Mn(III)-promoted synthesis of spiroannular tricyclic scaffolds via sulfonylation/dearomatization of biaryl ynones

Article abstract of DOI:10.1016/j.tet.2019.01.041

A Mn(III)-promoted radical oxidative ipso-annulation reaction of biaryl ynones with sodium sulfinates to construct various substituted spiro[5.5]trienones has been explored in this study. This protocol is characterized by mild reaction conditions, good su

Full text of DOI:10.1016/j.tet.2019.01.041

Accepted Manuscript
Mn(III)-promoted synthesis of spiroannular tricyclic scaffolds via sulfonylation/
dearomatization of biaryl ynones
Li Zhou, Yu Xia, Yu-Zhao Wang, Jun-Dan Fang, Xue-Yuan Liu
PII:
S0040-4020(19)30068-7
https://doi.org/10.1016/j.tet.2019.01.041
TET 30093
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 9 November 2018
Revised Date: 14 January 2019
Accepted Date: 17 January 2019
Please cite this article as: Zhou L, Xia Y, Wang Y-Z, Fang J-D, Liu X-Y, Mn(III)-promoted synthesis of
spiroannular tricyclic scaffolds via sulfonylation/dearomatization of biaryl ynones, Tetrahedron (2019),
doi: https://doi.org/10.1016/j.tet.2019.01.041.
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Mn(III)-promoted synthesis of spiroannular
tricyclic scaffolds via
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sulfonylation/dearomatization of biaryl
ynones
a
a
a
a
a,
Li Zhou , Yu Xia , Yu-Zhao Wang , Jun-Dan Fang , Xue-Yuan Liu ∗
a
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, PR China.

1
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Tetrahedron
journal homepage: www.elsevier.com
Mn(III)-promoted synthesis of spiroannular tricyclic scaffolds via
sulfonylation/dearomatization of biaryl ynones
a
a
a
a
a,
Li Zhou , Yu Xia , Yu-Zhao Wang , Jun-Dan Fang , Xue-Yuan Liu ∗
a
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, PR China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A Mn(III)-promoted radical oxidative ipso-annulation reaction of biaryl ynones with sodium
sulfinates to construct various substituted spiro[5.5]trienones has been explored in this study.
This protocol is characterized by mild reaction conditions, good substrates functional group
3 2
compatibility, cheap and easily prepared Mn(OAc) ·2H O, and it demonstrates a simple
Available online
operation.
Keywords:
Radical
2
009 Elsevier Ltd. All rights reserved.
Sulfonylation
Dearomatization
Spiro[5.5]trienone
1
0
1
. Introduction
arenesulfonic acids and their derivatives. Among them, sodium
sulfinates are also used as popular materials to directly synthesize
sulfonated compounds, owing to their readily availability,
Spirocompounds have received considerable attention due to
the special properties like conformational transmission, helical
structure and photochromismm. Meanwhile, certain spiro-
conjugated molecule has been the starting materials for the
construction of electroactive molecules 2which exhibiting
nonconventional optoelectronic properties. For example,
sprio[5.5]undecatetraenedione has been used to prepare spiro-
11
inexpensiveness and high air stability. Especially, radical
1
process
by
using
sodium
sulfinates
to
achieve
sulfonylation/cyclization involving alkynes has gained
2b
donors (TFE, BEDT-TTF) and acceptors (TCNQ, DCNOI).
Therefore, the development of efficient methods to synthesize
3
spirocarbocycles is still of high significant. The most frequent
strategy for the synthesis of spiro-molecular from readily
available aromatic compounds is dearomatization, which mainly
involves a 5-exo-trig cyclization to build spiro[4.5]decane core
4
structures and their analogues. To the best of our knowledge,
research
spiro[5.5]trienones has been rarely reported. Thus, a novel and
efficient method to construct various important
spiro[5.5]trienones is of high desireable.
on
different functional groups substituted
5
Sulfones are valuable synthetic intermediates in synthetic
6
chemistry. Meanwhile, it is also very crucial to synthesize the
molecules containing sulfone structure motifs because of their
applications in material sciences, agrochemicals and
7
pharmaceutical chemistry. Consequently, chemists have spared
no efforts to install this valuable functional group into organic
8
molecule. Conventional procedures are likely divided into two
9
modes: the oxidation of the corresponding sulfides and direct C-
Scheme 1 The strategies for radical sulfonylation involving alkynes.
S
bond formation by using benzenesulfonyl hydrazides,
—
——
∗
Corresponding author.
E-mail address: liuxuey@lzu.edu.cn (X.-Y. Liu).

2
Tetrahedron
g- MA
considerable attention. In 2017, Jiang’s gro
A
upCCrep
E
o
P
rte
T
d
E
A
D
T
N
ab
USCRIPT
le
1
catalyzed radical cascade sulfonylation/cyclization of 1,6-enynes
with sodium sulfinates (Scheme 1a).
a
11h
Optimization of reaction conditions
The same year, Bi’s
group reported that biphenyl acetylene reacted with sodium
O
O
O
S
O
sulfinates and trimethylsilyl azide (TMSN ) to synthesize 6-
SO2Na
3
O
oxidant
solvent
methyl sulfonylated phenanthridines via a silver-catalyzed
tandem carbon-carbon triple bond hydroazidation, radical
+
OMe
1
a
2a
3a
11i
sulfonylation and cyclization process (Scheme 1b). In 2018,
Kshirsagar’s group described that the visible light initiated
radical cascade cyclization reaction for the synthesis of 3-
sulfonylindoles from 1 2-alkynyl-azidoarenes and sodium
b
Entry
Oxidant (equiv.)
Solvent
Time (h)
Yield (%)
1
2
Mn(OAc) ·2H O (2.0)
3
2
Toluene
Toluene
Toluene
Toluene
Toluene
DCE
12
12
12
12
12
12
12
12
12
12
12
12
12
3
10
n.d.
n.d.
n.d.
trace
25
1j
sulfinates (Scheme 1c). Based on our ongoing interest in the
K
2
S
2
O
8
(2.0)
4
f, 4h
10f
dearomatization
and sulfonylation reactions, we expect to
3
TBHP (2.0)
Mn(OAc) ·4H O (2.0)
PhI(OAc) (2.0)
develop a new direct radical oxidative dearomatization of biaryl
ynones with sodium sulfinates to form the spiro[5.5]trienones
compounds in the presence of manganese(III) acetate (Scheme
4
2
2
5
2
1
d). This sulfonylation/dearomatization of biaryl ynones could
6
Mn(OAc)
Mn(OAc)
Mn(OAc)
Mn(OAc)
3
3
3
3
·2H
·2H
·2H
·2H
2
2
2
2
O (2.0)
O (2.0)
O (2.0)
O (2.0)
involve the simultaneous formation of C-S, C-C bond and the
cleavage of C-O bond in one step and make the formation of
quaternary carbon stereocenter. The project provides a simple
and efficient approach to obtain a series of sulfonated
spiro[5.5]trienones in moderate to excellent yields.
7
1,4-dioxane
40
8
CH
3
CH
2
OH
19
9
CH
3
COOH
15
10
Mn(OAc) ·2H O (2.0)
3
3
3
3
3
2
2
2
2
2
CH CN
3
trace
80
1
1
1
1
1
1
2
3
4
5
Mn(OAc)
Mn(OAc)
Mn(OAc)
Mn(OAc)
Mn(OAc)
·2H
·2H
·2H
·2H
O (2.0)
O (2.5)
O (3.0)
O (2.5)
HFIP
HFIP
HFIP
HFIP
HFIP
HFIP
HFIP
88
2
. Results and discussion
85
At the beginning of our studies, we chose biaryl ynone 1a and
88
sodium p-toluenesulfinate 2a as the model substrates to optimize
the reaction conditions (Table 1). Initially, the reaction was
carried out in the presence of Mn(OAc) ·2H O (2.0 equiv.) in
3
·2H
2
O (2.5)
0.5
0.5
0.5
88
c
16
Mn(OAc)
3
·2H
2
O (2.5)
81
3
2
toluene. Gratifyingly, the expected product 3a was obtained in
0% yield while a large amount of starting material was
1
7
-
n.d.
1
a
Reactions were carried out under the following conditions: 1a (0.2 mmol),
a (0.4 mmol), oxidant and solvent (2 mL), 25 °C under air. Isolated yields.
Under argon. DCE = 1,2-dichloroethane; HFIP = 1,1,1,3,3,3-hexafluoro-2-
propanol.
recovered (entry 1). The structure of 3a was unambiguously
b
2
c
confirmed by X-ray crystallographic analysis (see the Supporting
12
Information). In order to improve the yield of target product,
various oxidants were then screened (entries 2-5).
Mn(OAc) ·2H O was found to be effective oxidant. Next,
alkynone triple bond was replaced with thienyl and naphthyl, the
spiroannular dearomatization reaction also proceeded well, and
afforded corresponding products in 64% and 83% yields (3m,
n). Soon after, the study on the aryl group (R group) which
attaches to the carbonyl moiety was carried out. Both electron-
donating and withdrawing groups (3o-3r) also worked well in the
optimized conditions. Next, p-methoxyl-substituted aryl group
R group) was examined. The introduction of chlorine group in
the ortho-position to the -OMe produced the spiro compound 3s
in 51% yield. With the incorporation of single methoxyl group at
meta-position or two methoxyl group at ortho- and meta-
positions to the -OMe, we produced the corresponding
dearomatized compounds 3u in 76% or 3t in 83% yield. But the
ortho-position of the -OMe was substituted by single methoxyl
group, which formed 9,10-dimethoxy-7-phenyl-6-tosyl-5H-
dibenzo[a,c][7]annulen-5-one 3v in 61% yield. The structure was
3
2
through the investigation on various solvents, we found that
,1,1,3,3,3-hexafluoro-2-propanol (HFIP) can remarkably
1
2
3
improve the yield to 80% (entries 6-11). The cause of such a
phenomenon is that radical intermediates could be stabilized by
13
fluorinated solvent. Afterwards, adjusting the loadings of
Mn(OAc) ·2H O to 2.5 equiv. was found to be the best choice
3
3
2
(
and afforded 3a in 88% yield (entries 12, 12-13). Then, we
explored the optimal reaction time and found that it had almost
no effect on the yield of product 3a when the time was shortened
to 0.5 h (entries 14-15). Finally, product 3a can also be obtained
8
1% yield under argon conditions (Table 1, entry 16). Control
reaction demonstrated that Mn(OAc) ·2H O was essential in this
3
2
reactivity (entry 17). Eventually, we come up with that the
optimized reaction conditions were 0.2 mmol 1a and 0.4 mmol
2
a with 0.5 mmol Mn(OAc) ·2H O in the presence of HFIP (2.0
3 2
unambiguously determined by X-ray crystallographic analysis
see the Supporting Information). The substrate whose two
mL) at 25 °C under air for 0.5 h.
12
(
methoxyl groups were placed in the ortho-positions of the -OMe,
also gave the seven-membered ring product 3w in 83% yield.
Substrate having two meta-methoxy groups was also conducted
under the standard conditions and furnished the seven-membered
ring product 3x in 89% yield. For the formation of spiro products
and seven-membered ring products was due to the influence of
electronic effects on the phenyl directly attached to the methoxyl.
Then 1-(4'-hydroxy-[1,1'-biphenyl]-2-yl)-3-phenylprop-2-yn-1-
one was tested under optimized reaction conditions , and gave
product 3a in 29% yield. Ortho- and meta-methoxy substituted
biaryl ynones were also conducted under the standard reaction
conditions, regrettably, we could not obtain the desired products.
Finally, sodium sulfinates were investigated. Various sulfonate
With the optimized conditions in hand, we further explored the
scope and limitation of this radical sulfonylation/dearomatization
reaction between biaryl ynones 1 and sodium sulfinates 2 (Table
2
). Initially, the electronic effect of substituent groups on
1
aromatic ring (R group) connected with the triple bond was
investigated. Electron-donating groups and halogen groups were
proved to be competent candidates in this transformation and
they afforded the corresponding products (3a-f, 3i-l) in good
yields. In particular, the product bearing para-tert-butyl group
gave excellent yield (3d, 95% yield). 3g and 3h were obtained in
moderate yields when the para-position of aromatic ring was
occupied by -CN, or -COOMe. When distal position of the

3
Table 2
ACCEPTED MANBa
U
se
S
d
C
onRI
above experiments, a plausible mechanism was
P
T
a
proposed in Scheme 3. First, sulfonyl radical was generated in
situ from sodium sulfinate 2 oxidized by Mn(III) salt.
Subsequently, sulfonyl radical added to more electron-rich alpha
position of the conjugated alkynone 1 formed vinyl radical
intermediate A. Intermediate A then underwent a 6-exo-trig
cyclization to form the dearomatization intermediate B, which
oxidized by Mn(III) salt to generate the oxocarbenium ion C.
Substrate scope for the reaction
Demethylation of intermediate
C furnished the desired
sulfonylated spiro[5.5]trienones product 3.
Scheme 3 Proposed mechanism of the reaction.
To investigate the preparative practicality of this novel
method, a gram scale reaction of 1a was performed under
standard conditions (scheme 4). The product 3a could be
successfully obtained in 73% yield (0.987g) from 3 mmol 1a and
a
3 2
Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), Mn(OAc) ·2H O (0.5
b
mmol), HFIP (2.0 mL), 25 °C, air, 0.5 h. Isolated yields are shown. 1-(4'-
hydroxy-[1,1'-biphenyl]-2-yl)-3-phenylprop-2-yn-1-one reacted with 2a
under optimized reaction condition.
6
mmol 2a under optimized conditions.
salts reacted with 1a respectively under the optimized conditions,
which gave corresponding spiro compounds (3y-3ee) in moderate
to excellent yields.
To gain more insight into the pathway of the reaction, some
control experiments were conducted (Scheme 2). When 3.0
equiv. of TEMPO (2,2,6,6-tetramethylpiperindine-1-oxyl) was
added as radical scavenger to the standard conditions, the radical
Scheme 4 Gram-scale reaction.
3
. Conclusions
sulfonylation/dearomatization
suppressed (eq. 1). 3a couldn’t be obtained while vinyl sulfone 4
was isolated in 48% yield when another radical scavenger DPE
reaction
was
completely
In summary, we have developed a novel Mn(III)-promoted
sulfonyl radical addition/dearomative spirocyclization reaction
between biaryl ynones and sodium sulfinates. This method
obtained sulfonyl substituted spiro[5.5]trienones in moderate to
excellent yields with the construction of C-S, C-C bond and the
cleavage of C-O bond in one step. Based on the advantages of
simple operation and mild reaction conditions, we believe that
this project is significant for the synthesis of sulfonyl substituted
spirocyclic. Meanwhile, we expect this sulfonyl substituted
spirocyclic could be found in the natural products and it is useful
for pharmaceuticals and material electrochemistry in the future.
(1,1-diphenylethylene) was applied in the standard conditions
(eq. 2). Moreover, in the absence of substrate 1a, vinyl sulfone 4
could also be received in 20% yield (eq. 3). These results
indicated that the spiroannular dearomatization reaction might
involve a radical addition pathway.
4
4
. Experimental section
.1. General
All reagents were purchased from commercial suppliers and
used without further purification. Column chromatography was
1
carried out on silica gel (200-300 mesh). H NMR spectra were
13
recorded on 400 MHz in CDCl , C NMR spectra were recorded
3
19
on 100 MHz in CDCl and F NMR spectra were recorded on
3
3
76 MHz in CDCl . Chemical shifts (ppm) were recorded with
3
tetramethylsilane (TMS) as internal standard. IR spectra were
recorded on FT-IR spectrometer and only major peaks are
Scheme 2 Mechanistic studies.

4
Tetrahedron
ACCEPTED MANUSCRIPT
-
1
reported in cm . High-resolution mass spectral analysis
(d, J = 8.0 Hz, 2H), 7.58-7.54 (m, 1H), 7.50-7.46 (m, 1H), 7.32
(d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 7.22-7.20 (m, 1H),
7.06 (d, J = 8.4 Hz, 2H), 6.67 (d, J = 10.0 Hz, 2H), 6.31 (d, J =
(HRMS) date were measured on a Bruker Apex II. All products
1 13
were characterized by HRMS. Copies of the H NMR, C NMR
and F NMR spectra are provided in the Supporting Information.
The substrates were prepared according to literature
19
13
10.0 Hz, 2H), 2.41 (s, 3H), 1.31 (s, 9H). C NMR (100 MHz,
CDCl , δ, ppm): 184.2, 178.8, 162.6, 152.4, 147.0, 144.3, 140.2,
138.5, 137.1, 134.0, 130.9, 130.7, 130.3, 129.2, 128.8, 128.0,
1
3
5a, 14
procedure.
-
1
1
2
27.8, 126.8, 124.0, 52.8, 34.7, 31.2, 21.6. IR (neat, cm ): 2960,
902, 1623, 1597, 1452, 1309, 1159, 857, 814, 759. HRMS (ESI)
4
.2. General Procedure for Synthesis of 3
+
(m/z): calcd for C H O S ([M+H] ), 509.1781; found 509.1787.
32
28
4
In a 10 mL dried tube, substrates 1 (0.2 mmol, 1.0 equiv.),
4
.3.5. 2’-(4-fluorophenyl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
sodium sulfinates 2 (0.4 mmol, 2.0 equiv.), Mn(OAc) ·2H O (0.5
3
2
naphthalene]-2,5-diene-4,4’-dione (3e): 74.0 mg, 79% yield;
yellow solid, melting point 260-262 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.14 (dd, J = 7.6 Hz, J = 1.2 Hz, 1H), 7.84 (d, J
mmol, 2.5 equiv.) and HFIP (2.0 mL) were added. The reaction
1
o
mixture was stirred at 25 C for 0.5 h under air. After the reaction
3
was completed, the reaction mixture was concentrated in vacuo
and the residue was purified by column chromatography (silica
=
8
8.0 Hz, 2H), 7.60-7.56 (m, 1H), 7.51-7.47 (m, 1H), 7.30 (d, J =
.0 Hz, 2H), 7.22 (d, J = 7.6 Hz, 1H), 7.15-7.11 (m, 2H), 7.03 (t,
J = 8.8 Hz, 2H), 6.67 (d, J = 10.0 Hz, 2H), 6.34 (d, J = 10.0 Hz,
gel,
appropriate
mixture
of
petroleum
ether/ethyl
acetate/dichloromethane = 3:1:1) to afford products 3.
13
2
1
H), 2.41 (s, 3H). C NMR (100 MHz, CDCl , δ, ppm): 183.8,
3
78.5, 164.2, 161.3 (d, J = 87.0 Hz), 146.6, 144.6, 140.7, 138.2,
4
.3. Characterization data of Products:
.3.1. 2’-phenyl-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
136.9, 134.1, 131.0, 130.1, 129.5 (d, J = 3.0 Hz), 129.3, 129.1,
19
1
28.8, 128.0, 127.9, 114.4 (d, J = 22.0 Hz), 52.6, 21.6. F NMR
-1
4
(376 MHz, CDCl , δ, ppm): -111.1. IR (neat, cm ): 2955, 1663,
3
naphthalene]-2,5-diene-4,4’-dione (3a): 79.6 mg, 88% yield;
yellow solid, melting point 268-270 °C; H NMR (400 MHz,
CDCl ,δ, ppm): 8.15 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.87 (d, J
=
1
623, 1597, 1451, 1313, 1227, 1154, 847, 766. HRMS (ESI)
+
1
(m/z): calcd for C H FO S ([M+H] ), 471.1061; found
28 19 4
3
4
71.1069.
8.4 Hz, 2H), 7.59-7.55 (m, 1H), 7.51-7.47 (m, 1H), 7.39-7.29
(
(
m, 5H), 7.22 (d, J = 8.0 Hz, 1H), 7.14 (d, J = 6.8 Hz, 1H), 6.68
4
.3.6. 2’-(4-chlorophenyl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
13
d, J = 10.0 Hz, 2H), 6.31 (d, J = 10.0 Hz, 2H), 2.41 (s, 3H),
C
naphthalene]-2,5-diene-4,4-dione (3f): 78.2 mg, 80% yield;
brown solid, melting point 222-224 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.15 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.85 (d, J
=
NMR (100 MHz, CDCl , δ, ppm): 178.7, 162.0, 146.7, 144.5,
1
3
1
1
1
40.2, 138.3, 137.0, 134.0, 133.7, 130.9, 130.3, 129.2, 129.0,
-1
3
28.1, 127.8, 127.1, 52.7, 21.6. IR (neat, cm ): 2956, 1657,
8.0 Hz, 2H), 7.60-7.56 (m, 1H), 7.52-7.48 (m, 1H), 7.33-7.30
622, 1596, 1453, 1318, 1154, 856, 762, 716. HRMS (ESI) (m/z):
(
(
m, 4H), 7.22 (d, J = 7.6 Hz, 1H), 7.08 (d, J = 8.4 Hz, 2H), 6.66
d, J = 10.0 Hz, 2H), 6.35 (d, J = 10.0 Hz, 2H), 2.42 (s, 3H).
+
calcd for C H O S ([M+H] ), 453.1155; found 453.1159.
13
28
20
4
C
NMR (100 MHz, CDCl , δ, ppm): 183.8, 178.5, 160.6, 146.5,
3
4
.3.2.
2’-(p-tolyl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
144.7, 140.7, 138.2, 136.9, 135.5, 134.2, 132.1, 131.1, 130.2,
129.4, 129.3, 129.0, 128.5, 128.1, 127.9, 127.6, 52.5, 21.6. IR
naphthalene]-2,5-diene-4,4’-dione (3b): 84.0 mg, 90% yield;
grey solid, melting point 200-202 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.14 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.86 (d, J
1
-1
(neat, cm ): 2958, 1658, 1622, 1597, 1487, 1451, 1309, 1159,
+
3
858, 758. HRMS (ESI) (m/z): calcd for C H ClO S ([M+H] ),
28 19
4
=
8.4 Hz, 2H), 7.58-7.53 (m, 1H), 7.50-7.46 (m, 1H), 7.29 (d, J =
487.0765; found 487.0768.
8
7
1
.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H),
.03 (d, J = 8.0 Hz, 2H), 6.67 (d, J = 10.0 Hz, 2H), 6.32 (d, J =
0.0 Hz, 2H), 2.40 (s, 3H), 2.35 (s, 3H). C NMR (100 MHz,
13
4.3.7. 4-(4,4-dioxo-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
naphthalene]-2,5-dien-2’-yl)benzonitrile (3g): 60.0 mg, 63%
CDCl , δ, ppm): 184.2, 178.7, 162.5, 146.9, 144.3, 140.2, 139.2,
3
1
yield; yellow solid, melting point 152-154 °C; H NMR (400
1
1
1
38.4, 137.0, 133.9, 130.8, 130.2, 129.2, 128.8, 128.0, 127.8,
-1
MHz, CDCl δ, ppm): 8.16 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.85
3,
26.9, 52.8, 21.6, 21.3. IR (neat, cm ): 2957, 1659, 1621, 1596,
(d, J = 8.4 Hz, 2H), 7.65 (d, J = 8.8 Hz, 2H), 7.62-7.58 (m, 1H),
451, 1324, 1159, 857, 812, 760. HRMS (ESI) (m/z): calcd for
+
7.54-7.50 (m, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.4 Hz,
C H O S ([M+H] ), 467.1312; found 467.1316.
29
22
4
2
1
1
1
1
1
H), 7.23-7.21 (m, 1H), 6.67 (d, J = 10.0 Hz, 2H), 6.36 (d, J =
13
0.0 Hz, 2H), 2.43 (s, 3H). C NMR (100 MHz, CDCl , δ, ppm):
3
4
1
.3.3.
2’-(4-methoxyphenyl)-3’-tosyl-4’H-spiro[cyclohexane-
83.4, 178.2, 159.1, 146.0, 145.1, 140.7, 138.3, 137.7, 136.7,
34.4, 131.4, 130.9, 130.0, 129.6, 129.5, 129.0, 128.2, 128.1,
,1’-naphthalene]-2,5-diene-4,4’-dione (3c): 87.4 mg, 90%
1
yield; brown solid, melting point 230-232 °C; H NMR (400
MHz, CDCl , δ, ppm): 8.14 (dd, J = 7.6 Hz, J = 1.2 Hz, 1H), 7.86
-1
27.9, 118.0, 113.2, 52.1, 21.7. IR (neat, cm ): 2954, 2229,
3
659, 1619, 1596, 1452, 1314, 1154, 849, 729. HRMS (ESI)
(
(
d, J = 8.4 Hz, 2H), 7.58-7.54 (m, 1H), 7.50-7.46 (m, 1H), 7.29
d, J = 8.0 Hz, 2H), 7.23-7.21 (m, 1H), 7.08 (d, J = 8.8 Hz, 2H),
+
(m/z): calcd for C H NO S ([M+H] ), 478.1108; found
29
19
4
4
78.1109.
6
1
.85 (d, J = 8.8 Hz, 2H), 6.67 (d, J = 10.0 Hz, 2H), 6.35 (d, J =
13
0.0 Hz, 2H), 3.81 (s, 3H), 2.41 (s, 3H). C NMR (100 MHz,
CDCl , δ, ppm): 184.2, 178.8, 162.4, 160.3, 147.1, 144.4, 140.4,
4.3.8. Methyl 4-(4,4’-dioxo-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
3
1
1
1
38.5, 137.0, 134.0, 130.8, 130.3, 129.2, 128.8, 128.5, 128.0,
naphthalene]-2,5-dien-2’-yl)benzoate (3h): 66.5 mg, 65% yield;
-
1
1
27.8, 126.0, 112.7, 55.1, 53.0, 21.6. IR (neat, cm ): 2954, 1657,
brown solid, melting point 260-262 °C; H NMR (400 MHz,
622, 1597, 1450, 1308, 1249, 1160, 1031, 758. HRMS (ESI)
CDCl
= 8.4 Hz, 2H), 7.86 (d, J = 8.0 Hz, 2H), 7.60-7.56 (m, 1H), 7.52-
.48 (m, 1H), 7.31 (d, J = 8.0 Hz, 2H), 7.24-7.21 (m, 3H), 6.69
(d, J = 10.0 Hz, 2H), 6.32 (d, J = 10.0 Hz, 2H), 3.91 (s, 3H), 2.41
3
, δ, ppm): 8.15 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 8.02 (d, J
+
(m/z): calcd for C H O S ([M+H] ), 483.1261; found 483.1267.
29
22
5
7
4
1
.3.4. 2’-(4-(tert-butyl)phenyl)-3’-tosyl-4’H-spiro[cyclohexane-
13
,1’-naphthalene]-2,5-diene-4,4’-dione (3d): 97.0 mg, 95%
(s, 3H). C NMR (100 MHz, CDCl , δ, ppm): 183.6, 178.4,
3
1
yield; yellow solid, melting point 200-202 °C; H NMR (400
MHz, CDCl , δ, ppm): 8.14 (dd, J = 7.6 Hz, J = 1.2 Hz, 1H), 7.84
166.1, 160.6, 146.3, 144.8, 140.3, 138.2, 137.9, 136.8, 134.2,
131.1, 130.6, 130.1, 129.4, 129.3, 129.0, 128.2, 128.1, 127.8,
3

5
-
1
1
1
27.3, 52.3, 52.2, 21.6. IR (neat, cm ): 2953, 1729, 1658, 1597,
4.3.13. 2’-(thiophen-2-yl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
ACCEPTED MANUSCRIPT
452, 1307, 1272, 1160, 862, 717. HRMS (ESI) (m/z): calcd for
C H O S ([M+H] ), 511.1210; found 511.1217.
naphthalene]-2,5-diene-4,4’-dione (3m): 58.0 mg, 64% yield;
grey solid, melting point 210-212 °C; H NMR (400 MHz,
+
1
30
22
6
CDCl , δ, ppm): 8.10 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 8.4 Hz,
3
2
2
H), 7.59-7.55 (m, 1H), 7.49-7.45 (m, 2H), 7.28 (d, J = 8.4 Hz,
H), 7.23 (d, J = 7.6 Hz, 1H), 7.15 (d, J = 2.8 Hz, 1H), 7.06-7.04
4
.3.9.
2’-(o-tolyl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
naphthalene]-2,5-diene-4,4’-dione (3i): 83.5 mg, 90% yield;
yellow solid, melting point 260-262 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.16-8.14 (m, 1H), 7.86 (d, J = 8.4 Hz, 2H),
1
(m, 1H), 6.65 (d, J = 10.0 Hz, 2H), 6.44 (d, J = 9.6 Hz, 2H), 2.40
13
(s, 3H). C NMR (100 MHz, CDCl , δ, ppm): 184.4, 178.4,
3
3
1
1
55.5, 146.5, 144.4, 142.0, 138.5, 136.8, 134.2, 133.3, 131.4,
7
.59-7.54 (m, 1H), 7.52-7.48 (m, 1H), 7.30-7.27 (m, 3H), 7.22 (t,
J = 8.0 Hz, 2H), 7.12 (t, J = 7.6 Hz, 1H), 6.89 (d, J = 7.6 Hz,
H), 6.85 (dd, J = 10.0 Hz, J = 3.2 Hz, 1H), 6.48 (dd, J = 9.6 Hz,
J = 2.8 Hz, 1H), 6.34 (dd, J = 10.0 Hz, J = 1.6 Hz, 1H), 6.24 (dd,
31.0, 130.1, 129.3, 129.2, 128.9, 128.1, 126.8, 52.6, 21.7. IR
-1
(neat, cm ): 2956, 1659, 1622, 1596, 1452, 1307, 1153, 856,
1
+
7
4
4
1
57, 705. HRMS (ESI) (m/z): calcd for C H O S ([M+H] ),
26 18 4 2
59.0719; found 459.0724.
.3.14. 2’-(naphthalene-1-yl)-3’-tosyl-4’H-spiro[cyclohexane-
,1’-naphthalene]-2,5-diene-4,4’-dione (3n): 83.4 mg, 83%
13
J = 10.0 Hz, J = 1.6 Hz, 1H), 2.41 (s, 3H), 2.35 (s, 3H). C NMR
100 MHz, CDCl , δ, ppm): 183.9, 178.7, 162.4, 147.6, 145.4,
(
3
1
1
1
1
44.5, 140.4, 138.3, 137.6, 135.1, 134.0, 133.0, 131.1, 130.6,
30.4, 129.9, 129.3, 129.2, 129.1, 128.9, 128.0, 127.3, 125.4,
24.1, 53.5, 21.6, 21.2. IR (neat, cm ): 2959, 1658, 1622, 1596,
1
yield, yellow solid, melting point 226-228 °C; H NMR (400
MHz, CDCl , δ, ppm): 8.21 (dd, J = 7.6 Hz, J = 1.6 Hz, 1H),
7
1
7
-
1
3
.86-7.82 (m, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.66 (d, J = 8.0 Hz,
H), 7.55-7.51 (m, 2H), 7.49-7.47 (m, 1H), 7.45-7.42 (m, 1H),
.40-7.36 (m, 1H), 7.22-7.19 (m, 3H), 7.15-7.13 (m, 1H), 6.76
452, 1308, 1155, 858, 820, 760. HRMS (ESI) (m/z): calcd for
+
C H O S ([M+H] ), 467.1312; found 467.1317.
29
22
4
(dd, J = 10.0 Hz, J = 3.2 Hz, 1H), 6.58 (dd, J = 9.6 Hz, J = 3.2
4
.3.10. 2’-(2-chlorophenyl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
Hz, 1H), 6.36 (dd, J = 9.6 Hz, J = 1.6 Hz, 1H), 5.83 (dd, J = 10.4
Hz, J = 1.6 Hz, 1H), 2.36 (s, 3H). C NMR (100 MHz, CDCl , δ,
3
13
naphthalene]-2,5-diene-4,4’-dione (3j): 82.9 mg, 85% yield;
brown solid, melting point 274-276 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.14 (dd, J = 7.6 Hz, J = 0.8 Hz, 1H), 7.98 (d, J
=
1
ppm): 183.9, 178.7, 161.5, 147.9, 146.3, 144.7, 142.1, 138.0,
137.9, 134.2, 132.8, 131.1, 131.0, 130.7, 129.7, 129.5, 129.3,
129.2, 128.3, 127.5, 126.6, 126.1, 125.1, 123.9, 53.7, 21.7. IR
3
8.4 Hz, 2H), 7.60-7.56 (m, 1H), 7.52-7.48 (m, 1H), 7.42 (d, J =
-
1
8
1
6
1
.0 Hz, 1H), 7.35-7.29 (m, 3H), 7.26-7.22 (m, 2H), 7.18 (dd, J =
0.0 Hz, J = 3.2 Hz, 1H), 7.08 (dd, J = 7.6 Hz, J = 1.2 Hz, 1H),
.53 (dd, J = 10.0 Hz, J = 3.2 Hz, 1H), 6.38 (dd, J = 9.6 Hz, J =
.6 Hz, 1H), 6.31 (dd, J = 10.0 Hz, J = 1.6 Hz, 1H), 2.41 (s, 3H).
(neat, cm ): 2955, 1665, 1625, 1596, 1451, 1305, 1157, 857,
+
806, 739. HRMS (ESI) (m/z): calcd for C32H O S ([M+H] ),
22 4
503.1312; found 503.1317.
13
C NMR (100 MHz, CDCl , δ, ppm): 183.9, 178.3, 158.7, 147.2,
3
4
.3.15.
6’-phenyl-7’-tosyl-8’H-spiro[cyclohexane-1,5’-
1
1
5
1
45.6, 144.6, 141.0, 138.1, 137.5, 134.2, 132.4, 131.9, 131.3,
30.8, 130.4, 130.2, 129.3, 129.2, 128.2, 128.1, 127.5, 125.5,
naphtho[2,3-d][1,3]dioxole]-2,5-diene-4,8’-dione (3o): 81.6 mg,
1
8
2% yield; brown solid, melting point 282-284 °C; H NMR (400
-
1
3.2, 21.6. IR (neat, cm ): 2957, 1659, 1622, 1598, 1452, 1308,
MHz, CDCl , δ, ppm): 7.86 (d, J = 8.4 Hz, 2H), 7.52 (s, 1H),
3
156, 857, 780, 758. HRMS (ESI) (m/z): calcd for C H ClO S
28
19
4
7
2
3
.39-7.29 (m, 5H), 7.12 (d, J = 7.2 Hz, 2H), 6.63 (d, J = 10.0 Hz,
H), 6.58 (s, 1H), 6.31 (d, J = 10.0 Hz, 2H), 6.05 (s, 2H), 2.42 (s,
+
([M+H] ), 487.0765; found 487.0769.
13
H). C NMR (100 MHz, CDCl , δ, ppm): 183.9, 177.2, 161.1,
3
4
.3.11.
2’-(m-tolyl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
152.9, 149.1, 146.8, 144.4, 139.8, 138.4, 133.7, 133.6, 130.9,
129.2, 129.1, 128.8, 127.1, 127.0, 125.8, 106.8, 106.3, 102.4,
52.7, 21.6. IR (neat, cm ): 2921, 1664, 1626, 1595, 1479, 1322,
naphthalene]-2,5-diene-4,4’-dione (3k): 80.6 mg, 86% yield;
yellow solid, melting point 236-238 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.15 (dd, J = 7.6 Hz, J = 0.8 Hz, 1H), 7.85 (d, J
=
1
-1
1282, 1160, 1029, 873. HRMS (ESI) (m/z): calcd for C29
([M+H] ), 497.1053; found 497.1058.
H
20
O
6
S
3
+
8.0 Hz, 2H), 7.58-7.54 (m, 1H), 7.50-7.46 (m, 1H), 7.29 (d, J =
8
1
3
1
1
5
1
.0 Hz, 2H), 7.23-7.16 (m, 3H), 6.94 (d, J = 7.2 Hz, 1H), 6.89 (s,
H), 6.69-6.65 (m, 2H), 6.32-6.29 (m, 2H), 2.40 (s, 3H), 2.33 (s,
4
.3.16.
3’-phenyl-2-tosyl-1’H-spiro[cyclohexane-1,4’-
13
H). C NMR (100 MHz, CDCl , δ, ppm): 184.0, 178.7, 162.3,
3
phenanthrene]-2,5-diene-1’,4-dione (3p): 61.0 mg, 61% yield;
brown solid, melting point 304-306 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.27 (d, J = 8.8 Hz, 1H), 8.13 (d, J = 8.8 Hz,
1
Hz, 1H), 7.44-7.38 (m, 2H), 7.34-7.29 (m, 4H), 7.06 (d, J = 7.6
Hz, 2H), 6.77 (d, J = 10.0 Hz, 2H), 6.51 (d, J = 10.0 Hz, 2H),
2
1
1
1
46.8, 144.3, 140.0, 138.3, 136.9, 136.5, 133.9, 133.6, 130.7,
30.5, 130.2, 129.9, 129.1, 127.9, 127.7, 127.5, 126.9, 124.1,
3
-
1
2.6, 21.5, 21.3. IR (neat, cm ): 2950, 1659, 1620, 1596, 1451,
H), 8.00 (d, J = 8.8 Hz, 1H), 7.91-7.86 (m, 3H), 7.60 (t, J = 7.2
309, 1156, 864, 808, 758. HRMS (ESI) (m/z): calcd for
+
C H O S ([M+H] ), 467.1312; found 467.1316.
29
22
4
13
.41 (s, 3H). C NMR (100 MHz, CDCl , δ, ppm): 183.3, 179.1,
60.5, 147.1, 144.5, 141.2, 138.4, 136.3, 135.3, 133.6, 131.2,
31.0, 130.4, 130.0, 129.4, 129.2, 129.0, 128.7, 127.2, 125.9,
3
4
.3.12. 2’-(3-chlorophenyl)-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
naphthalene]-2,5-diene-4,4’-dione (3l): 81.2 mg, 84% yield;
yellow solid, melting point 236-238 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.15 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.85 (d, J
=
-
1
1
125.8, 122.7, 53.4, 21.6. IR (neat, cm ): 2952, 1654, 1621, 1597,
463, 1319, 1159, 806, 766, 702. HRMS (ESI) (m/z): calcd for
1
3
+
C H O S ([M+H] ), 503.1312; found 503.1317.
32
22
4
8.0 Hz, 2H), 7.60-7.56 (m, 1H), 7.52-7.48 (m, 1H), 7.36-7.26
(
(
m, 4H), 7.22 (d, J = 7.6 Hz, 1H), 7.07-7.05 (m, 2H), 6.70-6.65
m, 2H), 6.36-6.32 (m, 2H), 2.41 (s, 3H). C NMR (100 MHz,
13
4
.3.17. 7’-methyl-2’-phenyl-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
CDCl , δ, ppm): 183.7, 178.4, 159.8, 146.4, 146.3, 144.7, 140.6,
1
3
naphthalene]-2,5-diene-4,4’-dione (3q): 81.3 mg, 87% yield;
brown solid, melting point 241-243 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.04 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 8.4 Hz,
2
6.66 (d, J = 10.0 Hz, 2H), 6.31 (d, J = 10.0 Hz, 2H), 2.41 (s, 3H),
2
1
1
37.9, 136.7, 135.1, 134.2, 133.0, 131.0, 130.0, 129.3, 129.2,
-
1
28.9, 128.4, 128.0, 127.8, 127.1, 125.6, 52.3, 21.6. IR (neat, cm
3
1
)
: 2954, 1661, 1626, 1596, 1452, 1306, 1156, 857, 790, 763.
H), 7.38-7.28 (m, 6H), 7.13 (d, J = 7.2 Hz, 2H), 6.97 (s, 1H),
+
HRMS (ESI) (m/z): calcd for C H ClO S ([M+H] ), 487.0765;
found 487.0770.
28
19
4
13
.35(s, 3H). C NMR (100 MHz, CDCl , δ, ppm): 184.2, 178.5,
3
61.6, 146.9, 145.3, 144.4, 140.1, 138.4, 137.0, 133.7, 130.8,

6
Tetrahedron
1
1
30.3, 129.2, 129.1, 128.9, 128.1, 127.9, 127.1, 127.0, 52.6,
solid, melting point 184-186 °C; H NMR (400 MHz, CDCl , δ,
ACCEPTED MANUSCRIPT
3
-
1
2
1
1.8, 21.6. IR (neat, cm ): 2956, 1658, 1621, 1570, 1442, 1306,
156, 868, 781, 702. HRMS (ESI) (m/z): calcd for C H O S
ppm): 7.78 (d, J = 8.0 Hz, 1H), 7.68-7.64 (m, 1H), 7.49 (t, J = 7.6
Hz 2H), 7.44 (d, J = 8.0 Hz, 2H) 7.39-7.32 (m, 3H), 7.17 (s, 1H),
7.12 (d, J = 6.0 Hz, 3H), 6.60 (s, 1H), 6.34 (s, 1H), 3.95 (s, 3H),
29
22
4
+
([M+H] ), 467.1312; found 467.1318.
13
3
1
1
.50 (s, 3H), 2.37 (s, 3H). C NMR (100 MHz, CDCl , δ, ppm):
93.3, 150.1, 149.1, 147.8, 143.9, 143.8, 141.1, 138.7, 137.4,
35.1, 132.5, 131.2, 129.0, 128.9, 128.6, 128.3, 128.2, 127.6,
3
4
.3.18. 6’-chloro-2’-phenyl-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
naphthalene]-2,5-diene-4,4’-dione (3r): 72.5 mg, 75% yield;
yellow solid, melting point 246-248 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.09 (d, J = 2.4 Hz, 1H), 7.83 (d, J = 8.4 Hz,
-1
1
125.2, 114.6, 112.9, 56.0, 55.5, 21.5. IR (neat, cm ): 2969, 1668,
1
596, 1538, 1484, 1356, 1266, 1152, 1030, 775. HRMS (ESI)
3
+
(m/z): calcd for C H O S ([M+H] ), 497.1417; found 497.1426.
30 24 5
2
7
H), 7.50 (dd, J = 8.4 Hz, J = 2.4 Hz, 1H), 7.39-7.28 (m, 5H),
.17-7.11 (m, 3H), 6.65 (d, J = 10.0 Hz, 2H), 6.31 (d, J = 10.0
13
Hz, 2H), 2.41 (s, 3H). C NMR (100 MHz, CDCl , δ, ppm):
4.3.23.
8,9,10-trimethoxy-7-phenyl-6-tosyl-5H-
3
1
1
1
1
83.7, 177.6, 162.2, 146.2, 144.7, 140.1, 138.1, 135.8, 135.4,
34.1, 133.4, 131.5, 131.1, 129.6, 129.3, 128.9, 127.6, 127.1,
27.0, 52.3, 21.6. IR (neat, cm ): 2955, 1661, 1623, 1592, 1410,
dibenzo[a,c][7]annulen-5-one (3w): 87.8 mg, 83% yield; yellow
1
solid, melting point 112-114 °C; H NMR (400 MHz, CDCl , δ,
3
-
1
ppm): 7.82 (d, J = 7.6 Hz, 1H), 7.69-7.65 (m, 1H), 7.53 (d, J =
4.4 Hz, 2H), 7.22-7.13 (m, 3H), 7.03 (d, J = 8.4 Hz, 2H), 6.91 (d,
J = 8.4 Hz, 2H), 6.84 (s, 1H), 3.91 (s, 3H), 3.69 (s, 3H), 2.92 (s,
326, 1160, 865, 730, 701. HRMS (ESI) (m/z): calcd for
+
C H ClO S ([M+H] ), 487.0765; found 487.0770.
28
19
4
1
3
3
1
1
1
1
H), 2.27 (s, 3H). C NMR (100 MHz, CDCl , δ, ppm): 193.2,
3
54.6, 153.1, 146.4, 144.9, 143.4, 142.5, 141.7, 138.7, 138.0,
35.7, 134.5, 131.1, 128.8, 128.3, 128.2, 127.7, 127.6, 127.0,
25.3, 122.5, 108.4, 60.4, 59.3, 56.0, 21.3. IR (neat, cm ): 2940,
709, 1588, 1493, 1345, 1259, 1145, 1034, 771, 706. HRMS
ESI) (m/z): calcd for C H O S ([M+H] ), 527.1523; found
4
.3.19. 3-chloro-2’-phenyl-3’-tosyl-4’H-spiro[cyclohexane-1,1’-
naphthalene]-2,5-diene-4,4’-dione (3s): 50.0 mg, 51% yield;
brown solid, melting point 224-226 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.16 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 8.0 Hz,
2
7
7
-1
1
3
+
(
31
26
6
H), 7.62-7.57 (m, 1H), 7.54-7.50 (m, 1H), 7.40-7.37 (m, 2H),
.36-7.34 (m, 1H), 7.30 (d, J = 8.0 Hz, 2H), 7.22-7.20 (m, 1H),
.12-7.09 (m, 2H), 6.87 (d, J = 2.8 Hz, 1H), 6.70 (dd, J = 10.0
5
27.1534.
13
Hz, J = 3.2 Hz, 1H), 6.36 (d, J = 10.0 Hz, 1H), 2.41 (s, 3H).
C
4.3.24.
8,10-dimethoxy-7-phenyl-6-tosyl-5H-
NMR (100 MHz, CDCl , δ, ppm): 178.4, 177.1, 160.7, 147.0,
dibenzo[a,c][7]annulen-5-one (3x): 88.1 mg, 89% yield, yellow
3
1
1
1
1
1
44.7, 142.3, 140.4, 138.1, 136.0, 135.3, 134.3, 133.2, 130.1,
29.9, 129.6, 129.4, 129.3, 129.0, 128.3, 127.7, 127.3, 127.2,
27.1, 126.7, 54.3, 21.6. IR (neat, cm ): 2964, 1666, 1595, 1453,
solid, melting point 83-85 °C; H NMR (400 MHz, CDCl ,δ,
3
ppm): 7.85 (d, J = 8.0 Hz, 1H), 7.68-7.64 (m, 1H), 7.53-7.52 (m,
2H), 7.19-7.02 (m, 5H), 6.90 (d, J = 8.0 Hz, 2H), 6.69 (d, J = 2.4
-
1
305, 1157, 836, 767, 703, 690. HRMS (ESI) (m/z): calcd for
Hz, 1H), 6.29 (d, J = 2.4 Hz, 1H), 3.80 (s, 3H), 3.16 (s, 3H), 2.26
+
13
C H ClO S ([M+H] ), 487.0765; found 487.0771.
(s, 3H), C NMR (100 MHz, CDCl , δ, ppm): 193.3, 161.1,
28
19
4
3
1
1
1
1
60.5, 146.7, 144.7, 143.3, 141.9, 140.0, 138.5, 138.0, 135.6,
31.0, 128.7, 128.5, 128.0, 127.8, 127.5, 126.5, 125.1, 117.9,
06.6, 99.3, 55.4, 55.3, 21.3. IR (neat, cm ): 2938, 1708, 1600,
4
1
.3.20. 2,3-dimethoxy-2’-phenyl-3’-tosyl-4’H-spiro[cyclohexane-
-1
,1’-naphthalene]-2,5-diene-4,4’-dione (3t): 84.7 mg, 83% yield;
557, 1456, 1316, 1207, 1144, 1023, 737. HRMS (ESI) (m/z):
1
brown solid, melting point 212-214 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.12 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.86 (d, J
+
calcd for C H O S ([M+H] ), 497.1417; found 497.1422.
30
24
5
3
=
8.4 Hz, 2H), 7.57-7.53 (m, 1H), 7.49-7.45 (m, 1H), 7.39-7.37
(
7
3
m, 2H), 7.34-7.23 (m, 4H), 7.21 (d, J = 7.6 Hz, 1H), 7.16 (d, J =
.6 Hz, 1H), 6.33 (d, J = 9.6 Hz, 1H), 6.27 (d, J = 9.6 Hz, 1H),
13
.80 (s, 3H), 3.42 (s, 3H), 2.40 (s, 3H). C NMR (100 MHz,
4.3.25.
3'-((4-methoxyphenyl)sulfonyl)-2'-phenyl-4'H-
(3y):
spiro[cyclohexa[2,5]diene-1,1'-naphthalene]-4,4'-dione
90.9 mg, 97% yield; yellow solid, melting point 218-220 °C; H
1
CDCl , δ, ppm): 183.5, 178.8, 162.0, 158.7, 144.2, 141.4, 140.6,
NMR (400 MHz, CDCl ,δ, ppm): 8.18 (dd, J = 7.6 Hz, J = 1.2
3
3
1
1
40.1, 138.5, 137.8, 133.9, 133.3, 130.7, 129.8, 129.1, 128.9,
28.6, 127.7, 127.3, 127.1, 126.9, 126.4, 61.1, 60.5, 57.0, 21.5.
Hz, 1H), 7.94 (d, J = 8.8 Hz, 2H), 7.60-7.56 (m, 1H), 7.53-7.49
(m, 1H), 7.40-7.38 (m, 1H), 7.37-7.33 (m, 2H), 7.22 (dd, J = 7.6
Hz, J = 0.4 Hz, 1H), 7.13-7.11 (m, 2H), 6.97 (d, J = 8.8 Hz, 2H),
6.68 (d, J = 10.0 Hz, 2H), 6.32 (d, J = 10.0 Hz, 2H), 3.87 (s, 3H),
-
1
IR (neat, cm ): 2876, 1657, 1602, 1447, 1320, 1255, 1155, 1031,
+
7
5
4
1
67, 704. HRMS (ESI) (m/z): calcd for C H O S ([M+H] ),
30 24 6
13
13.1366; found 513.1371.
.3.21. 2-methoxy-2’-phenyl-3’-tosyl-4’H-spiro[cyclohexane-
,1’-naphthalene]-2,5-diene-4,4’-dione (3u): 73.0 mg, 76%
C NMR (100 MHz, CDCl , δ, ppm): 184.2, 178.9, 163.6, 161.6,
3
146.8, 140.4, 136.9, 134.1, 133.8, 132.5, 131.5, 130.9, 130.3,
129.3, 129.2, 128.1, 127.9, 127.1, 127.0, 113.8, 55.6, 52.6. IR
1
-1
yield; brown solid, melting point 241-243 °C; H NMR (400
MHz, CDCl , δ, ppm): 8.12 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H), 7.85
(neat, cm ): 1657, 1619, 1593, 1495, 1310, 1263, 1156, 1020,
+
860, 760. HRMS (ESI) (m/z): calcd for C H O S ([M+H] ),
3
28 20
5
(d, J = 8.0 Hz, 2H), 7.56-7.52 (m, 1H), 7.49-7.45 (m, 1H), 7.37-
469.1104; found 469.1110.
7
6
5
.28 (m, 5H), 7.16 (t, J = 8.0 Hz, 2H), 7.07 (d, J = 7.2 Hz, 1H),
.39 (d, J = 9.6 Hz, 1H), 6.28 (dd, J = 9.6 Hz, J = 1.2 Hz, 1H),
.55 (d, J = 0.8 Hz, 1H), 3.54 (s, 3H), 2.40 (s, 3H). C NMR
13
4.3.26.
spiro[cyclohexa[2,5]diene-1,1'-naphthalene]-4,4'-dione
6.2 mg, 69% yield, white solid, melting point 220-222 °C; H
3'-((4-nitrophenyl)sulfonyl)-2'-phenyl-4'H-
(3z):
(100 MHz, CDCl , δ, ppm): 186.5, 178.9, 171.9, 161.8, 144.3,
3
1
6
1
1
2
1
42.3, 140.8, 138.5, 137.7, 134.0, 133.2, 130.5, 129.5, 129.1,
29.0, 128.7, 127.7, 127.3, 126.9, 126.8, 126.7, 105.5, 56.0, 55.2,
NMR (400 MHz, CDCl ,δ, ppm): 8.32 (d, J = 8.8 Hz, 2H), 8.16
3
-
1
(d, J = 8.8 Hz, 2H), 8.11 (d, J = 6.8 Hz, 1H), 7.64-7.60 (m, 1H),
1.5. IR (neat, cm ): 2968, 1670, 1628, 1595, 1453, 1309, 1223,
7
.52 (t, J = 7.2 Hz, 1H), 7.46-7.42 (m, 1H), 7.40-7.36 (m, 2H),
161, 855, 798. HRMS (ESI) (m/z): calcd for C H O S
29
22
5
+
7.26 (d, J = 8.8 Hz, 1H), 7.18 (d, J = 6.8 Hz, 2H), 6.72 (d, J =
([M+H] ), 483.1261; found 483.1264.
13
1
0.0 Hz, 2H), 6.37 (d, J = 10.0 Hz, 2H), C NMR (100 MHz,
CDCl , δ, ppm): 183.8, 178.5, 164.2, 150.3, 146.9, 146.1, 139.1,
3
4
.3.22.
9,10-dimethoxy-7-phenyl-6-tosyl-5H-
137.2, 134.5, 133.0, 131.2, 130.0, 129.7, 129.5, 128.0, 127.3,
126.9, 123.8, 52.8. IR (neat, cm ): 3098, 1664, 1625, 1600, 1529,
-
1
dibenzo[a,c][7]annulen-5-one (3v): 60.3 mg, 61% yield; yellow

7
1
450, 1302, 1160, 769, 684. HRMS (ESI) (m/z): calcd for
NMR (400 MHz, CDCl ,δ, ppm): 8.31 (dd, J = 7.6 Hz, J = 1.2
3
ACCEPTED MANUSCRIPT
+
C H NO S ([M+H] ), 484.0849; found 484.0856.
Hz, 1H), 7.67-7.63 (m, 1H), 7.61-7.57 (m, 1H), 7.37-7.33 (m,
27
17
6
1
2
2
H), 7.30-7.27 (m, 3H), 7.08-7.05 (m, 2H), 6.73 (dd, J = 10.0 Hz,
H), 6.34 (dd, J = 10.0 Hz, 2H), 3.41-3.35 (m, 1H), 1.17-1.13 (m,
4
.3.27.
3’-((4-chlorophenyl)sulfonyl)-2’-phenyl-4’H-
13
H), 1.03-0.97 (m, 2H), C NMR (100 MHz, CDCl , δ, ppm):
3
spiro[cyclohexane-1,1’-naphthalene]-2,5-diene-4,4’-dione (3aa):
3
NMR (400 MHz, CDCl , δ, ppm): 8.15 (dd, J = 7.6 Hz, J = 0.8
Hz, 1H), 7.93 (d, J = 8.4 Hz, 2H), 7.61-7.57 (m, 1H), 7.53-7.51
1
184.0, 179.7, 161.0, 146.7, 139.0, 137.2, 134.3, 133.4, 130.8,
1
3
8.9 mg, 41% yield; brown solid, melting point 288-290 °C; H
-1
30.0, 129.3, 129.1, 128.0, 126.9, 52.4, 32.8, 5.7. IR (neat, cm ):
3
052, 1663, 1623, 1595, 1454, 1319, 1151, 887, 729, 709. HRMS
+
(ESI) (m/z): calcd for C H O S ([M+H] ), 403.0999; found
24
18
4
(m, 1H), 7.49-7.48 (m, 1H), 7.47-7.46 (m, 1H), 7.43-7.39 (m,
4
03.1002.
1
6
H), 7.37-7.33 (m, 2H), 7.24-7.22 (m, 1H), 7.14-7.11 (m, 2H),
.67 (d, J = 10.0 Hz, 2H), 6.33 (d, J = 10.4 Hz, 2H). C NMR
13
1
(100 MHz, CDCl , δ, ppm): 183.9, 178.7, 162.9, 146.5, 140.3,
4.3.32. (2-tosylethene-1,1-diyl)dibenzene (4): H NMR (400
3
1
1
1
39.9, 139.8, 137.1, 134.3, 133.5, 131.1, 130.5, 130.1, 129.5,
29.4, 129.0, 128.1, 127.9, 127.2, 127.0, 52.8. IR (neat, cm ):
MHz, CDCl , δ, ppm): 7.47 (d, J = 8.0 Hz, 2H), 7.39-7.34 (m,
3
-
1
2H), 7.31-7.27 (m, 4H), 7.21-7.19 (m, 2H), 7.14 (d, J = 8.0 Hz,
13
658, 1623, 1597, 1454, 1317, 1154, 1086, 788, 764, 715. HRMS
2H), 7.10-7.08 (m, 2H), 6.99 (s, 1H), 2.37 (s, 3H). C NMR (100
+
(ESI) (m/z): calcd for C H ClO S ([M+H] ), 473.0609; found
MHz, CDCl , δ, ppm): 154.6, 143.7, 139.2, 138.6, 135.5, 130.2,
27
17
4
3
4
73.0614.
129.7, 129.3, 128.9, 128.8, 128.5, 128.2, 127.8, 127.7, 21.5.
+
HRMS (ESI) (m/z): calcd for C H O S ([M+H] ), 335.1100;
21
18
2
found 335.1100.
4
1
.3.28.
3’-(methylsulfonyl)-2’-phenyl-4’H-spiro[cyclohexane-
,1’-naphthalene]-2,5-diene-4,4’-dione (3bb): 70.4 mg, 94%
Acknowledgments
1
yield; white solid, melting point 276-278 °C; H NMR (400 MHz,
CDCl , δ, ppm): 8.31 (dd, J = 7.6 Hz, J = 0.8 Hz, 1H), 7.67-7.63
We thank the National Natural Science Foundation of China
(NSF 21472074) for financial support.
3
(m, 1H), 7.61-7.57 (m, 1H), 7.40-7.36 (m, 1H), 7.33-7.29 (m,
3
=
H), 7.10 (d, J = 7.2 Hz, 2H), 6.70 (d, J = 10.0 Hz, 2H), 6.36 (d, J
10.0 Hz, 2H), 3.32 (s, 3H). C NMR (100 MHz, CDCl , δ,
3
13
ppm): 184.0, 179.7, 162.5, 146.5, 139.7, 137.4, 134.5, 133.3,
31.1, 130.0, 129.5, 128.2, 128.1, 127.3, 127.0, 52.6, 45.8. IR
References and notes
1
-
1
(
7
3
neat, cm ): 2956, 2869, 1665, 1601, 1455, 1306, 1150, 854, 751,
21. HRMS (ESI) (m/z): calcd for C H O S ([M+H] ),
22 16 4
+
1. (a) Grochowski, J.; Rutkowska, M.; Rys, B.; Serda, P.; Snatzke, G. Chem.
Ber. 1992, 125, 1837-1841. (b) Favaro, G.; Masetti, F.; Mazzucato, U.;
Ottavi, G.; Allegrini, P.; Malatesta, V. J. Chem. Soc., Faraday Trans.
77.0842; found 377.0846.
1
1
2
5
994, 90, 333-338. (c) Jamrozik, J.; Schab, S. Monatshefte für Chemie
994, 125, 1145-1151. (d) Minkin, V. I. Chem. Rev. 2004, 104, 2751-
776. (e) Naumov, P.; Yu, P.; Sakurai, K. J. Phys. Chem. A 2008, 112,
810-5814.
4
.3.29.
3'-(ethylsulfonyl)-2'-phenyl-4'H-
(3cc):
spiro[cyclohexa[2,5]diene-1,1'-naphthalene]-4,4'-dione
9.1 mg, 63% yield, yellow solid, melting point 285-287 °C; H
2
3
. (a) Maslak, P.; Chopra, A.; Moylan, C. R.; Wortmann, R.; Lebus, S.;
Rheingold, A. L.; Yap, G. P. A. J. Am. Chem. Soc. 1996, 118, 1471-1481.
(b) Sandín, P.; Martínez-Grau, A.; Sánchez, L.; Seoane, C.; Pou-Amérigo,
R.; Ortí, E.; Martín, N. Org. Lett. 2005, 7, 295-298. (c) Wilbuer, J.;
Schnakenburg, G.; Esser, B. Eur. J. Org. Chem. 2016, 2016, 2404-2412.
. (a) González-López de Turiso, F.; Curran, D. P. Org. Lett. 2005, 7, 151-
1
4
NMR (400 MHz, CDCl ,δ, ppm): 8.30 (dd, J = 7.6 Hz, J = 1.2
Hz, 1H), 7.67-7.63 (m, 1H), 7.61-7.57 (m, 1H), 7.39-7.35 (m,
3
1
2
=
1
1
H), 7.32-7.29 (m, 3H), 7.09-7.07 (m, 2H), 6.71 (d, J = 10.0 Hz,
H), 6.35 (d, J = 10.0 Hz, 2H), 3.54 (q, J = 7.2 Hz, 2H), 1.30 (t, J
7.2 Hz, 3H), C NMR (100 MHz, CDCl , δ, ppm): 184.1,
1
54. (b) Lanza, T.; Leardini, R.; Minozzi, M.; Nanni, D.; Spagnolo, P.;
13
3
Zanardi, G. Angew. Chem. Int. Ed. 2008, 47, 9439-9442. (c) Glushkov, V.
A.; Stryapunina, O. G.; Gorbunov, A. A.; Maiorova, O. A.; Slepukhin, P.
A.; Ryabukhina, S. Y.; Khorosheva, E. V.; Sokol, V. I.; Shklyaev, Y. V.
Tetrahedron 2010, 66, 721-729. (d) Rodríguez-Solla, H.; Concellón, C.;
Tuya, P.; García-Granda, S.; Díaz, M. R. Adv. Synth. Catal. 2012, 354,
79.8, 163.8, 146.6, 137.5, 137.3, 134.5, 133.2, 131.0, 129.9,
29.5, 129.3, 128.2, 128.0, 127.1, 126.9, 52.7, 51.2, 6.9. IR (neat,
-
1
cm ): 3043, 1666, 1624, 1596, 1452, 1311, 1145, 857, 798, 757.
HRMS (ESI) (m/z): calcd for C H O S ([M+H] ), 391.0999;
found 391.1003.
+
23
18
4
2
95-300. (e) Reddy, C. R.; Prajapti, S. K.; Warudikar, K.; Ranjan, R.; Rao,
B. B. Org. Biomol. Chem. 2017, 15, 3130-3151. (f) Xia, Y.; Wang, L.-J.;
Wang, J.; Chen, S.; Shen, Y.; Guo, C.-H.; Liang, Y.-M. J. Org. Chem.
2
2
017, 82, 12386-12394. (g) Liu, Y.; Song, R.-J.; Li, J.-H. Chem. Commun.
017, 53, 8600-8603.
4
.3.30.
3'-(naphthalen-2-ylsulfonyl)-2'-phenyl-4'H-
spiro[cyclohexa[2,5]diene-1,1'-naphthalene]-4,4'-dione (3dd):
6
NMR (400 MHz, CDCl ,δ, ppm): 8.55 (s, 1H), 8.14 (dd, J = 7.6
Hz, J = 1.2 Hz, 1H), 8.01-7.94 (m, 3H), 7.90 (d, J = 8.0 Hz, 1H),
7
7
1
CDCl , δ, ppm): 184.1, 178.8, 162.4, 146.7, 140.2, 138.0, 136.9,
1
1
4. (a) Zhuo, C.-X.; Zhang, W.; You, S.-L. Angew. Chem. Int. Ed. 2012, 51,
12662-12686. (b) Kong, W.; Casimiro, M.; Fuentes, N.; Merino, E.;
Nevado, C. Angew. Chem. Int. Ed. 2013, 52, 13086-13090. (c) Han, G.;
Wang, Q.; Liu, Y.; Wang, Q. Org. Lett. 2014, 16, 5914-5917. (d) Ouyang,
X.-H.; Song, R.-J.; Li, Y.; Liu, B.; Li, J.-H. J. Org. Chem. 2014, 79,
1
5.2 mg, 67% yield; white solid, melting point 254-256 °C; H
3
.68-7.61 (m, 2H), 7.60-7.56 (m, 1H), 7.51-7.47 (m, 1H), 7.45-
.36 (m, 3H), 7.23-7.21 (m, 1H), 7.19-7.17 (m, 2H), 6.70 (d, J =
0.0 Hz, 2H), 6.34 (d, J = 10.0 Hz, 2H), C NMR (100 MHz,
4
582-4589. (e) Wang, L.-J.; Wang, A.-Q.; Xia, Y.; Wu, X.-X.; Liu, X.-Y.;
Liang, Y.-M. Chem. Commun. 2014, 50, 13998-14001. (f) Hua, H.-L.; He,
Y.-T.; Qiu, Y.-F.; Li, Y.-X.; Song, B.; Gao, P.; Song, X.-R.; Guo, D.-H.;
Liu, X.-Y.; Liang, Y.-M. Chem. Eur. J. 2015, 21, 1468-1473. (g) Wen, J.;
Wei, W.; Xue, S.; Yang, D.; Lou, Y.; Gao, C.; Wang, H. J. Org. Chem.
13
3
35.2, 134.2, 133.6, 131.9, 131.0, 130.2, 129.6, 129.4, 129.3,
29.2, 128.7, 128.1, 127.9, 127.4, 127.2, 127.1, 123.5, 52.7. IR
2
015, 80, 4966-4972. (h) Jin, D.-P.; Gao, P.; Chen, D.-Q.; Chen, S.;
Wang, J.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2016, 18, 3486-3489. (i)
Ouyang, X.-H.; Song, R.-J.; Liu, B.; Li, J.-H. Chem. Commun. 2016, 52,
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Kanematsu, M.; Hamada, Y. Org. Lett. 2010, 12, 5020-5023. (k) Wu, Q.-
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-
1
(neat, cm ): 3049, 1657, 1619, 1452, 1325, 1160, 1128, 1069,
+
7
4
62, 712. HRMS (ESI) (m/z): calcd for C H O S ([M+H] ),
31 20 4
89.1155; found 489.1161.
4
.3.31.
3'-(cyclopropylsulfonyl)-2'-phenyl-4'H-
(3ee):
5
. (m) Zhang, H.; Gu, Z.; Xu, P.; Hu, H.; Cheng, Y.; Zhu, C. Chem.
Commun. 2016, 52, 477-480. (n) Zhang, H.; Zhu, C. Org. Chem. Front.
017, 4, 1272-1275.
spiro[cyclohexa[2,5]diene-1,1'-naphthalene]-4,4'-dione
2.6 mg, 78% yield, white solid, melting point 276-278 °C; H
1
6
2

8
Tetrahedron
ACCEPTED MANUSCRIPT
5
. (a) Chen, Y.; Liu, X.; Lee, M.; Huang, C.; Inoyatov, I.; Chen, Z.; Perl, A.
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. (a) Harrak, Y.; Casula, G.; Basset, J.; Rosell, G.; Plescia, S.; Raffa, D.;
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