7.20-7.40 (m, 7H), 7.57 (d, J = 8.0 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 20.9, 22.1,
27.9, 31.5, 57.9, 94.8, 121.5, 122.3, 124.3, 126.5, 127.0, 127.47, 127.52, 128.1, 128.9, 129.7,
134.2, 141.2, 144.7, 145.8, 151.3, 152.6, 162.3; IR (neat):  3057, 2958, 2919, 2853, 1626, 1594,
1462, 1257, 1018, 791, 696 cm-1; HRMS (DART-FTICR) Calcd. for C27H24I [M+H]+: 475.0917,
found: 475.0921.
8-(1-iodo-2,2-diphenylvinyl)-3a-methyl-1,2,3,3a-tetrahydrocyclopenta[a]indene (2v) (minor).
1
o
Yield: 29%, 27 mg, 1.5:1 dr (determined by H NMR); White needles; Mp; 160-162 C; Eluent:
PE/EA = 200/1. 1H NMR (400 MHz, CDCl3, TMS) δ 0.59-0.67 (m, 1H), 1.15-1.22 (m, 1H), 1.23
(s, 3H), 1.45-1.74 (m, 2H), 1.86-2.09 (m, 1H) 2.10-2.35 (m, 1H), 6.92-6.98 (m, 1H), 7.02-7.18 (m,
5H), 7.20-7.40 (m, 7H), 7.52 (d, J = 7.2 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 20.9,
27.9, 31.3, 57.4, 94.2, 120.5, 122.3, 124.4, 126.8, 127.3, 127.7, 128.7, 129.7, 134.9, 140.6, 145.7,
145.9, 150.2, 150.9, 159.2; IR (neat):  3057, 2958, 2919, 2853, 1626, 1594, 1462, 1257, 1018,
791, 696 cm-1; HRMS (DART-FTICR) Calcd. for C27H24I [M+H]+: 475.0917, found: 475.0921.
General procedure for the synthesis of compounds 3y and 4y; To a stirred solution of
compounds 3-(2-(1-cyclobutylidenepropyl)phenyl)-1,1-diphenylprop-2-yn-1-ol 1y (76 mg, 1.0
equiv) in DCE (2 mL) was added I2 (101 mg, 2 equiv). The resulted mixture was stirred at 80 oC
for 4 h. After quenching the remaining I2 by Na2SO3 solution and removing solvent under reduced
pressure, the residue was purified by a column chromatography on silica gel (petroleum ether /
ethyl acetate = 200 / 1) to afford the corresponding product mixtures 3y in 63% yield (62 mg) and
4y in 28% yield (20 mg).
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(3aS,8S,8aR)-5-bromo-2'-iodo-3a-methyl-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopen
ta[a]indene-8,1'-indene] (3s). Yield: 41%, 45 mg; Light yellow needles; Mp: 137-139 oC; Eluent:
1
PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.62 (s, 3H), 1.80-2.00 (m, 4H), 2.20-2.35
7
8
9
(m, 2H), 3.07-3.12 (m, 1H), 6.38 (d, J = 8.4, 1H), 7.08-7.24 (m, 5H), 7.42-7.52 (m, 6H); 13C{1H}
NMR (100 MHz, CDCl3, TMS) δ 28.4, 29.8, 29.9, 42.1, 57.4, 62.1, 70.6, 110.5, 120.0, 122.0,
123.0, 126.1, 126.2, 126.7, 127.0, 128.3, 128.5, 129.3, 130.4, 135.9, 141.6, 143.0, 150.9, 155.2,
156.8; IR (neat):  3345, 1683, 1137, 1104, 756, 710 cm-1; HRMS (DART-FTICR) Calcd. for
C27H23BrI [M+H]+: 553.0022, found: 553.0018.
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(3aS,8S,8aR)-2'-iodo-3a-methyl-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopenta[a]inde
ne-8,1'-indene] (3v). Yield: 70%, 66 mg; White needles; Mp: 128-130 oC; Eluent: PE/EA = 200/1.
1H NMR (400 MHz, CDCl3, TMS) δ 1.63 (s, 3H), 1.75–1.92 (m, 3H), 1.93-2.05 (m, 1H),
2.18-2.40 (m, 2H), 3.08-3.14 (m, 1H), 6.52 (d, J = 7.6 Hz, 1H), 7.06-7.15 (m, 5H), 7.20-7.31 (m,
2H), 7.36-7.54 (m, 5H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 28.5, 29.97, 30.0, 42.1, 57.3,
61.8, 71.1, 111.6, 119.9, 123.1, 123.6, 124.4, 126.0, 126.4, 127.1, 128.16, 128.20, 128.43, 129.3,
136.1, 141.6, 143.8, 150.5, 153.0, 157.2; IR (neat):  3162, 3063, 3023, 2944, 2918, 2845, 1645,
1441, 1259, 1021, 747, 699 cm-1; HRMS (DART-FTICR) Calcd. for C27H24I [M+H]+: 475.0917,
found: 475.0921.
(3aS,8R,8aR)-3a-methyl-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopenta[a]indene-8,1'-
o
1
indene] (4v). Yield: 73%, 51 mg; White needles; Mp: 148-150 C; Eluent: PE/EA = 200/1. H
NMR (400 MHz, CDCl3, TMS) δ 1.66 (s, 3H), 1.67-1.90 (m, 5H), 1.96-2.05 (m, 1H), 2.93-2.98
(m, 1H), 6.52 (d, J = 8.0 Hz, 1H), 6.58 (s, 1H), 7.00 (t, J = 7.2 Hz, 1H), 7.09-7.18 (m, 2H),
7.20-7.28 (m, 3H), 7.34-7.40 (m, 1H), 7.46 (t, J = 7.6 Hz, 2H), 7.52 (d, J = 7.6 Hz, 1H), 7.66 (d, J
= 7.2 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 27.0, 29.6, 32.5, 43.0, 56.7, 60.5, 66.7,
120.3, 123.2, 123.4, 123.6, 126.0, 126.4, 126.9, 127.65, 127.73, 128.6, 135.8, 139.2, 141.9, 143.2,
144.2, 152.8, 156.8; IR (neat):  3060, 2943, 2922, 2852, 1482, 1442, 1263, 1072, 869, 698 cm-1;
HRMS (DART-FTICR) Calcd. for C27H25 [M+H]+: 349.1951, found: 349.1948.
(3aS,8S,8aR)-2'-iodo-6-methoxy-3a-methyl-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclop
o
enta[a]indene-8,1'-indene] (3w). Yield: 74%, 74 mg; Light yellow needles; Mp: 148-150 C;
1
Eluent: PE/EA = 100/1. H NMR (400 MHz, CDCl3, TMS) δ 1.61 (s, 3H), 1.75-1.83 (m, 3H),
1.84-1.89 (m, 1H), 2.15-2.21 (m, 1H), 2.30-2.38 (m, 1H), 3.06-3.12 (m, 1H), 3.65 (s, 3H),
6.01-6.03 (m, 1H), 6.85-6.89 (m, 1H), 7.09-7.13 (m, 4H), 7.14-7.20 (m, 1H), 7.42-7.45 (m, 1H),
7.47-7.54 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 28.5, 30.1, 30.2, 42.3, 55.3, 56.6,
62.4, 71.1, 108.9, 111.3, 114.8, 119.9, 123.1, 124.1, 126.0, 126.4, 127.7, 128.2, 128.4, 128.5,
129.4, 136.1, 141.5, 145.1, 145.4, 150.6, 157.1, 159.2; IR (neat):  3345, 1683 1137 1104, 756,
710 cm-1; HRMS (ESI-TOF) Calcd. for C28H26IO [M+H]+: 505.1023, found: 505.1014.
(3aS,8S,8aR)-5-chloro-2'-iodo-3a-methyl-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopen
o
ta[a]indene-8,1'-indene] (3x). Yield: 58%, 59 mg; White needles; Mp: 137-139 C; Eluent:
1
PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.62 (s, 3H), 1.75-2.05 (m, 4H), 2.17-2.45
(m, 2H), 3.08-3.14 (m, 1H), 6.44 (d, J = 8.4 Hz, 1H), 7.04-7.16 (m, 5H), 7.25-7.27 (m, 1H),
7.40-7.52 (m, 5H), 7.50 (d, J = 8.4 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 28.4, 29.8,
29.9, 42.1, 57.3, 62.1, 70.5, 110.7, 120.0, 123.0, 123.9, 125.7, 126.2, 126.7, 127.6, 128.3, 128.5,
129.3, 133.8, 135.9, 141.6, 142.4, 150.9, 154.8, 156.8; IR (neat):  3063, 2940, 2921, 2857, 1593,
1451, 1072, 749, 699 cm-1; HRMS (DART-FTICR) Calcd. for C27H23ClI [M+H]+: 509.0527,
found: 509.0524.
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The Journal of Organic Chemistry
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(3aS,8S,8aR)-3a-ethyl-2'-iodo-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopenta[a]indene
-8,1'-indene] (3y). Yield: 63%, 62 mg; A colorless liquid; Eluent: PE/EA = 200/1. 1H NMR (400
MHz, CDCl3, TMS) δ 1.00-1.10 (m, 3H), 1.59-2.02 (m, 6H), 2.20-2.34 (m, 2H), 3.22-3.30 (m,
1H), 6.52 (d, J = 7.2 Hz, 1H), 7.06-7.28 (m, 7H), 7.30-7.54 (m, 5H); 13C{1H} NMR (100 MHz,
CDCl3, TMS) δ 10.1, 28.5, 30.0, 33.8, 40.0, 58.0, 61.8, 71.3, 112.2, 119.9, 123.1, 123.9, 124.5,
126.0, 126.5, 127.1, 127.7, 128.4, 129.3, 136.1, 140.2, 141.9, 144.3, 151.8, 157.2; IR (neat): 
3152, 3063, 2972, 2872, 1478, 1450, 1376, 1089, 1046, 879, 698 cm-1; HRMS (DART-FTICR)
Calcd. for C28H26I [M+H]+: 489.1074, found: 489.1070.
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(3aS,8R,8aR)-3a-ethyl-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopenta[a]indene-8,1'-in
dene] (4y). Yield: 28%, 20 mg; White needles; Mp: 146-148 oC; Eluent: PE/EA = 200/1. 1H NMR
(400 MHz, CDCl3, TMS) δ 1.07 (t, J = 7.2 Hz, 3H), 1.60-1.78 (m, 3H), 1.80-2.06 (m, 5H),
1.80-2.01 (m, 5H), 3.09-3.15 (m, 1H), 6.51 (d, J = 7.6 Hz, 1H), 6.58 (s, 1H), 7.00 (t, J = 7.2 Hz,
1H), 7.04-7.28 (m, 5H), 7.34-7.40 (m, 1H), 7.45 (t, J = 7.6 Hz, 2H), 7.52 (d, J = 7.6 Hz, 1H), 7.65
(d, J = 7.2 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 10.3, 26.8, 32.7, 34.0, 40.1, 56.7,
61.2, 66.7, 120.3, 123.2, 123.5, 124.0, 126.0, 126.4, 126.8, 127.4, 127.7, 128.5, 135.7, 140.20,
140.24, 142.1, 142.9, 144.7, 151.8, 156.9; IR (neat):  3065, 3021, 2954, 2858, 1479, 1448, 1332,
1260, 1090, 1026, 772, 746, 699 cm-1; HRMS (DART-FTICR) Calcd. for C28H26 [M]+: 362.2035,
found: 362.2022.
(3aS,8S,8aR)-3a-hexyl-2'-iodo-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopenta[a]inden
1
e-8,1'-indene] (3z). Yield: 83%, 90 mg; A yellow liquid; Eluent: PE/EA = 200/1. H NMR (400
MHz, CDCl3, TMS) δ 0.85-0.95 (m, 3H), 1.28-1.42 (m, 7H), 1.53-1.71 (m, 1H), 1.75-2.05 (m,
6H), 2.22-2.34 (m, 2H), 3.25-3.31 (m, 1H), 6.52 (d, J = 8.0 Hz, 1H), 7.05-7.25 (m, 6H), 7.30-7.55
(m, 6H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 14.1, 22.7, 25.6, 28.5, 30.10, 30.13, 31.8, 40.3,
41.7, 58.5, 61.4, 71.4, 112.2, 119.9, 123.0, 123.9, 124.5, 126.0, 126.5, 127.1, 128.0, 128.1, 128.4,
129.3, 136.1, 141.8, 144.2, 150.3, 152.1, 157.2; IR (neat):  3060, 2963, 2925, 2872, 1488, 1450,
1406, 1250, 1073, 748, 698 cm-1; HRMS (DART-FTICR) Calcd. for C32H34I [M+H]+: 545.1700,
found: 545.1696.
(3aS,8R,8aR)-3a-hexyl-3'-phenyl-2,3,3a,8a-tetrahydro-1H-spiro[cyclopenta[a]indene-8,1'-in
1
dene] (4z). Yield: 16%, 13 mg; A yellow liquid; Eluent: PE/EA = 200/1. H NMR (400 MHz,
CDCl3, TMS) δ 0.85-0.95 (m, 5H), 1.28-1.42 (m, 7H), 1.53-1.71 (m, 2H), 1.75-2.05 (m, 5H),
3.10-3.15 (m, 1H), 6.56-6.58 (m, 1H), 6.94-7.00 (m, 1H), 7.05-7.25 (m, 7H), 7.30-7.55 (m, 2H),
7.62-7.67 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 25.7, 26.7, 32.7, 40.6, 41.9, 57.2,
60.7, 66.7, 120.2, 123.2, 123.4, 124.0, 126.0, 126.4, 126.8, 127.4, 127.7, 128.5, 135.7, 140.2,
142.0, 142.9, 144.5, 152.0, 156.8.
(3aR,8S,8aR)-2'-iodo-3'-phenyl-3a-(3-phenylpropyl)-2,3,3a,8a-tetrahydro-1H-spiro[cyclope
o
nta[a]indene-8,1'-indene] (3aa). Yield: 32%, 37 mg; White needles; Mp: 170-172 C; Eluent:
1
PE/EA = 200/1. H NMR (400 MHz, CDCl3, TMS) δ 1.60-2.07 (m, 8H), 2.00-2.32 (m, 2H),
2.60-2.78 (m, 2H), 3.20-3.27 (m, 1H), 6.48-6.53 (m, 1H), 6.95-7.15 (m, 4H), 7.17-7.32 (m, 8H),
7.35-7.52 (m, 5H); 13C{1H} NMR (100 MHz, CDCl3, TMS) δ 27.4, 28.5, 30.3, 36.5, 41.2, 58.6,
61.3, 71.4, 112.0, 119.9, 123.0, 124.0, 124.5, 125.8, 126.1, 126.4, 127.2, 127.7, 128.3, 128.4,
129.4, 136.2, 140.1, 141.8, 142.3, 144.2, 150.5, 152.0, 157.1; IR (neat):  3070, 3018, 2950, 2868,
1600, 1450, 1073, 1028, 843, 754, 699 cm-1; HRMS (DART-FTICR) Calcd. for C35H32I [M+H]+:
579.1543, found: 579.1539.
(3aR,8R,8aR)-3'-phenyl-3a-(3-phenylpropyl)-2,3,3a,8a-tetrahydro-1H-spiro[cyclopenta[a]i
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