Visible-Light-Mediated Manganese-Catalyzed Allylation Reactions of Unactivated Alkyl Iodides

Article abstract of DOI:10.1021/acs.joc.0c00861

Herein, we report a protocol for visible-light-mediated allylation reactions between unactivated alkyl iodides and allyl sulfones under mild conditions with catalysis by inexpensive and readily available Mn₂(CO)₁₀. This protocol is compatible with a wide array of sensitive functional groups and has a broad substrate scope with regard to both alkyl iodides and allyl sulfones.

Full text of DOI:10.1021/acs.joc.0c00861

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Article
Visible-Light-Mediated Manganese-Catalyzed
Allylation Reactions of Unactivated Alkyl Iodides
Xiaochen Wang, Jianyang Dong, Yongqiang Li, Yuxiu Liu, and Qingmin Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c00861 • Publication Date (Web): 08 May 2020
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The Journal of Organic Chemistry
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Visible-Light-Mediated Manganese-Catalyzed Allylation Reactions
of Unactivated Alkyl Iodides
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†
†
†
†
*†‡
Xiaochen Wang, Jianyang Dong, Yongqiang Li, Yuxiu Liu and Qingmin Wang
†State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, College of
Chemistry, Nankai University, Tianjin 300071, People’s Republic of China
‡Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300071, People’s Republic of
China
Supporting Information Placeholder
ABSTRACT: Herein, we report a protocol for visible-light-mediated
allylation reactions between unactivated alkyl iodides and allyl
sulfones under mild conditions with catalysis by inexpensive and
R1
Mn(0) (15 mol%), Hantzsch ester (1.5 eq)
R
I
+
R
SO2Ph
DMSO, 36 W blue LED
R1

mild and efficient inexpensive and abundant (Mn) catalyst 27 examples up to 81% yield
readily available Mn
2
(CO)10. This protocol is compatible with a wide
array of sensitive functional groups and has a broad substrate scope with regard to both the alkyl iodide and the allyl sulfone
INTRODUCTION
catalysts with unactivated alkyl iodides (ca. −1.67 V vs. SCE for
1
0
ethyl iodide) to generate alkyl radicals is difficult.
Photoirradiation of decacarbonyldimanganese, Mn
known to cause homolytic cleavage of the weak Mn–Mn bond
Radical allylation is an efficient method for constructing
3
3
2
(CO)10, is
C(sp )–C(sp ) bonds and is particularly useful for organic
synthesis because it introduces an allyl group, which is a versatile
−
1
1
(~150 kJ mol ) to form two manganese-centered pentacarbonyl
handle for further functionalization. Most of the reported free
1
1
radicals [·Mn(CO)
5
]. These radicals can extract iodine atoms
radical allylation reactions use allylstannane as the source of the
2
from alkyl iodides in a process that is not limited by the reduction
allyl group, but this organotin reagent is toxic and difficult to
1
2,13
potential of the metal or the redox properties of the catalyst.
Therefore, the use of Mn (CO)10 as a catalyst would solve the
remove from product mixture. Interest in the use of photoredox
catalysis in organic synthesis has grown rapidly in recent years,
3
2
problem posed by the low reduction potential of alkyl iodides,
which hampers their reduction by common photocatalysts to
and there have been several reports of visible-light-mediated
photoredox radical allylation reactions with alkyl carboxylic
1
4
4
5
6
generate alkyl radicals. However, for successful catalytic
turnover, the active catalyst, [·Mn(CO) ], would have to be
regenerated from Mn(CO) I under the reaction conditions. Herein
acids, carboxylic acid active esters, alkyl trifluoroborates,
7
8
5
Katritzky pyridinium salts, or silicates as free radical precursors
with allyl sulfones as radical acceptors (Scheme 1A). Although
these allylation processes are much simpler and use less-toxic
reagents than previously reported reactions, most of them require
the use of noble metals such as iridium and ruthenium, and the
radical precursors often must be prefunctionalized. Therefore, it
would be a significant advance if these expensive catalysts could
be replaced with a cheap, earth-abundant 3d transition metal, such
as manganese, and if the substrate scope could be expanded to
include widely available organic compounds that are commonly
used as building blocks in medicinal chemistry, such as alcohols
and alkyl iodides.
5
we report that we have succeeded in developing a protocol for
efficient visible-light-mediated allylation reactions of unactivated
2
alkyl iodides with Mn (CO)10 as catalyst via a unique mechanism
(Scheme 1C).
Scheme 1. Photoredox-mediated allylation reactions.
In 2018, the Ryu group reported the use of alkyl iodides as
radical precursors for photocatalytic allylation reactions (Scheme
9
1
B), but high-energy xenon or ultraviolet lamps are required,
which limits the functional group tolerance and thus the substrate
scope of the process. Because alkyl iodides are readily available
and inexpensive, we wished to develop a practical, mild protocol
with a broader functional group tolerance and without the
requirement for high-energy UV light. To do so, we needed to
overcome the challenge posed by the fact that efficient excited-
state quenching of ruthenium- and iridium-based photoredox
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Page 2 of 9
A) Visible-light-mediated allylation of alkanes
Ph
the success of the reaction (entries 9 and 10), while the absence of
HE were proven detrimental for the whole protocol (entry 11).
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
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2
2
2
2
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5
5
5
5
5
5
5
5
6
Ph
R
COOX
R
BF3K
N
R
With satisfactory conditions in hand, we explored the substrate
scope of the reaction, beginning with the unactivated alkyl iodide
(Scheme 2). A wide range of primary alkyl iodides 1 reacted with
allyl sulfone 2b to give desired products 4–11 in moderate yields.
Specifically, primary iodides of linear alkanes gave 4–6 in 52%–
58% yields; and (iodomethyl)cyclobutane gave 7, with an intact
cyclobutane ring, in 61% yield. Benzyl iodide, phenethyl iodide,
and phenylpropyl iodide were also suitable substrates, giving 8, 9,
and 10 in 53%, 63%, and 56% yields, respectively. Notably, the
R1
(X = H/Nphth)
R1
R
Si(cat)2
Y
Ph
SO2Ar
R
R
Ru/Ir/riboflavin tetraacetate/Na2-Eosin Y/Cu
photoredox visible light
B) Allylation of alkyl iodides
R1
R1
PdCl2 /t-BuNC/LiCl
R
I
+
SO2Ph
Xe/black light

low functional group tolerance
high-energy UV/Xe light
0
1
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9
0
1
2
3
4
5
6
7
8
9
0
3
C) This work
reaction of 4-iodophenethyl iodide occurred selectively at the sp
C–I bond to afford 11 in 50% yield. Next, we examined the
suitability of secondary iodoalkanes. The yields obtained with
these substrates were higher than those with the primary iodides
because secondary alkyl radicals are more stable and more
nucleophilic than primary radicals. Acyclic secondary iodides
afforded target products 12 and 13 in yields of 71% and 56%,
respectively. Subsequently we explored various cyclic
iodoalkanes to determine the effects of ring size; five-, six-, eight-,
and twelve-membered-ring iodoalkanes all gave the
corresponding products (14–17) in moderate to good yields. The
sterically bulky substrate 2-iodoadamantane afforded 18 in 72%
yield. This reaction was also applicable to secondary alkanes
containing an aryl moiety (19 and 20). In addition, reaction of 1-
iodoadamantane, a tertiary iodoalkane, proceeded smoothly,
leading to the formation of 21 in 78% yield. Finally, we
investigated the applicability of the protocol for biologically
relevant substrates and found that the allylation reactions of
iodomenthol and 3-iodocholesterol, which were prepared in one
step from the corresponding alcohols, smoothly afforded target
products 22 and 23 in moderate yields. Product of this reaction
R1
R1
Mn (CO)
2
10
R
I
+
SO2Ph
R
Hantzsch Ester
6 W blue LED
3


broad scope
mild conditions
no prefunctionalization required
inexpensive photocatalyst
RESULTS AND DISCUSSION
Table 1. Optimization of Reaction Conditions.a
CO2Et
SO2Ph
Mn2(CO)10 (15 mol %)
I
+
HE (1.5 equiv), DMSO (0.2 M)
EtO2C
36 W blue LED, rt, 24 h, Ar
3
1a
2a
entry
photocatalyst
Mn (CO)10
Ir(ppy)
[Ru(bpy) ]Cl
[Ru(bpy) ](PF
Ir[dF(CF )ppy]
Mn (CO)10
Mn
solvent
DMSO
DMSO
DMSO
DMSO
DMSO
MeOH
Acetone
DMF
yield (%) b
81 (66 c)
NR
1
2
2
3
3
3
2
·6H
2
O
NR
1
5
will underwent a Giese reaction with alkyl iodide account for a
modest yield.
4
3
6
)
2
NR
5
3
2
(dtbbpy)PF
6
NR
Scheme 2. Substrate scope with respect to the alkyl iodide.a
6
2
73
7
2
(CO)10
(CO)10
(CO)10
—
55
8
Mn
Mn
2
53
9 d
DMSO
DMSO
DMSO
NR
2
1
0
NR
1
1 e
Mn
2
(CO)10
16
aReaction conditions, unless otherwise noted: 1a (0.3 mmol) and
2a (0.6 mmol) photocatalyst (0.045 mmol), Hantzsch ester (HE,
0.45 mmol), and solvent (1.5 mL) under Ar atmosphere.
b
1
Determined by H NMR spectroscopy using dibromomethane as
c
d
an internal standard. NR = no reaction. Isolated yield. Performed
e
in the absence of light. Performed in the absence of HE..
We commenced our studies using 2-iodo-2,3-dihydro-1H-
indene (1a) and ethyl 2-((phenylsulfonyl)methyl)acrylate (2a) as
model substrates to investigate the optimal reaction conditions
(
Table 1). We were pleased to find that in the presence of 15 mol
%
Mn (CO)10 and 1.5 equiv of Hantzsch ester (HE) as a reducing
2
agent, irradiation of 1a and 2a in DMSO with a 36 W blue LED at
room temperature under argon provided an excellent yield of
desired product 3 (entry 1). Screening of various photocatalysts
revealed that Ir(ppy)
Ir[dF(CF )ppy] (dtbbpy)PF
entries 2–5). MeOH, acetone, and DMF proved to be inferior
solvents to DMSO (entries 6–8). Control experiments
demonstrated that Mn (CO)10, and visible light were essential for
3
3 6 2 3 2 2
, [Ru(bpy) ](PF ) , [Ru(bpy) ]Cl ·6H O, or
3
2
6
failed to afford the target product
(
2
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The Journal of Organic Chemistry
Mn2(CO)10 (15 mol %)
R
CO2CH2Ph
SO2Ph
decreased to 5 mol %) and gave 3 in 60% yield (0.82g). Acrylate
R
I
+
1
2
3
4
5
6
7
8
9
HE (1.5 equiv), DMSO (0.2 M)
36 W blue LED, rt, 24 h, Ar
PhH2CO2C
4—23
3, which is a Michael receptor, underwent a Giese reaction with 4-
1
2b
2.0 equiv
15
iodophenethyl iodide to afford 30; and subsequent hydrolysis
1.0 equiv
with KOH afforded carboxylic acid 31; that is, we were able to
use the method described herein to synthesize structurally
complex carboxylic acids. Finally, iodide 32(obtained by reaction
of 4-iodophenethyl iodide and 2a) smoothly underwent Suzuki
coupling with an arylboronic acid or Sonagashira coupling with
phenylacetylene to provide moderate yields of corresponding
products 33 and 34, respectively.
From primary alkyl radicals
CO2CH2Ph
CO2CH2Ph
CO2CH2Ph
4
, 53% (44%)
CO2CH2Ph
5, 52% (41%)
CO2CH2Ph
6, 58% (50%)
CO2CH2Ph
9, 63% (52%)
7
, 61% (54%)
CO2CH2Ph
8, 53% (52%)
From secondary alkyl radicals
Scheme 4. Applications of the protocol.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
CO2CH2Ph
CO2CH2Ph
I
1
0, 56% (45%)
11, 50% (44%)
12, 71% (62%)
CO2Et
Mn2(CO)10 (5 mol %)
I
+
SO2Ph
HE (1.5 equiv), DMSO (0.2 M)
6 W blue LED, rt, 24 h, Ar
CO2CH2Ph
PhH2CO2C
EtO C
3, 0.82g, 60%
3
2
1a
2a
CO2CH2Ph
I
Mn2(CO)10 (10 mol %)
13, 56% (50%)
14, 68% (59%)
15, 71% (63%)
I
EtO2C
HE (1.5 equiv), DMSO (0.1 M)
36 W blue LED, rt, 24 h, Ar
3
0, 35%
I
CO2CH2Ph
CO2CH2Ph
KOH
CO2CH2Ph
dioxane, CH3OH, H2O
HO2C
16, 75% (68%)
CO2CH2Ph
17, 56% (54%)
18,72% (63%)
From tertiary alkyl radicals
CO2CH2Ph
31, 85%
I
I
2
CO Et
I
Mn (CO) (15 mol %)
2
10
PhH2CO2C
+
SO2Ph
HE (1.5 equiv), DMSO (0.2 M)
6 W blue LED, rt, 24 h, Ar
I
CO Et
2
2a
3
32, 50%
19, 65% (64%)
20, 67% (65%)
21, 78% (65%)
ArB(OH)2, Pd(OAc)2
K2CO3, PPh3,100 o
Allylation of biorelevant ioidides
C
toluene, EtOH, H2O
CO2Et
33, 54%
34, 58%
PhCH2O2C
CO2CH2Ph
Ph
PdCl2(PPh3)2, CuI
22, 62% (51%), dr = 68/32
23, 66% (65%), dr = 72/28
Et3N, 80 o
C
CO2Et
aUnless otherwise noted, reactions were performed on a 0.3 mmol
scale under the conditions listed in entry 1 of Table 1. Isolated
yields are given in parentheses.
Having explored the substrate scope of this visible-light-
mediated reaction, we turned our attention to its mechanism
(Scheme 5). (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO)
and 1,1-diphenylethylene were used as radical scavengers to
determine whether the reaction proceeded via a radical process.
We found that TEMPO (2.5 equiv) completely inhibited the
formation of 3, and TEMPO adduct 2,6-di-tert-butyl-4-methyl
phenoxy-2,3-dihydro-1H-indene 35 was detected by mass
spectrometry. In addition, the corresponding product of radical
trapping, 2-(2,2-diphenylvinyl)-2,3-dihydro-1H-indene (36), was
isolated from the reaction in the presence of 1,1-diphenylethylene,
further supporting the intermediacy of an alkyl radical. To
confirm the mechanism, we next performed a radical clock
Furthermore, we explored various allyl sulfone substrates to
determine their suitability for this radical allylation reaction
Scheme 3). When 2-iodo-2,3-dihydro-1H-indene (1a) was used
as the radical precursor, the yields were satisfactory, ranging from
49% to 81%. Allyl sulfones with various substituents (Me, Et, Bu
and alkyne esters) smoothly delivered the corresponding allylated
products (3 and 24–26) in good yields. In addition to the esters,
benzoyl compounds containing either an electron-donating
methoxy group (27) or an electron-withdrawing bromine atom
(
t
(
28) or trifluoromethyl group (29) were viable allyl sulfone
substrates.
experiment;
specifically,
allylation
of
2b
with
(
iodomethyl)cyclopropane gave ring-opened product 37, and
a
Scheme 3. Substrate scope with respect to the allyl sulfone.
allylation with 6-iodohex-1-ene gave a 2.7:1 mixture of 38a and
38b in 47% yield via a 5-exo radical cyclization. Taken together,
the results of these experiments clearly point to a radical pathway.
Moreover, a light/dark experiment showed that coupling product 3
could be formed in the dark (see ESI), which implies a radical
chain propagation mechanism.
1
Mn2(CO)10 (15 mol %)
R1
R
I
+
SO2Ph
HE (1.5 equiv), DMSO (0.2 M)
36 W blue LED, rt, 24 h, Ar
1a
2
3, 24–29
1.0 equiv
2.0 equiv
O
O
CO2Et
CO2CH3
CO2t-Bu
O
3
, 81% (66%)
O
24, 77% (68%)
25, 69% (60%)
26, 55% (54%)
O
Scheme 5. Mechanistic Experiments.
OCH3
Br
CF3
29, 49% (42%)
27, 68% (60%)
28, 62% (51%)
aUnless otherwise noted, reactions were performed on a 0.3 mmol
scale under the conditions shown in entry 1 of Table 1. Isolated
yields are given in parentheses.
To demonstrate the synthetic applications of the method
(Scheme 4), we carried out a gram-scale reaction (6.0 mmol)
between 1a with 2a, which was complete within 24 h under the
standard conditions (except that the amount of catalyst was
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EXPERIMENTAL SECTION
Page 4 of 9
(1)
CO2CH2Ph
SO2Ph
Mn2(CO)10 (15 mol %)
O
I
+
+
N
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
HE (1.5 equiv), DMSO (0.2 M)
PhH2CO2C
3
6 W blue LED, rt, 24 h, Ar
General Method and Materials. Reagents were purchased
from commercial sources and were used as received. Blue light-
emitting diode (LED) (36 W, max = 455 nm) purchased from
JIADENG (LS) was used for blue light irradiation. A fan attached
to the apparatus was used to maintain the reaction temperature at
room temperature. The material of the irradiation vessel was
1
a
2b
TEMPO (2.5 equiv)
3, 0%
35, detected by HRMS
Ph
Ph
CO2CH2Ph
SO2Ph
Mn2(CO)10 (15 mol %)
I +
+
HE (1.5 equiv), DMSO (0.2 M)
6 W blue LED, rt, 24 h, Ar
PhH2CO2C
3
1a
2b
1,1-diphenylethylene (2.5 equiv)
3, 25%
36, 7%
(2)
I
CO2CH2Ph
Mn2(CO)10 (15 mol %)
CO2CH2Ph
SO2Ph
+
+
1
13
borosilicate glass. H and C Nuclear Magnetic Resonance
NMR) spectra were recorded on Bruker Avance 400 Ultrashield
HE (1.5 equiv), DMSO (0.2 M)
36 W blue LED, rt, 24 h, Ar
2
b
37, 7%
(
Mn2(CO)10 (15 mol %)
NMR spectrometers. Chemical shifts (δ) were given in parts per
million (ppm) and were measured downfield from internal
tetramethylsilane. High-resolution mass spectrometry (HRMS)
data were obtained on an FTICR-MS instrument (Ionspec 7.0 T).
The melting points were determined on an X-4 microscope
melting point apparatus and are uncorrected. Conversion was
monitored by thin layer chromatography (TLC). Flash column
chromatography was performed over silica gel (100-200 mesh).
CO2CH2Ph
SO2Ph
CO2CH2Ph
+
I
HE (1.5 equiv), DMSO (0.2 M)
6 W blue LED, rt, 24 h, Ar
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
CO2CH2Ph
38a. 34%
2b
38b. 13%
aSee ESI for experimental details.
On the basis of these mechanistic experiments and previous
reports, we propose the mechanism depicted in Scheme 6. First,
upon irradiation with the blue LED, Mn
form [·Mn(CO) ], which abstracts iodine from 2-iodo-2,3-
dihydro-1H-indene (1a) to generate nucleophilic radical species A
and Mn(CO) I. The iodine-abstraction step is irreversible, owing
to the difference between the dissociation energies of the Mn–I
2
(CO)10 is homolyzed to
5
General Procedures for Synthesis of Alkyl Iodides.
16
According to literature reports, alkyl iodides are prepared by the
5
corresponding alcohols. The spectral data of the alkyl iodides are
1
6
−1
3
consistent with the literature data.
5
bond of Mn(CO) I (67 kcal mol ) and the C(sp )–I bond of 2-
Preparation of Allyl Sulfone. According to literature reports,17
−
1 12
iodo-2,3-dihydro-1H-indene (60 kcal mol ). Radical A then
adds to allyl sulfone 2a to afford radical intermediate B, which
undergoes β-fragmentation to give allylated product 3 and
The spectral data of the allyl sulfone are consistent with the
1
7
literature data. 2a and 2b is prepared according to the same
1
7
literature and spectral data of them are consistent with the
2
phenylsulfonyl radical (PhSO ·, C). Sulfonyl radical C abstracts
17
literature data.
the hydrogen atom from HE to afford benzenesulfinic acid 39 or
loss of sulfur dioxide to form a phenyl radical, which then
abstracts the hydrogen atom from HE. And the resulting dienyl
Radical trapping experiments. To a 8 mL glass vial was
added Mn
.3 mmol, 1.0 equiv), 2b (190 mg, 0.6 mmol, 2.0 equiv), TEMPO
117 mg, 0.75 mmol, 2.5 equiv) or 1,1-dipheny -lethylene (135
2
(CO)10 (17.55 mg, 0.045 mmol, 15 mol %), 1a (73 mg,
0
(
radical may react with Mn(CO)
5
I to regenerate the active catalyst
[·Mn(CO)
occur.
5
]. A ionic reduction of Mn(CO) I by HE may also
5
mg, 0.75 mmol, 2.5 equiv), HE (114 mg, 0.45 mmol, 1.5 equiv)
and 1.5mL of DMSO. The reaction mixture was degassed by
bubbling with Ar for 15 s with an outlet needle and the vial was
sealed with PTFE cap. The mixture was then stirred rapidly and
irradiated with a 36 W Blue LED (approximately 2 cm away from
the light source) at room temperature for 24 h.
Scheme 6. Proposed Mechanism
CO2Et
SO2Ph
Mn2(CO)10 (15 mol %)
I
+
HE (1.5 equiv), DMSO (0.2 M)
36 W blue LED, rt, 24 h, Ar
EtO2C
3
Procedure for Giese reaction (synthesis of 30). To a 8 mL
1
a
2a
glass vial was added Mn
2
(CO)10 (11.7 mg, 0.03 mmol, 10 mol %),
(
CO)5Mn-Mn(CO)5
3
(69 mg, 0.3 mmol, 1.0 equiv), 1-iodo-4-(2-iodoethyl)benzene
hv
(215 mg, 0.6 mmol, 2.0 equiv), HE (114 mg, 0.45 mmol, 1.5
equiv) and 3.0 mL of DMSO. The reaction mixture was degassed
by bubbling with Ar for 15 s with an outlet needle and the vial
was sealed with PTFE cap. The mixture was then stirred rapidly
and irradiated with a 36 W Blue LED (approximately 2 cm away
from the light source) at room temperature for 24 h. The mixture
was diluted with 10 mL of aqueous 1 M NaHCO solution, and
extracted with DCM (3 × 20 mL). The combined organic extracts
2 4
were washed with brine (40 mL), dried over Na SO , and
I
1a
Mn(CO)5
EtO2C
EtO2C
CO2Et
N
H I
A
CO2Et
SO2Ph
2a
3
CO2Et
SO2Ph
N
H
I-Mn(CO)5
EtO2C
B
concentrated in vacuo. Purification of the crude product by flash
chromatography on silica gel using the indicated solvent system
afforded the desired product.
+
SO2
SO2H
EtO2C
Hydrolysis of ester (synthesis of 31). To an oven dried
Schlenk tube was added synthesized pure ester 30 (268 mg, 0.58
mmol, 1.0 equiv) ， KOH (98 mg, 1.74 mmol, 3.0 equiv), the
solvent(6 ml) is 1/1/1 by volume of dioxane, methanol and water.
The tube was evacuated and backfilled with Ar (this process was
repeated three times). The mixture was then stirred rapidly and
3
39
EtO2C
CO2Et
C
N
H
In conclusion, we have developed a new protocol for visible-
light-mediated allylation reactions of unactivated alkyl iodides
with catalysis by Mn (CO)10, an inexpensive complex of an earth-
2
abundant metal, and with HE as reducing agent. This versatile
protocol tolerates a variety of functional groups and has a broad
scope with regard to both the alkyl iodide and the allyl sulfone.
Moreover, the allylated products contain a reactive terminal olefin
moiety that can act as a handle for further functionalization.
o
warm up to 110 C for 24h. After finishing the reaction, added 1M
HCl to adjust the system pH to 2, and extracted with ethyl acetate
(3 × 25 mL). The combined organic extracts were washed with
brine (75 mL), dried over Na
get pure product.
Procedure for Suzuki coupling reaction (synthesis of 33).
Synthesized pure compound 32 (69 mg, 0.2 mmol, 1.0 equiv),
2 3
phenylboronic acid(44 mg, 0.22 mmol, 1.1 equiv), K CO (55 mg,
2 4
SO , and concentrated in vacuum to
ACS Paragon Plus Environment

Page 5 of 9
The Journal of Organic Chemistry
0
.4 mmol, 2.0 equiv), Pd(OAc)
2
(2.2 mg, 0.01 mmol, 5.0 mol %),
139.8, 126.2, 125.6, 124.5, 60.7, 38.8, 38.3, 37.8, 14.2. HRMS
+
1
2
3
4
5
6
7
8
9
PPh (9 mg, 0.03mmol, 0.15 equiv), toluene (2.3 mL, 0.113M),
3
(ESI-TOF) m/z: [M + Na] Calcd for C15
H
18NaO
2
253.1199;
equal mixture of ethanol/water (0.113 mL, 0.565 M) were taken
into a re-sealable pressure tube (13 x 100 mm) and was allowed it
to stir at 100 C with heating mantle for 24h. After finishing the
reaction, the solvent mixture was evaporated and again diluted
with dicholomethane (20 mL). This diluted mixture was then
passed through a celite bed followed by the washing of this bed
with additional amount of dicholomethane (20 mL). This
combined organic layer was washed with water (1 x 20 mL) using
a separating funnel. The collected organic layer was dried over
Found 253.1198
benzyl 2-methylenepentanoate (4)
According to the general procedure. Colorless oil (27.2 mg, 44%)
Yield determined by H NMR: 53%. R
o
1
f
= 0.40 (Petroleum
3
1
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.40 – 7.30 (m,
5H), 6.20 (s, 1H), 5.55 (d, J = 1.2Hz, 1H), 5.20 (s, 2H), 2.30 (t, J
= 7.5 Hz, 2H), 1.55 – 1.44 (m, 2H), 0.92 (t, J = 7.4 Hz, 3H).
1
3
1
C{ H} NMR (100 MHz, CDCl
3
) δ 167.2, 140.6, 136.2, 128.6,
128.1, 128.0, 125.0, 66.3, 33.9, 21.5, 13.7. HRMS (ESI-TOF) m/z:
+
MgSO
4
and solvent was evaporated under reduced pressure. This
2
[M + Na] Calcd for C13H16NaO 227.1043; Found 227.1042
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
crude product was then subjected to purification using flash
column chromatography to get pure product.
Procedure for Sonagashira coupling reaction (synthesis of
34). Synthesized pure compound 32 (69 mg, 0.2 mmol, 1.0 equiv),
phenylacetylene (31 mg, 0.3 mmol, 1.5 equiv), CuI(3.8 mg, 0.02
benzyl 2-methylenehexanoate (5)
According to the general procedure. Colorless oil (26.7 mg, 41%)
Yield determined by H NMR: 52%. R
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
1
f
= 0.40 (Petroleum
) δ 7.41 – 7.29 (m,
1
3
5H), 6.18 (s, 1H), 5.54 (s, 1H), 2.32 (t, J = 7.6 Hz, 2H), 1.50 –
1.40 (m, 2H), 1.37 – 1.28 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H).
mmol, 0.1 equiv), PdCl
Et N (2 ml) were taken into a re-sealable pressure tube (13 x 100
mm) and was allowed it to stir at 80 C with heating mantle for
4h. After finishing the reaction, add water to quench the reaction,
2 3 2
(PPh ) (7 mg, 0.01 mmol, 5.0 mol %),
1
3
1
3
C{ H} NMR (100 MHz, CDCl
3
) δ 167.2, 140.9, 136.2, 128.5,
o
128.1, 128.0, 124.8, 66.3, 31.6, 30.6, 22.3, 13.9.HRMS (ESI-
TOF) m/z: [M + Na] Calcd for C14
241.1197
benzyl 2-methylenenonanoate (6)
According to the general procedure. Colorless oil (39.1 mg, 50%)
Yield determined by H NMR: 58%. R
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.39 – 7.30 (m,
5H), 6.18 (d, J = 0.8 Hz, 1H), 5.54 (d, J = 1.2 Hz, 1H), 5.20 (s,
2H), 2.36 – 2.27 (m, 2H), 1.50 – 1.42 (m, 2H), 1.32 – 1.23 (m,
8H), 0.88 (t, J = 6.8 Hz, 3H). C{ H} NMR (100 MHz, CDCl ) δ
3
167.2, 140.8, 136.2, 128.6, 128.1, 128.0, 124.8, 66.3, 31.9, 31.82,
29.2, 29.1, 28.4, 22.7, 14.1. HRMS (ESI-TOF) m/z: [M + H]
25 2
Calcd for C17H O 261.1849; Found 261.1845
benzyl 4-cyclobutyl-2-methylenebutanoate (7)
According to the general procedure. Colorless oil (39.3 mg, 54%)
Yield determined by H NMR: 61%. R
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
5H), 6.18 (d, J = 4.0 Hz, 1H), 5.54 (d, J = 3.2 Hz, 1H), 5.20 (d, J =
4.8 Hz, 2H), 2.26 – 2.17 (m, 2H), 2.08 – 1.98 (m, 2H), 1.87 – 1.75
+
2
2
H18NaO 241.1199; Found
the solvent mixture was evaporated and again diluted with ethyl
acetate (20 mL x 3). This combined organic layer was washed
with water (1 x 20 mL) using a separating funnel. The collected
1
organic layer was dried over Na
2
SO
4
and solvent was evaporated
f
= 0.40 (Petroleum
3
1
under reduced pressure. This crude product was then subjected to
purification using flash column chromatography to get pure
product.
13
1
Gram-scale Reaction. To a 100 ml oven dried Schlenk tube
was added Mn
6.0 mmol, 1.0 equiv), 2a (3.051g, 12.0 mmol, 2.0 equiv), HE
2.28 g, 9.0 mmol, 1.5 equiv) and 30 mL of DMSO. The tube was
2
(CO)10 (117 mg, 0.3 mmol, 5 mol %), 1a (1.45g,
+
(
evacuated and backfilled with Ar three times. The mixture was
then stirred rapidly and irradiated under 36W blue LED at room
temperature for 24 h. The mixture was diluted with 50 mL of
1
f
= 0.40 (Petroleum
) δ 7.46 – 7.27 (m,
1
aqueous 1 M NaHCO
mL). The combined organic extracts were washed with brine (200
mL), dried over Na SO , and concentrated in vacuum. After
3
solution, and extracted with DCM (3 × 100
3
2
4
1
3
1
purification by flash column chromatography on silica gel, the
product 3 was obtained in 60% yield (0.82g).
(m, 2H), 1.65 – 1.51 (m, 4H), 1.31 – 1.21 (m, 1H). C{ H} NMR
(100 MHz, CDCl ) δ 167.2, 140.8, 136.2, 128.6, 128.1, 128.0,
124.7, 66.3, 35.7, 35.6, 29.6, 28.2, 18.4. HRMS (ESI-TOF) m/z:
3
Experimental
Procedures
and
Product
+
[
M + Na] Calcd for C16
benzyl 2-methylene-4-phenylbutanoate (8)
According to the general procedure. Colorless oil (41.7 mg, 52%)
2
H20NaO 267.1356; Found 267.1354
Characterization
General Procedure for the allylation of unactivated alkyl
iodides. To a 8 mL glass vial was added Mn (CO)10 (17.55 mg,
.045 mmol, 15 mol %), 1 (0.3 mmol, 1.0 equiv), 2 (0.6 mmol,
.0 equiv), HE (114 mg, 0.45 mmol, 1.5 equiv) and 1.5 mL of
2
1
Yield determined by H NMR: 53%. R
f
= 0.40 (Petroleum
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.34 – 7.23 (m,
H), 7.22 – 7.14 (m, 2H), 7.13 – 7.04 (m, 3H), 6.13 (s, 1H), 5.44
s, 1H), 5.13 (s, 2H), 2.76 – 2.66 (m, 2H), 2.61 – 2.52 (m, 2H).
0
2
1
3
5
DMSO. The reaction mixture was degassed by bubbling with Ar
for 15 s with an outlet needle and the vial was sealed with PTFE
cap. The mixture was then stirred rapidly and irradiated with a 36
W Blue LED (approximately 2 cm away from the light source) at
room temperature for 24 h. The mixture was diluted with 10 mL
(
1
3
1
C{ H} NMR (100 MHz, CDCl
3
) δ 166.9, 141.4, 139.9, 136.1,
1
3
28.6, 128.5, 128.4, 128.2, 128.1, 126.0, 125.8, 66.5, 34.9,
4.0.HRMS (ESI-TOF) m/z: [M + H] Calcd for C18H O
19 2
+
267.1380; Found 267.1379
benzyl 2-methylene-5-phenylpentanoate (9)
According to the general procedure. Colorless oil (44.3 mg, 52%)
of aqueous 1 M NaHCO
0 mL). The combined organic extracts were washed with brine
(40 mL), dried over Na SO , and concentrated in vacuo.
3
solution, and extracted with DCM (3×
2
2
4
1
Yield determined by H NMR: 63%. R
f
= 0.40 (Petroleum
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.39 – 7.29 (m,
H), 7.29 – 7.22 (m, 2H), 7.20 – 7.12 (m, 3H), 6.21 (s, 1H), 5.55
s, 1H), 5.19 (s, 2H), 2.63 (t, J = 7.6 Hz, 2H), 2.37 (t, J = 7.6 Hz,
Purification of the crude product by flash chromatography on
silica gel using the indicated solvent system afforded the desired
product.
Product Characterization
ethyl 2-((2,3-dihydro-1H-inden-2-yl)methyl)acrylate (3)
1
3
5
(
13
1
2
3
H), 1.86 – 1.75 (m, 2H). C{ H} NMR (100 MHz, CDCl ) δ
167.1, 142.1, 140.4, 136.1, 128.6, 128.5, 128.4, 128.2, 128.1,
According to the general procedure. Colorless oil (45.8 mg, 66%)
1
125.9, 125.3, 66.4, 35.5, 31.6, 30.1. HRMS (ESI-TOF) m/z: [M +
Yield determined by H NMR: 81%. R
f
= 0.40 (Petroleum
) δ 7.17 (dd, J =
.2, 3.6 Hz, 2H), 7.11 (dd, J = 5.6, 3.2 Hz, 2H), 6.20 (d, J = 0.8
Hz, 1H), 5.56 (d, J = 0.8 Hz, 1H), 4.21 (q, J = 7.2 Hz, 2H), 3.03
+
1
Na] Calcd for C H NaO 303.1356; Found 303.1352
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
19 20
2
benzyl 2-methylene-6-phenylhexanoate (10)
According to the general procedure. Colorless oil (39.5 mg, 45%)
5
1
Yield determined by H NMR: 56%. R
f
= 0.40 (Petroleum
) δ 7.40 – 7.29 (m,
5H), 7.29 – 7.23 (m, 2H), 7.19 – 7.11 (m, 3H), 6.18 (s, 1H), 5.52
(dd, J = 15.2, 7.2 Hz, 2H), 2.71 (dd, J = 14.4, 7.2 Hz, 1H), 2.62
1
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
(
7
dd, J = 15.2, 6.8 Hz, 2H), 2.47 (d, J = 7.2 Hz, 2H), 1.30 (t, J =
.2 Hz, 3H). C{ H} NMR (100 MHz, CDCl ) δ 167.3, 143.1,
3
13
1
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 9
(
s, 1H), 5.18 (s, 2H), 2.60 (t, J = 7.2 Hz, 2H), 2.35 (t, J = 7.2 Hz,
According to the general procedure. Colorless oil (55.2 mg, 54%)
1
3
1
1
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2H), 1.69 – 1.60 (m, 2H), 1.56 – 1.48 (m, 2H). C{ H} NMR
100 MHz, CDCl ) δ 167.1, 142.5, 140.6, 136.2, 128.6, 128.4,
28.3, 128.2, 128.1, 125.7, 125.1, 66.4, 35.8, 31.8, 31.0, 28.1.
Yield determined by H NMR: 56%. R
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
f
= 0.40 (Petroleum
) δ 7.39 – 7.28 (m,
1
(
1
3
3
5H), 6.21 (d, J = 1.6 Hz, 1H), 5.51 (d, J = 1.2 Hz, 1H), 5.19 (s,
2H), 2.23 (d, J = 7.2 Hz, 2H), 1.72 – 1.62 (m, 1H), 1.36 – 1.19 (m,
+
HRMS (ESI-TOF) m/z: [M + Na] Calcd for C20H22NaO
2
3
1
3
1
17.1512; Found 317.1510
3
22H). C{ H} NMR (100 MHz, CDCl ) δ 167.3, 139.8, 136.2,
benzyl 5-(4-iodophenyl)-2-methylenepentanoate (11)
According to the general procedure. Colorless oil (53.9 mg, 44%)
128.6, 128.1, 128.1, 126.2, 66.4, 38.0, 32.6, 29.0, 24.5, 23.9, 23.5,
+
23.4, 21.8. HRMS (ESI-TOF) m/z: [M + H] Calcd for C23
H
35
O
2
1
Yield determined by H NMR: 50%. R
f
= 0.40 (Petroleum
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.56 (d, J =
.4 Hz, 2H), 7.40 – 7.29 (m, 5H), 6.89 (d, J = 8.4 Hz, 2H), 6.21 (s,
H), 5.54 (s, 1H), 5.19 (s, 2H), 2.56 (t, J = 7.6 Hz, 2H), 2.38 –
343.2632; Found 343.2627
benzyl 4-(adamantan-2-yl)-2-methylenebutanoate (18)
1
3
8
1
2
According to the general procedure. Colorless oil (59 .0mg, 63%)
1
Yield determined by H NMR: 72%. R
f
= 0.40 (Petroleum
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
3
1
1
.30 (m, 2H), 1.82 – 1.72 (m, 2H). C{ H} NMR (100 MHz,
) δ 167.0, 141.7, 140.2, 137.4, 136.1, 130.6, 128.6, 128.2,
28.1, 125.4, 90.9, 66.5, 34.9, 31.5, 29.9. HRMS (ESI-TOF) m/z:
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.42 – 7.27 (m,
CDCl
3
5H), 6.20 (s, 1H), 5.51 (s, 1H), 5.19 (s, 2H), 2.47 (d, J = 7.2 Hz,
2H), 1.94 – 1.79 (m, 7H), 1.69 (d, J = 12.5 Hz, 6H), 1.50 (d, J =
1
+
13
1
[M + Na] Calcd for C19
benzyl 4-methyl-2-methylenepentanoate (12)
According to the general procedure. Colorless oil (53.9 mg, 62%)
H
20INaO
2
429.0322; Found 429.0319
3
12.6 Hz, 2H). C{ H} NMR (100 MHz, CDCl ) δ 167.3, 139.7,
1
8
136.2, 128.6, 128.1, 128.0, 125.8, 66.4, 43.1, 39.2, 38.4, 35.3,
+
31.5, 31.4, 28.2, 28.0. HRMS (ESI-TOF) m/z: [M + H] Calcd for
1
Yield determined by H NMR: 71%. R
f
= 0.40 (Petroleum
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.32 – 7.21 (m,
H), 6.14 (d, J = 1.6 Hz, 1H), 5.44 (d, J = 1.2 Hz, 1H), 5.11 (s,
C
21
H
27
O
2
311.2006; Found 311.2001
1
3
(S)-benzyl 4-methyl-2-methylene-5-phenylpentanoate (19)
5
2
=
According to the general procedure. Colorless oil (56.5 mg, 64%)
1
H), 2.12 (dd, J = 7.2, 0.8 Hz, 2H), 1.78 – 1.68 (m, 1H), 0.81 (d, J
Yield determined by H NMR: 65%. R
f
= 0.40 (Petroleum
) δ 7.39 – 7.29 (m,
13
1
1
6.8 Hz, 6H). C{ H} NMR (100 MHz, CDCl
3
) δ 167.2, 140.6,
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
136.2, 128.6, 128.1, 128.0, 125.0, 66.3, 33.9, 21.5, 13.7.HRMS
5H), 7.24 (t, J = 7.2 Hz, 2H), 7.16 (t, J = 7.2 Hz, 1H), 7.09 (d, J =
7.2 Hz, 2H), 6.24 (s, 1H), 5.53 (s, 1H), 5.23 – 5.12 (m, 2H), 2.67
(dd, J = 13.2, 5.6 Hz, 1H), 2.44 (dd, J = 13.6, 5.6 Hz, 1H), 2.35
(dd, J = 13.6, 8.4 Hz, 1H), 2.13 (dd, J = 13.6, 8.4 Hz, 1H), 2.06 –
+
(
2
ESI-TOF) m/z: [M + H] Calcd for C14
19.1377
R)-benzyl 4-methyl-2-methylenehexanoate (13)
According to the general procedure. Colorless oil (36.7 mg, 50%)
19 2
H O 219.1380; Found
(
1
3
1
1.93 (m, 1H), 0.81 (d, J = 6.4 Hz, 3H). C{ H} NMR (100 MHz,
CDCl ) δ 167.2, 141.0, 139.4, 136.2, 129.2, 128.6, 128.2, 128.1,
126.6, 125.3, 66.4, 43.4, 39.6, 34.0, 19.0. HRMS (ESI-TOF) m/z:
1
Yield determined by H NMR: 56%. R
f
= 0.40 (Petroleum
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.42 – 7.26 (m,
5H), 6.21 (s, 1H), 5.51 (s, 1H), 5.18 (s, 2H), 2.44 – 2.33 (m, 1H),
3
1
3
+
2
[M + Na] Calcd for C20H22NaO 317.1512 ; Found 317.1508
2
1
.12 – 2.01 (m, 1H), 1.63 – 1.52 (m, 1H), 1.43 – 1.29 (m, 1H),
benzyl 2-((2,3-dihydro-1H-inden-2-yl)methyl)acrylate (20)
1
3
1
.19 – 1.07 (m, 1H), 0.90 – 0.81 (m, 6H). C{ H} NMR (100
) δ 167.3, 139.7, 136.2, 128.5, 128.1, 128.0, 126.1,
6.3, 39.4, 33.5, 29.3, 18.8, 11.4. HRMS (ESI-TOF) m/z: [M +
According to the general procedure. Colorless oil (57.3 mg, 65%)
1
MHz, CDCl
3
Yield determined by H NMR: 67%. R
f
= 0.40 (Petroleum
) δ 7.49 – 7.27 (m,
1
6
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
+
H] Calcd for C15
H
21
O
2
233.1536; Found 233.1532
5H), 7.15 (d, J = 2.4 Hz, 2H), 7.11 (d, J = 2.8 Hz, 2H), 6.25 (s,
1H), 5.59 (s, 1H), 5.20 (s, 2H), 3.01 (dd, J = 15.2, 7.5 Hz, 2H),
2.70 (dt, J = 14.4, 7.2 Hz, 1H), 2.60 (dd, J = 15.6, 6.8 Hz, 2H),
benzyl 2-(cyclopentylmethyl)acrylate (14)
According to the general procedure. Colorless oil (43.1 mg, 59%)
1
13
1
Yield determined by H NMR: 68%. R
f
= 0.40 (Petroleum
) δ 7.41 – 7.28 (m,
H), 6.18 (s, 1H), 5.54 (s, 1H), 5.19 (s, 2H), 2.33 (d, J = 7.2 Hz,
H), 2.09 – 1.99 (m, 1H), 1.79 – 1.66 (m, 2H), 1.66 – 1.56 (m,
3
2.49 (d, J = 7.2 Hz, 2H). C{ H} NMR (100 MHz, CDCl ) δ
1
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
167.1, 143.1, 139.6, 136.1, 128.6, 128.2, 128.1, 126.2, 124.5, 66.5,
+
5
2
2
38.9, 38.1. HRMS (ESI-TOF) m/z: [M + Na] Calcd for
C
20
H
20NaO
2
315.1356; Found 315.1352
benzyl 2-(adamantan-1-ylmethyl)acrylate (21)
According to the general procedure. Colorless oil (60.6 mg, 65%)
1
3
1
H), 1.55 – 1.46 (m, 2H), 1.19 – 1.05 (m, 2H). C{ H} NMR
) δ 167.3, 140.4, 136.2, 128.5, 128.1, 128.0,
125.4, 66.3, 38.6, 38.2, 32.4, 25.0. HRMS (ESI-TOF) m/z: [M +
(
100 MHz, CDCl
3
1
Yield determined by H NMR: 78%. R
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.41 – 7.29 (m,
f
= 0.40 (Petroleum
+
1
H] Calcd for C16
H
20
O
2
245.1536; Found 245.1533
3
benzyl 2-(cyclohexylmethyl)acrylate (15)
According to the general procedure. Colorless oil (48.7 mg, 63%)
5H), 6.23 (s, 1H), 5.44 (s, 1H), 5.18 (s, 2H), 2.17 (s, 2H), 1.91 (s,
3H), 1.66 (d, J = 12.0 Hz, 3H), 1.57 (d, J = 11.6 Hz, 3H), 1.43 (s,
1
13
1
Yield determined by H NMR: 71%. R
f
= 0.40 (Petroleum
) δ 7.38 – 7.31 (m,
H), 6.20 (d, J = 1.6 Hz, 1H), 5.50 (d, J = 1.2 Hz, 1H), 5.19 (s,
2H), 2.21 (d, J = 7.2 Hz, 2H), 1.70 – 1.65 (m, 4H), 1.50 – 1.40 (m,
6H). C{ H} NMR (100 MHz, CDCl
3
) δ 168.0, 137.3, 136.2,
1
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
128.5, 128.2, 128.1, 127.5, 66.5, 45.5, 42.1, 37.0, 33.3, 28.7.
+
5
HRMS (ESI-TOF) m/z: [M + Na] Calcd for C21H30NaO
2
333.1825; Found 333.1819
1
3
1
1H), 1.25 – 1.07 (m, 4H), 0.92 – 0.83 (m, 2H). C{ H} NMR
100 MHz, CDCl ) δ 167.3, 139.2, 136.2, 128.5, 128.1, 128.0,
26.1, 66.3, 40.0, 36.6, 33.1, 26.5, 26.2. HRMS (ESI-TOF) m/z:
benzyl
2-(((1R,2S,5R)-2-isopropyl-5-
(
1
[
3
methylcyclohexyl)methyl)acrylate (22)
According to the general procedure. Colorless oil (50.0 mg, 51%)
+
1
M + H] Calcd for C17
H
23
O
2
259.1693; Found 259.1690
Yield determined by H NMR: 62%. dr = 68/32. R
f
= 0.40
) δ
1
benzyl 2-(cyclooctylmethyl)acrylate (16)
(Petroleum ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
According to the general procedure. Colorless oil (58.3 mg, 68%)
7.41 – 7.25 (m, 5H), 6.22 (d, J = 1.2 Hz, 1H), 5.52 (d, J = 6.0 Hz,
1H), 5.49 (s, 1H), 5.24 – 5.14 (m, 2H), 2.85 (dd, J = 13.2, 2.8 Hz,
0.68H), 2.38 (dd, J = 13.6, 2.8 Hz, 0.32H), 2.25 (t, J = 12.8 Hz,
0.32H), 2.09 (dd, J = 7.6, 3.2 Hz, 0.32H), 2.04 (ddd, J = 13.6, 6.8,
2.8 Hz, 0.68H), 1.74 – 1.69 (m, 1.29H), 1.63 (ddd, J = 10.8, 10.4,
4.0 Hz, 2.75H), 1.45 (d, J = 11.2 Hz, 0.32H), 1.43 – 1.37 (m,
0.68H), 1.25 (s, 0.32H), 1.21 (ddd, J = 11.6, 6.6, 3.6 Hz, 0.68H),
1.07 (dd, J = 12.8, 9.2 Hz, 0.32H), 0.98 (d, J = 2.8 Hz, 0.32H),
0.95 (dd, J = 9.2, 6.0 Hz, 0.68H), 0.93 – 0.86 (m, 5H), 0.85 (d, J =
2.8 Hz, 0.68H), 0.82 (d, J = 6.4 Hz, 2H), 0.78 (d, J = 6.4 Hz, 1H),
1
Yield determined by H NMR: 75%. R
f
= 0.40 (Petroleum
) δ 7.43 – 7.23 (m,
1
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
5H), 6.20 (d, J = 1.6 Hz, 1H), 5.50 (d, J = 1.2 Hz, 1H), 5.19 (s,
2
1
1
3
H), 2.21 (d, J = 7.2 Hz, 2H), 1.79 – 1.68 (m, 1H), 1.63 – 1.37 (m,
1
3
1
3
2H), 1.30 – 1.18 (m, 2H). C{ H} NMR (100 MHz, CDCl ) δ
66.4, 138.9, 135.3, 127.6, 127.2, 127.1, 125.2, 65.4, 39.6, 35.1,
1.0, 26.3, 25.3, 24.4. HRMS (ESI-TOF) m/z: [M + H] Calcd for
+
C
19
H
27
O
2
287.2006; Found 287.2002
benzyl 2-(cyclododecylmethyl)acrylate (17)
ACS Paragon Plus Environment

Page 7 of 9
The Journal of Organic Chemistry
0
.73 (d, J = 6.8 Hz, 2H), 0.45 (dd, J = 24.4, 11.6 Hz, 0.68H).
C{ H} NMR (100 MHz, CDCl ) δ 167.3, 140.1, 139.7, 136.1,
3
(100 MHz, CDCl
126.2, 124.5, 124.2, 114.0, 113.6, 55.5, 39.0, 39.0, 38.3. HRMS
(ESI-TOF) m/z: [M + H] Calcd for C20
293.1531
1-(4-bromophenyl)-2-((2,3-dihydro-1H-inden-2-
yl)methyl)prop-2-en-1-one (28)
3
) δ 197.0, 163.3, 147.5, 143.1, 132.1, 130.2,
1
3
1
1
2
3
4
5
6
7
8
9
+
1
3
2
28.6, 128.2, 128.2, 126.6, 126.1, 66.4, 66.4, 47.9, 40.9, 37.8,
7.6, 36.3, 35.8, 35.3, 33.6, 32.6, 29.4, 28.1, 26.6, 25.7, 25.0, 24.3,
21 2
H O 293.1536; Found
+
2.8, 21.8, 21.6, 20.6, 15.1. HRMS (ESI-TOF) m/z: [M + H]
31 2
Calcd for C21H O 315.2319; Found 315.2314
benzyl 2-(((3S,10S,13R,17R)-10,13-dimethyl-17-((R)-6-
methylheptan-2-yl)hexadecahydro-1H-cyclopenta[a]phenanthren-
3-yl)methyl)acrylate (23)
According to the general procedure. Colorless oil (51.9 mg, 51%)
1
Yield determined by H NMR: 62%. R
ether/EtOAc, 10/1). H NMR (400 MHz, CDCl
f
= 0.40 (Petroleum
) δ 7.72 (q, J =
1
3
According to the general procedure. Colorless oil (74.8 mg, 65%)
8.4 Hz, 4H), 7.31 – 7.26 (m, 2H), 7.25 – 7.21 (m, 2H), 5.99 (s,
1H), 5.73 (s, 1H), 3.15 (dd, J = 10.4, 6.4 Hz, 2H), 2.80 (s, 1H),
1
Yield determined by H NMR: 66%. dr = 72/28. R
(
f
= 0.40
) δ
1
13
1
Petroleum ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
3
2.78 (s, 4H). C{ H} NMR (100 MHz, CDCl ) δ 197.0, 147.1,
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
7
5
2
.39 – 7.28 (m, 5H), 6.22 (s, 0.72H), 6.19 (s, 0.28H), 5.50 (s, 1H),
.18 (s, 2H), 2.42 (t, J = 6.6 Hz, 1.44H), 2.29 – 2.15 (m, 0.55H),
.01 – 1.87 (m, 2H), 1.84 – 1.76 (m, 1H), 1.67 – 1.60 (m, 2H),
142.9, 136.5, 131.6, 131.1, 127.4, 126.6, 126.3, 124.5, 124.4, 39.0,
+
38.3, 38.2. HRMS (ESI-TOF) m/z: [M + Na] Calcd for
C
19
H
17BrNaO 363.0355; Found 363.0349
1.55 – 1.44 (m, 4H), 1.39 – 1.30 (m, 5H), 1.26 – 1.19 (m, 4H),
1.09 (dd, J = 20.0, 7.0 Hz, 9H), 1.02 – 0.96 (m, 3H), 0.90 (d, J =
2-((2,3-dihydro-1H-inden-2-yl)methyl)-1-(4-
(trifluoromethyl)phenyl)prop-2-en-1-one (29)
6
0
1
5
3
2
.3 Hz, 4H), 0.86 (d, J = 6.5 Hz, 8H), 0.77 (s, 2H), 0.74 (s, 1H),
According to the general procedure. Colorless oil (42.0 mg, 42%)
1
3
1
1
.64 (s, 4H). C{ H} NMR (100 MHz, CDCl
3
) δ 167.3, 140.2,
Yield determined by H NMR: 49%. R
f
= 0.40 (Petroleum
) δ 7.92 (d, J =
1
36.2, 128.5, 128.1, 128.0, 126.0, 66.4, 66.3, 56.7, 56.6, 56.4,
4.7, 54.7, 46.6, 42.6, 40.3, 40.1, 40.0, 39.6, 38.5, 37.2, 36.4, 36.2,
6.0, 35.9, 35.6, 35.4, 34.6, 33.1, 32.5, 32.2, 32.0, 29.0, 28.8, 28.3,
ether/EtOAc, 10/1). H NMR (400 MHz, CDCl
3
8.0 Hz, 2H), 7.81 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 4.0 Hz, 2H),
7.23 (dd, J = 5.2, 3.2 Hz, 2H), 6.07 (s, 1H), 5.77 (s, 1H), 3.24 –
13
1
8.1, 24.8, 24.2, 23.9, 23.9, 22.9, 22.6, 21.1, 20.8, 18.7, 12.4, 12.1,
3.13 (m, 2H), 2.82 (s, 1H), 2.79 (s, 3H). C{ H} NMR (100 MHz,
CDCl ) δ 197.0, 147.0, 142.9, 141.0, 133.6 (q, J = 32.7 Hz), 129.7,
128.5, 126.3, 125.3 (q, J = 3.7 Hz), 124.5, 39.0, 38.2, 38.0.
+
11.8. HRMS (ESI-TOF) m/z: [M + Na] Calcd for C38
H
58NaO
2
3
5
69.4329 ; Found 569.4330
methyl 2-((2,3-dihydro-1H-inden-2-yl)methyl)acrylate (24)
According to the general procedure. Colorless oil (43.9 mg, 68%)
+
17 3
HRMS (ESI-TOF) m/z: [M + Na] Calcd for C20H F NaO
353.1124; Found 353.1123
(R)-ethyl 2-((2,3-dihydro-1H-inden-2-yl)methyl)-5-(4-
iodophenyl)pentanoate (30)
1
Yield determined by H NMR: 77%. R
f
= 0.40 (Petroleum
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.21 – 7.15 (m,
H), 7.15 – 7.09 (m, 2H), 6.21 (s, 1H), 5.57 (s, 1H), 3.76 (s, 3H),
3.03 (dd, J = 15.2, 7.2 Hz, 2H), 2.69 (dd, J = 14.4, 7.2 Hz, 1H),
1
3
2
According to the general procedure. Colorless oil (48.2 mg, 35%)
1
R
f
= 0.40 (Petroleum ether/EtOAc, 20/1). H NMR (400 MHz,
1
3
1
2
.61 (dd, J = 15.2, 6.8 Hz, 2H), 2.47 (d, J = 7.2 Hz, 2H). C{ H}
NMR (100 MHz, CDCl ) δ 167.8, 143.1, 139.6, 126.2, 125.9,
24.5, 51.9, 38.8, 38.2, 37.8. HRMS (ESI-TOF) m/z: [M + Na]
Calcd for C14 239.1043; Found 239.1043
CDCl ) δ 7.57 (d, J = 8.4 Hz, 2H), 7.16 (dd, J = 8.4, 4.0 Hz, 2H),
3
3
7.14 – 7.08 (m, 2H), 6.90 (d, J = 8.4 Hz, 2H), 4.14 (q, J = 7.2 Hz,
2H), 3.02 (ddd, J = 26.8, 15.6, 7.6 Hz, 2H), 2.55 (dt, J = 13.2, 6.4
Hz, 4H), 2.47 (td, J = 9.2, 4.8 Hz, 1H), 2.43 – 2.34 (m, 1H), 1.93
– 1.83 (m, 1H), 1.71 – 1.63 (m, 1H), 1.62 – 1.54 (m, 3H), 1.53 –
+
1
H
16NaO
2
tert-butyl 2-((2,3-dihydro-1H-inden-2-yl)methyl)acrylate (25)
According to the general procedure. Colorless oil (46.2 mg, 60%)
13
1
1.44 (m, 1H), 1.24 (t, J = 7.2 Hz, 3H). C{ H} NMR (100 MHz,
CDCl ) δ 176.2, 143.2, 143.1, 141.7, 137.4, 130.6, 126.2, 126.2,
124.4, 124.4, 60.3, 44.6, 39.5, 39.0, 38.6, 38.4, 35.3, 32.4, 29.0,
1
Yield determined by H NMR: 69%. R
f
= 0.40 (Petroleum
) δ 7.21 – 7.15 (m,
H), 7.15 – 7.07 (m, 2H), 6.11 (d, J = 1.6 Hz, 1H), 5.48 (d, J = 1.2
Hz, 1H), 3.02 (dd, J = 14.8, 7.2 Hz, 2H), 2.69 (dt, J = 14.0, 7.1 Hz,
H), 2.61 (dd, J = 15.2, 6.8 Hz, 2H), 2.44 (d, J = 6.8 Hz, 2H), 1.50
3
1
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
+
2
14.4. HRMS (ESI-TOF) m/z: [M + H] Calcd for C23
463.1128; Found 463.1131
H28IO
2
1
(
(R)-2-((2,3-dihydro-1H-inden-2-yl)methyl)-5-(4-
iodophenyl)pentanoic acid (31)
1
3
1
s, 9H). C{ H} NMR (100 MHz, CDCl
3
) δ 166.6, 143.2, 141.3,
1
26.2, 124.7, 124.5, 80.6, 38.9, 38.5, 37.9, 28.1. HRMS (ESI-
According to the general procedure. Yellow solid (214.1 mg,
+
1
TOF) m/z: [M + Na] Calcd for C17
281.1513
H
22NaO
2
281.1512; Found
3
85%) M.p. = 80 – 82 °C. H NMR (400 MHz, CDCl ) δ 7.50 (d, J
= 7.6 Hz, 2H), 7.13 – 7.01 (m, 4H), 6.84 (d, J = 7.6 Hz, 2H), 3.05
– 2.87 (m, 2H), 2.55 – 2.44 (m, 4H), 2.44 – 2.34 (m, 2H), 1.91 –
pent-4-yn-1-yl 2-((2,3-dihydro-1H-inden-2-yl)methyl)acrylate
26)
According to the general procedure. Colorless oil (46.0 mg, 54%)
1
3
1
(
1.77 (m, 1H), 1.68 – 1.47 (m, 5H), 1.18 (s, 2H). C{ H} NMR
(100 MHz, CDCl ) δ 142.0, 141.9, 140.5, 136.3, 129.5, 125.2,
123.4, 123.3, 89.9, 43.4, 38.4, 37.8, 37.3, 37.1, 34.2, 31.0, 28.7,
3
1
Yield determined by H NMR: 55%. R
f
= 0.40 (Petroleum
3
1
+
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl ) δ 7.21 – 7.15 (m,
4 2
27.8. HRMS (ESI-TOF) m/z: [M + NH ] Calcd for C21H27INO
2H), 7.15 – 7.09 (m, 2H), 6.21 (s, 1H), 5.58 (s, 1H), 4.26 (t, J =
6.4 Hz, 2H), 3.03 (dd, J = 14.8, 7.2 Hz, 2H), 2.70 (dt, J = 14.0, 7.2
Hz, 1H), 2.62 (dd, J = 15.2, 6.8 Hz, 2H), 2.47 (d, J = 7.2 Hz, 2H),
452.1081; Found 452.1072
ethyl 5-(4-iodophenyl)-2-methylenepentanoate (32)
According to the general procedure. Colorless oil (51.6 mg, 50%)
1
2
6
1
1
2
.32 (td, J = 7.2, 2.4 Hz, 2H), 1.97 (t, J = 2.4 Hz, 1H), 1.91 (d, J =
R
f
= 0.40 (Petroleum ether/EtOAc, 20/1). H NMR (400 MHz,
1
3
1
.8 Hz, 2H). C{ H} NMR (100 MHz, CDCl
3
) δ 167.2, 143.0,
CDCl ) δ 7.59 (d, J = 7.6 Hz, 2H), 6.94 (d, J = 7.6 Hz, 2H), 6.15
3
39.6, 126.2, 125.9, 124.5, 83.0, 69.1, 63.3, 38.8, 38.3, 37.8, 27.6,
(s, 1H), 5.52 (s, 1H), 4.20 (dd, J = 14.0, 6.8 Hz, 2H), 2.58 (t, J =
7.6 Hz, 2H), 2.32 (t, J = 7.2 Hz, 2H), 1.77 (dt, J = 14.4, 7.2 Hz,
+
5.4. HRMS (ESI-TOF) m/z: [M + Na] Calcd for C18
91.1356; Found 291.1355
H20NaO
2
13
1
2H), 1.29 (t, J = 6.8 Hz, 3H). C{ H} NMR (100 MHz, CDCl
3
) δ
2-((2,3-dihydro-1H-inden-2-yl)methyl)-1-(4-
methoxyphenyl)prop-2-en-1-one (27)
According to the general procedure. Colorless oil (52.2 mg, 60%)
167.2, 141.7, 140.5, 137.4, 130.6, 124.7, 90.8, 60.7, 34.9, 31.4,
+
29.9, 14.2. HRMS (ESI-TOF) m/z: [M + H] Calcd for C14H18IO
2
345.0346; Found 345.0344
1
Yield determined by H NMR: 68%. R
f
= 0.40 (Petroleum
ether/EtOAc, 10/1). H NMR (400 MHz, CDCl ) δ 8.12 (d, J =
.5 Hz, 2H), 7.50 – 7.44 (m, 2H), 7.43 – 7.37 (m, 2H), 7.23 (d, J =
.5 Hz, 2H), 6.06 (s, 1H), 5.84 (s, 1H), 4.16 (s, 3H), 3.39 – 3.29
ethyl 5-([1,1':4',1''-terphenyl]-4-yl)-2-methylenepentanoate
(33)
According to the general procedure. White solid (40.1 mg, 54%)
1
3
8
8
1
M.p. = 104 – 106 °C. R
NMR (400 MHz, CDCl
f
= 0.40 (Petroleum ether/EtOAc, 4/1). H
) δ 7.69 – 7.63 (m, 5H), 7.62 (s, 1H),
1
3
1
(m, 2H), 2.99 (d, J = 5.3 Hz, 1H), 2.95 (s, 4H). C{ H} NMR
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 9
7
.56 (d, J = 8.0 Hz, 2H), 7.45 (t, J = 7.6 Hz, 2H), 7.34 (t, J = 7.2
ACKNOWLEDGMENT
We are grateful to the National Natural Science Foundation of
China (21732002, 21672117, 21772104, 31760527) for generous
financial support for our programs.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Hz, 1H), 7.27 (d, J = 8.0 Hz, 2H), 6.17 (s, 1H), 5.55 (s, 1H), 4.21
(q, J = 7.2 Hz, 2H), 2.69 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.6 Hz,
1
3
1
2
H), 1.92 – 1.79 (m, 2H), 1.30 (t, J = 7.2 Hz, 3H). C{ H} NMR
) δ 167.3, 141.4, 140.8, 140.7, 140.0, 139.9,
(100 MHz, CDCl
3
1
3
38.2, 129.0, 128.8, 127.5, 127.4, 127.3, 127.1, 127.0, 124.7, 60.7,
5.1, 31.6, 30.1, 14.3. HRMS (ESI-TOF) m/z: [M + H] Calcd for
REFERENCES
+
(1) (a) Yamamoto, Y.; Asao, N. Selective Reactions Using Allylic
C
26
H
27
O
2
371.2006; Found 371.2003
ethyl 2-methylene-5-(4-(phenylethynyl)phenyl)pentanoate (34)
According to the general procedure. Colorless oil (36.8 mg, 58%).
Metals. Chem. Rev. 1993, 93, 2207. (b) Yus, M.; González-
Gómez, C-C.; Foubelo, F. Diastereoselective Allylation of
Carbonyl Compounds and Imines: Application to the Synthesis of
Natural Products. Chem. Rev. 2013, 113, 5595.
1
R
f
= 0.40 (Petroleum ether/EtOAc, 4/1). H NMR (400 MHz,
CDCl ) δ 7.47 – 7.41 (m, 2H), 7.37 (d, J = 8.0 Hz, 2H), 7.30 –
.20 (m, 3H), 7.08 (d, J = 8.0 Hz, 2H), 6.07 (s, 1H), 5.44 (s, 1H),
.12 (q, J = 7.2 Hz, 2H), 2.56 (t, J = 7.6 Hz, 2H), 2.26 (t, J = 7.6
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(2) (a) Gerster, M.; Audergon, L.; Moufid, N.; Renaud, P. Simple
7
4
and Efficient Stereocontrol of Radical Allylations of β-hydroxy
Esters. Tetrahedron Lett, 1996, 37, 6335. (b) Diter, P.; Warchol,
T.; Wakselman, C.; Blazejewski, J.- C. Radical Allylation of
Trifluoromethylated Xanthates: Use of DEAD for Removing the
Allyltributyltin Excess. Tetrahedron Lett. 2001, 42, 859. (c) Ryu,
I.; Kreimerman, S.; Niguma, T.; Minakata, M.; Komatsu, M. Luo,
Z.; Curran, D. P. Synthesis of Perfluorinated Allylic Compounds
by Radical Allylation and Their Purification over Fluorous
Reverse-phase Silica. Tetrahedron Lett. 2001, 42, 947. (d)
Chowdhry, M. (I).; Horton, P. N.; Hursthouse, M. B.; Wood, M.
E. α-Allylation of α-Amino Acids via 1,5-Hydrogen Atom
Transfer. Tetrahedron Lett. 2009, 50, 3400. (e) Fhal, A. R.;
Renaud, P. Enantioselective Radical Allylation of α-Iodoamides
Using Chiral Aluminum Based Lewis Acids. Tetrahedron Lett.
1997, 38, 2661. (f) Keck, G.E.; Yates, J. B. Carbon-carbon Bond
Formation via the Reaction of Trialkylallylstannanes with Organic
Halides. J. Am. Chem. Soc. 1982, 104, 5829. (g) Sibi, M. P.;
Rheault, T. R. Higher Selectivity at Higher Temperatures! Effect
of Precursor Stereochemistry on Diastereoselectivity in Radical
Allylations. Insight into the Role of the Lewis Acid. J. Am. Chem.
Soc. 2000, 122, 8873. (h) Cardinal-David, B.; Guérin, B.;
Guindon, Y. Synthesis of Tertiary and Quaternary Stereogenic
13
1
Hz, 2H), 1.78 – 1.65 (m, 2H), 1.21 (t, J = 7.2 Hz, 3H). C{ H}
NMR (100 MHz, CDCl ) δ 167.2, 142.6, 140.6, 131.6, 131.6,
128.5, 128.4, 128.1, 124.7, 123.5, 120.7, 89.6, 88.9, 60.7, 35.4,
3
+
3
1.5, 29.9, 14.3. HRMS (ESI-TOF) m/z: [M + Na] Calcd for
341.1512; Found 341.1511
-(2,2-diphenylvinyl)-2,3-dihydro-1H-indene (36)
According to the general procedure. White solid (6.0 mg, 7%)
22 2
C H22NaO
1
9
2
1
M.p. = 63 – 65 °C. R
(400 MHz, CDCl ) δ 7.39 – 7.32 (m, 2H), 7.32 – 7.26 (m, 2H),
7.26 – 7.22 (m, 5H), 7.21 – 7.19 (m, 1H), 7.18 – 7.13 (m, 2H),
7
2
1
1
1
f
= 0.50 (Pure petroleum ether). H NMR
3
.12 – 7.08 (m, 2H), 6.20 (dd, J = 10.0, 2.8 Hz, 1H), 3.21 (dt, J =
4.0, 8.0 Hz, 1H), 3.03 (dd, J = 15.2, 8.0 Hz, 2H), 2.87 (dd, J =
1
3
1
3
5.2, 8.4 Hz, 2H). C{ H} NMR (100 MHz, CDCl ) δ 143.1,
42.4, 141.5, 140.3, 133.6, 129.9, 128.5, 128.2, 127.9, 127.3,
27.1, 127.1, 126.3, 124.4, 40.7, 40.5. HRMS (ESI-TOF) m/z: [M
+
+
H] Calcd for C23
H
21 297.1638; Found 297.1633
benzyl 2-methylenehept-6-enoate (37)
According to the general procedure. Colorless oil (5.0 mg, 7%)
1
Yield determined by H NMR: 10%. R
f
= 0.40 (Petroleum
ether/EtOAc, 40/1). H NMR (400 MHz, CDCl ) δ 7.37 – 7.20 (m,
H), 6.13 (s, 1H), 5.73 (ddt, J = 16.8, 10.0, 6.4 Hz, 1H), 5.49 (s,
H), 5.13 (s, 2H), 4.91 (dd, J = 20.4, 13.6 Hz, 2H), 2.35 – 2.21 (m,
1
3
5
1
2
Centers:ꢀ
A Diastereoselective Tandem Reaction Sequence
13
1
Combining Mukaiyama and Free Radical-Based Allylation. J.
Org. Chem. 2005, 70, 776.
H), 2.05 – 1.94 (m, 2H), 1.52 – 1.47 (m, 2H). C{ H} NMR
) δ 167.1, 140.5, 138.4, 136.1, 128.6, 128.1,
128.0, 125.2, 114.8, 66.4, 33.2, 31.3, 27.6. HRMS (ESI-TOF) m/z:
(100 MHz, CDCl
3
(3) (a) Zhou, Q.-Q.; Zou, Y.-Q.; Lu, L.-Q.; Xiao, W.-J. Visible-
+
Light-Induced Organic Photochemical Reactions through Energy-
Transfer Pathways. Angew. Chem., Int. Ed. 2019, 58, 1586. and
references cited therein. (b) Xuan, J.; Hea, X.-K.; Xiao, W.-J.
Visible light-promoted ring-opening functionalization of three-
membered carbo- and heterocycles. Chem. Soc. Rev., 2020, 49.
DOI:10.1039/c9cs00523d (c) Chen, Y.-Y,; Lu, L.-Q.; Yu, D.-G.;
Zhu, C.-J.; Xiao, W.-J. Visible light-driven organic photochemical
synthesis in China. Sci. China Chem., 2019, 62, 24 (d) Cai, B.-G.;
Xuan, J.; Xiao, W.-J. Visible light-mediated CP bond formation
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Feng, Z.‐J.; Deng, Q.‐H.; Chen, J.‐R.; Lu, L.‐Q.; Xiao, W.‐J.;
Alper, H. Redox‐Neutral α‐Allylation of Amines by Combining
Palladium Catalysis and Visible‐Light Photoredox Catalysis.
Angew. Chem., Int. Ed. 2015, 54, 1625 (f) Feng, Z.-J.; Zeng, T.-
T.; Xuan, J.; Liu, Y.-H.; Lu, L.-Q.; Xiao, W.‐J. C–H allylation of
N-aryl-tetrahydroisoquinolines by merging photoredox catalysis
with iodide catalysis. Sci. China Chem. 2016, 59, 171 (g) Shukla,
G.; Alam, T.; Srivastava, H. K.; Kumar, R.; Patel, B. K. Visible-
Light-Mediated Ir(III)-Catalyzed Concomitant C3 Oxidation and
C2 Amination of Indoles. Org. Lett. 2019, 21, 3543 (h) Alam, T.;
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[M + H] Calcd for C15
19 2
H O 231.1380; Found 231.1382
benzyl 2-methylenenon-8-enoate (38a) benzyl 4-cyclopentyl-2-
methylenebutanoate (38b)
According to the general procedure. Colorless oil (35.8 mg, 47%)
1
Yield determined by H NMR: 54%. R
f
= 0.40 (Petroleum
) δ 7.45 – 7.29 (m,
5H), 6.18 (d, J = 4.4 Hz, 0.92H), 5.80 (ddd, J = 17.0, 6.7, 3.5 Hz,
1
ether/EtOAc, 20/1). H NMR (400 MHz, CDCl
3
0
1
1
3
.75H), 5.55 (s, 1H), 5.20 (s, 2H), 4.96 (dd, J = 21.8, 13.7 Hz,
.5H), 2.38 – 2.27 (m, 2H), 2.03 (dd, J = 13.7, 6.8 Hz, 1.56H),
.81 – 1.72 (m, 0.86H), 1.51 – 1.44 (m, 2.17H), 1.42 – 1.29 (m,
1
3
1
.21H), 1.26 (s, 0.34H), 1.09 (s, 0.65H). C{ H} NMR (100
) δ 167.2, 141.1, 140.8, 139.0, 136.2, 128.6, 128.1,
MHz, CDCl
3
128.0, 124.9, 124.7, 114.3, 66.4, 39.7, 35.0, 33.7, 32.6, 31.8, 31.2,
28.7, 28.2, 25.2. HRMS (ESI-TOF) m/z: [M + Na] Calcd for
C H22NaO 259.1693 ; Found 259.1692
17 2
+
ASSOCIATED CONTENT
Supporting Information Available: Experimental procedures
and spectroscopic data for all new compounds. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
1
0.1021/acs.orglett.0c01235
Corresponding Author
(4) (a) Duan, Y.; Zhang, M.; Ruzi, R.; Wu, Z.; Zhu, C. The Direct
*
E-mail: wangqm@nankai.edu.cn.
Decarboxylative Allylation of N-arylglycine Derivatives by
Photoredox Catalysis. Org. Chem. Front. 2017, 4, 525. (b)
Ramirez, N. P.; Lana-Villarreal, T.; Gonzalez-Gomez, J. C. Direct
Notes
The authors declare no competing financial interest.
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The Journal of Organic Chemistry
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