Visible-light-induced 1,2-alkylarylation of alkenes with a-C(sp3)–H bonds of acetonitriles involving neophyl rearrangement under transition-metal-free conditions

Article abstract of DOI:10.1016/j.tetlet.2018.11.025

An efficient visible-light-induced difunctionalization of alkenes with a-C(sp³)–H bonds of nitriles is described for the constructing of diverse 5-oxo-pentanenitriles under transition-metal-free conditions. This protocol proceeds via the functi

Full text of DOI:10.1016/j.tetlet.2018.11.025

Accepted Manuscript
Visible-light-induced 1,2-alkylarylation of alkenes with a-C(sp3)–H bonds of
acetonitriles involving neophyl rearrangement under transition-metal-free con-
ditions
Qiao-Lin Wang, Zan Chen, Cong-Shan Zhou, Bi-Quan Xiong, Pan-Liang
Zhang, Chang-An Yang, Yu Liu, Quan Zhou
PII:
S0040-4039(18)31353-4
https://doi.org/10.1016/j.tetlet.2018.11.025
TETL 50410
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
28 September 2018
24 October 2018
9 November 2018
Please cite this article as: Wang, Q-L., Chen, Z., Zhou, C-S., Xiong, B-Q., Zhang, P-L., Yang, C-A., Liu, Y., Zhou,
Q., Visible-light-induced 1,2-alkylarylation of alkenes with a-C(sp3)–H bonds of acetonitriles involving neophyl
rearrangement under transition-metal-free conditions, Tetrahedron Letters (2018), doi: https://doi.org/10.1016/
j.tetlet.2018.11.025
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Graphical Abstract
Visible-light-induced 1,2-alkylarylation of
alkenes with a-C(sp3)–H bonds of
acetonitriles involving neophyl
rearrangement under transition-metal-free
conditions
Leave this area blank for abstract info.
Qiao-Lin Wang, Zan Chen, Cong-Shan Zhou, Bi-Quan Xiong, Pan-Liang Zhang, Chang-An Yang, Yu Liu,*
Quan Zhou*
O
R
Eosin Y
CN
Ar1
cyclobutanone O-(4-(trifluoromethyl)benzoyl) oxime
HO
Ar1
+
CH3CN, Ar, 100 oC, 5 W blue LED light
Ar2
H
CN
Ar2
R
good functional group tolerance
31 examples up to 85% yield
tr ansition-metal-f ree
strong-oxidant-free

1
Tetrahedron Letters
Visible-light-induced 1,2-alkylarylation of alkenes with a-C(sp3)–H bonds of
acetonitriles involving neophyl rearrangement under transition-metal-free conditions
Qiao-Lin Wang, Zan Chen, Cong-Shan Zhou, Bi-Quan Xiong, Pan-Liang Zhang, Chang-An Yang, Yu
Liu, Quan Zhou
Department of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient visible-light-induced difunctionalization of alkenes with a-C(sp3)–H bonds of
nitriles is described for the constructing of diverse 5-oxo-pentanenitriles under transition-metal-
free conditions. This protocol proceeds via the functionalization of C(sp3)−H bond and radical
addition/intramolecular 1,2-aryl migration processes, which features a wide scope of substituted
α,α-diaryl allylic alcohols. The results of kinetic isotope experiments show that the cleavage of
C(sp3)–H bond of acetonitriles is a rate-limiting step.
Available online
Keywords:
1,2-Alkylarylation
Visible light photoredox catalysis
C–H functionalization
Acetonitriles
2009 Elsevier Ltd. All rights reserved.
α,α-Diaryl allylic alcohols
1. Introduction
alkyl radicals mainly generated from cleavage of C–X, C–C or
C(sp3)–H bonds. However, 1,2-alkylarylation of α,α-diaryl allylic
alcohol with C(sp3)–H bonds in alcohols, ethers, alkanes, nitriles,
amines have made great progress. In 2016, Cheng’s group
developed the peroxide facilitated [3+2] cyclization of α,α-diaryl
allylic alcohols with sec-alcohols via neophyl rearrangements
under transition-metal-free conditions.9c Ji’s group presented the
novel and straightforward strategy for the synthesis of α-aryl-β-
alkylated ketones by peroxide initiated difunctionalization of aryl
allylic alcohols with ethers (open-chain and cyclic ethers)
without any metal catalyst, which formed two new carbon–
carbon bonds in one step.9d In 2014, Tu and co-workers described
the Ni-mediated difunctionalization of inactive alkenes with the
α-C(sp3)–H bonds of N, N-substituted amides for the building of
α-aryl-γ-amine ketones.9g Li and Ji groups reported the oxidative
difunctionalization of allylic alcohols with the C(sp3)–H bonds of
acetonitriles,9a,9b ketones9e or alkanes9f. Unfortunately, most of
these conversions exist the defects of harsh reaction conditions,
such as expensive catalysts, high temperatures, strong oxidants or
limitation to the start materials. Hence, a simple and economic,
environmentally benign method for difunctionalization of α,α-
diaryl allylic alcohols with C(sp3)–H bonds is lacking.
Recently, the direct C–H functionalization for the constructing
of carbon-carbon bonds or carbon-hetero bonds has been even
more attractive strategy for its playing an important role in
building complex molecules.1 As a result, many chemists pay
their attention to the development of new strategy for radical
C(sp3)–H functionalization.2,3 Especially, significant advances
have been made in selective activation of C(sp3)–H bond in
alcohols, ethers, alkanes, amines and other activated compounds.4
However, it is a more taxing target for functionalization of
C(sp3)–H in simple nitriles under mild conditions.
Nitriles, commonly exist in bioactive molecules and natural
products, are important synthetic intermediates in organic
synthesis, agricultural and pharmaceutical chemistry, as well as
polymers and materials science.5 Thus, the preparation and
utilization of organonitriles have become one of the most popular
and interesting topics in organic and biological chemistry.6
The difunctionalization of alkenes has become a class of
powerful and efficient chemical transformation in organic
synthesis, by that two functional groups can be contemporaneous
introduced into a double bond.7 In recent years, aryl allylic
alcohols were proved to be practicable substrates for
difuctionalization of alkenes,8–16 which deliver a series of α-aryl-
β-substituted ketones via 1,2-migration. Through this method, a
series of radicals such as alkyl,9 acyl,10 CF3,11 N3,12 S,13 P,14 Si,15
Se-contained16 radicals, were introduced to the radical-mediated
Recently, organic chemists have paid close attention to the
visible-light photoredox catalysis for the view of economy and
environment-friendliness.17 Particularly, organic photosensitizers,
usually organic small molecular dyes, which have been widely
used as photocatalysts in pharmaceutical and organic synthesis.18
Eosin Y, a common photocatalyst, can avoid metal remain in the
difunctionalization of aryl allylic alcohols (Scheme 1, a). The
———
 Corresponding authors.
E-mail addresses: lyxtmj_613@163.com (Y. Liu), mmzhq1985@126.com (Q. Zhou).

2
Tetrahedron
final products. Additionally, eosin Y is greener than the
additive and Eosin Y (5 mol%) as photocatalyst, under an argon
transition-metal based photocatalysts.18d–k According to the
previous researches on α,α-diaryl allylic alcohols and our works
on the development of visible-light phororedox catalysis,19 we
also present the first visible-light-induced difunctionalization of
α,α-diaryl allylic alcohols with α-C(sp3)–H bonds of nitriles for
the building of 5-oxo-pentanenitriles under transition-metal-free
and oxidant-free conditions with high efficiency and selectivity.
atmosphere at 100 C by irradiation with a 5 W blue LED light
o
for 24 h, afforded the target α-aryl-γ-cyano ketone 3aa in 78%
yield (entry 1). Firstly, we examined the effect of additives, a
series of additives such as cyclobutanone O-(4-nitrobenzoyl)
oxime (additive II), cyclobutanone O-benzoyl oxime (additive
III), and 4-MeOC6H4N2BF4 (additive IV)19a,c,d were conducted
(entries 2–4). The results indicated that all of the additives could
afford the desired product 3aa, albeit with lower yields (entries
2–4). However, the 4-MeOC6H4N2BF4, an excellent radical
initiator, could not improve the yield of this 1,2-alkylarylation
process (entry 4). Remarkably, the reaction could not occur
without additional additive (entry 5). Next, the transition-metal
photocatalysts Ir(ppy)3 or Ru(bpy)2Cl2 were also tested, the
results revealed that they were failed in improving the reaction
yield (entries 6–7 vs entry 1). Additionally, the transformation
could not occur without photocatalyst or visible-light irradiation
(entries 8–9). The amount of Eosin Y also effected the reaction
and 5 mol% was the best choice according to the reaction yields
(entries 10–11 vs. entry 1). Other solvents (toluene, THF,
dichloromethane) were also tested in presence of MeCN (5
equiv) as the reactant, and using THF as solvent could afford the
target product in 68% yield (entries 12–14). Unfortunately, other
light sources such as 3 W blue LED light, 36 W compact
fluorescent light or sunlight showed less efficient than 5 W blue
LED light (entries 15–17 vs. entry 1). The reaction performed at
80 oC or 120 oC only afforded target product 3aa in 63% or 65%
yield respectively (entries 18–19). Furthermore, the presented
transformation was easily scaled up to 1 gram in moderate yield
(entry 20).
a) Previous work:
O
HO
Ar1
transition-metal/oxidant
Ar1
R
R
+
Ar2
Ar2
R = alkyl, acyl, CF3-, N3-, S-, P-, Si-, Se-contained groups
b) This work: visible-light-mediated difuncitonalization of allylic alcohols
R
O
visible light
HO
Ar1
CN
Ar1
+
Ar2
transition-metal-fr ee
oxidant-free
H
CN
Ar2
R
Scheme 1. Oxidative radical functionalization of allylic alcohols.
2. Results and Discussion
Based on the visible-light photoredox catalysis strategy, we
initially chose 1,1-diphenylprop-2-en-1-ol (1a) and acetonitrile
(2a) as the model substrates to optimize the reaction conditions
(Table 1). Firstly, the α,α-diaryl allylic alcohol 1a (0.2 mmol)
reacted with acetonitrile 2a (2 mL) in presence of cyclobutanone
O-(4-(trifluoromethyl)-benzoyl) oxime (additive I, 1.5 equiv) as
Table 1
Optimization of the reaction conditions a
With these established conditions, we set out to research the
substrates scope of allylic alcohols (1) and nitriles (2) (Table 2).
Firstly, a series of nitriles, including pentanenitrile (2b), 2-
methoxyacetonitrile (2c), phenylacetonitrile (2d) or malononitrile
(2e), were examed by using 1,1-diphenylprop-2-en-1-ol (1a),
cyclobutanone O-(4-(trifluoromethyl)benzoyl) oxime (additive I)
and Eosin Y (products 3ab–ae). To our delighted, pentanenitrile
(2b) was suitable for this transformation, affording the target
product 3ab in 70% yield. However, utilizing 2-
methoxyacetonitrile (2c) or 2-phenylacetonitrile (2d) in the 1,2-
alkylarylation failed to construct 5-oxo-pentanenitriles 3 (3ac and
3ad), due to the hydrogen abstraction of 2c and 2d was difficult.
Furthermore, malononitrile (2e) could delivered the desired
product 3ae in good yield under the optimal conditions (3ae).
Next, a range of symmetric α,α-diaryl allylic alcohol 1 with
acetonitrile 2a were tested under the optimal conditions. Allylic
alcohols (1b–g), with the same aryl groups on the α position,
such as aryl rings with electron-donating groups (Me or OMe) or
electron-withdrawing groups (F, Cl or Br) all transformed
smoothly to generate the desired products 3 in moderate to
excellent yields (3ba–ga). On the other hand, allylic alcohols
with two different aryl rings were proved suitable for this
difunctionalization and afforded the desired corresponding
products 3 in moderate to good yields (3ha–xa). The results
showed that the migration activities of aryl groups depended on
the electronic effects and sterical hindrance properties of
substituents on the aryl groups: according to the electronic effect,
the electron-deficient aryl groups were more easily proceed
migration than electron-rich ones, and according to the steric
hindrance property, the migration reactivity order of aryl groups
is para > meta > ortho. Actually, the electronic effects and
sterical hindrance properties of substituents on the aryl groups
worked together. Interestingly, when utilizing 1-(4-
fluorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-ol 1h in this
transformation gave two isomers 3ha and 3ha’ (5 : 1) and the
isomers could be easily isolated by silica column
O
Eosin Y, additive
HO
Ph
CN
+
H
CN
CH3CN, Ar, 100 oC
5 W blue LED light
Ph
Ph
Ph
3aa
1a
2a
Entry
1
Variation from the standard conditions
None
Additive II instead of additive I
Additive III instead of additive I
Additive IV instead of additive I
Without additive
Ir(ppy)3 instead of Esoin Y
Ru(bpy)2Cl2 instead of Eosin Y
Without Eosin Y
Without additional light
Eosin Y (2 mol %)
Eosin Y (10 mol %)
Toluene instead of MeCN
THF instead of MeCN
DCM instead of MeCN
None
Yield %
78
52
43
18
0
71
63
0
2b
3c
4d
5
6
7
8c
9d
0
10
11
12e
13e
14e
15f
16g
17h
18
19
67
77
28
68
23
70
64
52
63
65
72
None
None
At 80 oC
At 120 oC
20i
a
None
Reaction conditions: 1a (0.2 mmol), MeCN 2a (2 mL), Eosin Y (5
mol %), cyclobutanone O-(4-(trifluoromethyl)benzoyl) oxime (additive I, 1.5
equiv) at 100 oC under an argon atmosphere and 5 W blue LED light for 24 h.
b additive II: cyclobutanone O-(4-nitrobenzoyl) oxime.
c additive III: cyclobutanone O-benzoyl oxime.
d additive IV: 4-MeOC6H4N2BF4.
e
MeCN (5 equiv, 1 mmol).
f 3 W blue LED light instead of 5 W blue LED light.
g 36 W compact fluorescent light instead of 5 W blue LED light.
h sunlight instead of 5 W blue LED light.
i 1a (1.0 g, 4.76 mmol) and MeCN 2a (10 mL) for 48 h.

3
a
chromatography. Alcohols 1i–k have an unsubstituted aryl ring
and a 2-substitued ary ring on the α position, gave the
unsubstituted aryl ring migrating α-aryl-γ-cyano ketones 3ia–ka
as the major products. In these transformation, the steric effects
overruled the electronic effects due to the steric hinderance in the
formation of spiro intermediate and always afforded the
migration product with the unsubstituted-Ar groups. However,
allylic alcohol 1l with an unsubstituted aryl ring and a m-Me-
substituted aryl ring on the α position underwent the 1,2-
alkylarylation providing the Ph-migration product (3la) and m-
Me-Ph-migration product (3la’) in 1 : 1, and the total yield was
81%, which combined the effects of the electronic effects and
sterical hindrance acting together. Alcohol 1m with an
unsubstituted aryl ring and a m-CF3-substituted aryl ring on the α
position took place the m-CF3-Ph group migration as the major
process, affording the target product 3ma in 74% yield. A similar
rearrangement was suitable for allylic alcohols 1n–r, which with
an unsubstituted α-aryl ring and a 4-substituted α-aryl ring, the
electronic effects were more important than the steric effects so
that the electron-withdrawing and relatively neutral Ar groups
migrated while electron-donating groups (OMe or Me) did not
migrate (3na–ra).
Reaction conditions: 1 (0.2 mmol), 2 (2 mL), Eosin Y (5 mol%),
cyclobutanone O-(4-(trifluoromethyl)benzoyl) oxime (additive I, 1.5 equiv)
at 100 oC under an argon atmosphere and 5 W blue LED light for 24 h.
b
The d.r. value ratio of product 3ab was detected by GC-MS analysis of
the crude product.
c The ratio of 3 and its isomer was determined by 1H NMR analysis of the
isolated product, only major product was shown.
d The ratio of 3 and its isomer was determined by GC-MS analysis of the
crude product, only major product was shown.
However, allylic alcohols 1s–u with two substituents on one
aryl group, could go through the 1,2-alkylarylation and
selectively furnished the major products 3sa–ua in good yields.
As for allylic alcohols 1s, the electronic effects and sterical
hindrance properties of the two Me groups worked together so
that this reaction afforded the unsubstituted-Ar groups migrated
product as the major product (3sa). As for allylic alcohols 1t, the
electronic effects overruled the steric effects and afforded the
migration product with the difluro-substituted-Ar groups (3ta).
As for allylic alcohols 1u, the steric effects were more important
than the electronic effects, provided the Ph-migration product as
the major product (3ua). Furthermore, substrate 1v was viable in
the construction of 5-oxo-pentanenitriles, giving the phenyl group
migrated product 3va in 80% yield. To our surprise, substrates
1w and 1x could go through the 1,2-migration process and give
the solely targeted products 3wa and 3xa, respectively, due to the
relative lower aromaticity of pyridinyl groups. However, the
allylic alcohols 1y–z with an α-Ph and an α-alkyl group were not
compatible for this reaction system (3ya–za). Notably, the 1,2-
migration process was suitable for 2-(pyridin-4-yl)but-3-en-2-ol
(1aa), proceed via the migration of pyridin-4-yl group and
afforded the sole product 3aaa in 45% yield, due to the nitrogen
atom of pyridine could afford a more stable intermediate in these
transformations.
Control experiments was conducted by using acetone 4 instead
of nitrile 2 to react with allylic alcohols 1a under the standard
conditions. We were pleased to find that the corresponding
products 5 were obtained in moderate yields (eq 1, Scheme 2).
Previously studies showed that this transformation went through
a radical process.9a,b,19a,d,e,20 Several control experiments were
proceeded to demonstrate the reaction pathway. The allylic
alcohol 1a reacted with nitrile 2a under the standard conditions in
the presence of TEMPO, hydroquinone or BHT (2,6-di-tert-
butyl-4- methylphenol), and the reaction was almost completely
suppressed (eq 2, Scheme 2). The results indicated that this
difunctionalization may proceed via a radical pathway. From the
result of kinetic isotope effect (kH/kD = 12.3), it is believed that
the cleavage of C(sp3)–H bonds in acetonitriles is a rate-limiting
step, by using 1a reacted with 2a and 2a-D3 (eq 3, Scheme 2).9e
Table 2 Reaction Scope of alkenes (1) with nitriles (2).a
O
R
HO
Ar1
CN
Eosin Y (5 mol %), additive I
CH3CN, Ar, 100 o
Ar1
Ar2
+
H
CN
Ar2
3
R
C
5 W blue LED light
2
1
O
O
R1 = R2 = Me, 3ba, 82%
CN
Ph
CN
R1 = R2 = OMe,
, 84%
3ca
Ph
R
R1 = R2 = F, 3da, 85%
R1 = R2 = Cl, 3ea, 84%
R1 = R2 = Br, 3fa, 77%
R = CH2CH2CH3, 3ab, 70% (1:1)b
R = OMe, 3ac, trace
R1
3ad
R = Ph,
R = CN, 3ae, 85%
, trace
R2
R
O
O
O
CN
CN
CN
MeO
R = Me, 3ia, 75% (>99:1)d
F
c
3ja
, 72% (4:1)
R = F,
3ha, 80% (5:1)
R = Cl, 3ka, 76% (>99:1)d
3ga
, 71%
O
O
O
CN
CN
CN
R1
R2
R
c
3na
R2 = Ph, 3pa, 79% (17:3)d
c
R1 = OMe,
, 80% (5:1)
3la
R = Me,
, 81% (1:1)
R = CF3, 3ma, 74% (4:1)c
d
R1 = Me, 3oa, 83% (2:1)c
R2 = F,
, 80% (15:1)
3qa
R2 = Cl, 3ra, 82% (20:1)d
O
Cl
O
O
CN
CN
CN
F
O
O
O
HO
Ph
Eosin Y (5 mol %), Additve I
CH3CN, Ar, 100 o
Cl
(1)
+
Ph
Ph
Ph
F
C
3sa, 80% (2:1)c
3ta, 73% (9:1)c
3ua, 73% (7:3)c
Ph
5 W blue LED light
1a
4
5
O
, 66%
O
O
CN
CN
O
CN
I
Eosin Y (5 mol %), Additve
HO
Ph
CN
+
CH3CN, Ar, 100 o
C
H
CN
Ph
N
(2)
(3)
Ph
5 W blue LED light
Radical Inhibitor
N
1a
2a
3aa, trace
3va, 80% (>99:1)d
3wa
d
d
, 72% (>99:1)
3xa
, 70% (>99:1)
Radical Inhibitor = T EMPO, hydroquinone or BHT
O
O
O
O
CH3CN
2a
+
CD3CN
2a-D3
CN
CN
CN
I
HO
Ph
Eosin Y (5 mol %), Additve
CH3CN, Ar, 100 o
CN
H(D)
+
Ph
Ph
C
Ph H(D)
5 W blue LED light
kH/D = 12.3
1a
3aa + 3aa-D2 = 68%
N
3ya,0%
3za, 0%
3aaa, 45%
Scheme 2. Control experiments.
According to the experiment results and literature reports,8–20
plausible mechanism is presented in Scheme 3. Photocatalyst
a

4
Tetrahedron
Eosin Y is being photoexcited by blue LED light, and converts
and 100 MHz, respectively. The chemical shifts are given in parts
per million (ppm) on the delta (δ) scale. High-resolution mass
spectra (HRMS) were obtained on an Agilent mass spectrometer
using ESI-TOF (electrospray ionization-time of flight).
into strong reductant Eosin Y*.18 Then, this Eosin Y* undergoes
reductive quenching by O-(4-(trifluoromethyl)benzoyl) oxime to
give the iminyl radical A and Eosin Y•+ radical cation via single
electron transfer (SET).
4.2 General procedure.
H
OR
N
CN
N
To a Schlenk tube were added 1 (0.2 mmol), 2 (1.5 eqiuv, 0.3
mmol), Eosin
CN
C
C-C single
bond cleavage
CN
-OR
Y
(5 mol%, 0.004 mmol), additive
I
B
CN
A
SET
HO
(cyclobutanone O-(4-(trifluoromethyl)benzoyl) oxime, 1.5 equiv,
0.3 mmol), CH3CN (2 mL). Then the mixture was stirred at 100
oC (oil bath temperature) in argon atmosphere (1 atm) under 5 W
blue LED light for 24 h until complete consumption of starting
material as monitored by TLC and GC-MS analysis. After the
reaction was finished, the reaction mixture was washed with
brine. The aqueous phase was re-extracted with EtOAc (3 × 10
mL). The combined organic extracts were dried over Na2SO4 and
concentrated in vacuum. The residue was purified by silica gel
flash column chromatography (hexane/ethyl acetate = 5 : 1 to 3 :
1) to afford the desired products 3.
Ph
Eosin Y *
Ph
1a
+
Eosin Y
Redox-neutral Cycle
HO
Ph
CN
hv
Ph
D
1,5-ipso
cyclizaiton
T
E
S
OH
Esoin Y
HO
CN
1,2-aryl
migration
CN
Ph
Ph
OH
F
E
CN
+
Ph
Ph
O
G
Acknowledgments
RO-
-ROH
CN
Ph
Ph
We thank the Scientific Research Fund of Education
Department of Hunan Provincial (No. 16A087), Natural Science
Foundation of Hunan Province (No. 2018JJ3208) and National
Natural Science Foundation of China (No. 21602056) for
financial support.
3aa
Scheme 3. Proposed mechanism.
The iminyl radical A undergoes a ring-opening homolytic C–C
single bond cleavage, and generates a unstable cyanoalkyl radical
B.20 Then, hydrogen abstraction of 2a by unstable cyanoalkyl
radical B produces a more stable cyanomethyl radical C.
Therefore, the concentration of cyanomethyl radical C is much
higher than that of cyanoalkyl radical B probably due to their
stability. Next, radical addition of cyanomethyl radical C to the
carbon–carbon double bond of allylic alcohols furnishes a new
alkyl radical intermediate D. Within intermediate D,
intramolecular 5-ispo cyclization provides spiro[2,5]octadienyl
radical E, follows by 1,2-aryl migration to give benzyl radical
intermediate F. Subsequently, radical F is oxidized by the
oxidizing Eosin Y•+ species to afford the carbocation intermediate
G with regeneration of Eosin Y, closing the photocatalytic cycle.
Finally, a base-mediated deprotonation of the carbocation
intermediate G by RO-, which resulted from the fragmentation of
O-(4-(trifluoromethyl)benzoyl) oxime, gives the 5-oxo-
pentanenitrile 3aa and ROH.
Supplementary Material
Supplementary data associated with this article can be found in
the online version.
References and notes
1. (a) Chen X, Engle K-M, Wang D-H, Yu J-Q. Angew Chem Int Ed. 2009;
48:5094–5115;
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Front. 2018; 5:998–1002;
(c) Chen K, Li X, Zhang S-Q, Shi B-F. Org Chem Front. 2016; 3:204–
208;
(d) Yin X-S, Li Y-C, Yuan J, Gu W-J, Shi B-F. Org Chem Front. 2015;
2:119–123;
(e) Liu B, Zhang Z-Z, Li X, Shi B-F. Org Chem Front. 2016; 3:897–900;
(f) Rao W-H, Shi B-F. Org Chem Front. 2016; 3:1028–1047;
(g) Xie Z-Q, Peng J-L, Zhu Q. Org Chem Front. 2016; 3:82–86;
(h) Xiong Z, Wang J, Wang Y-H, Luo S, Zhu Q, Org Chem Front. 2017;
4:1768–1771.
3. Conclusion
In conclusion, we have described the first visible-light-
mediated difunctionalization of α,α-aryl allylic alcohols with the
α-C(sp3)–H bonds of nitriles under transition-metal-free and
oxidant-free conditions, during which two new carbon-carbon
bonds were formed in this transformation via a C(sp3)–H bond
functionalization and 1,2-aryl migration process. This
difunctionalization of alkenes avoids limitations commonly
associated with transition-metal and strong oxidant mediated
C(sp3)–H bond activation. The further applications of the
developed method in synthesis of bioactive compounds and
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6
Tetrahedron
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7
Highlight
 The 1,2-alkylarylation occurs under
transition-metal-free and oxidant-free
conditions.
 A variety of improtant 5-oxo-
pentanenitriles were obtained.
 The results proved that the cleavage of
C(sp3)–H bond of acetonitrile is a rate-
limiting step.

8
Tetrahedron
Graphical Abstract
Leave this area blank for abstract info.
Visible-light-induced 1,2-alkylarylation of
alkenes with a-C(sp3)–H bonds of
acetonitriles involving neophyl
rearrangement under transition-metal-free
conditions
Qiao-Lin Wang, Zan Chen, Cong-Shan Zhou, Bi-Quan Xiong, Pan-Liang Zhang, Chang-An Yang, Yu Liu,*
Quan Zhou*
O
R
Eosin Y
CN
Ar1
cyclobutanone O-(4-(trifluoromethyl)benzoyl) oxime
HO
Ar1
+
CH3CN, Ar, 100 oC, 5 W blue LED light
Ar2
H
CN
Ar2
R
good functional group tolerance
31 examples up to 85% yield
tr ansition-metal-f ree
strong-oxidant-free