Visible-Light-Enabled Stereodivergent Synthesis of E- and Z-Configured 1,4-Dienes by Photoredox/Nickel Dual Catalysis

Article abstract of DOI:10.1002/anie.201909543

A stereodivergent reductive coupling reaction between allylic carbonates and vinyl triflates to furnish both E- and Z-configured 1,4-dienes has been achieved by visible-light-induced photoredox/nickel dual catalysis. The mild reaction conditions allow good compatibility of both vinyl triflates and allylic carbonates. Notably, the stereoselectivity of this synergistic cross-electrophile coupling can be tuned by an appropriate photocatalyst with a suitable triplet-state energy, providing a practical and stereodivergent means to alkene synthesis. Preliminary mechanistic studies shed some light on the coupling step as well as the control of the stereoselectivity step.

Full text of DOI:10.1002/anie.201909543

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
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Accepted Article
Title: Visible-Light-Enabled Stereodivergent Synthesis of (E)- and
(Z)-1,4-Dienes via Photoredox/Nickel Dual Catalysis**
Authors: Fan SONG, Fang WANG, Lei GUO, Xiaoliang FENG, Yanyan
ZHANG, and Lingling Chu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201909543
Angew. Chem. 10.1002/ange.201909543
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http://dx.doi.org/10.1002/ange.201909543

10.1002/anie.201909543
Angewandte Chemie International Edition
COMMUNICATION
Visible-Light-Enabled Stereodivergent Synthesis of (E)- and (Z)-
1,4-Dienes via Photoredox/Nickel Dual Catalysis**
Fan Song,# Fang Wang,# Lei Guo, Xiaoliang Feng, Yanyan Zhang, Lingling Chu*
Abstract: A stereodivergent reductive coupling reaction between
allylic carbonates and vinyl triflates to furnish both (E)- and (Z)-1,4-
dienes has been achieved via visible-light-induced photoredox/nickel
dual catalysis. The mild conditions allow for good compatibility of
both vinyl triflates and allylic carbonates. Notably, the
stereoselectivity of this synergistic cross-electrophile coupling can be
tuned by an appropriate photocatalyst with a suitable triplet state
energy, providing a practice and stereodivergent means to alkene
synthesis. Preliminary mechanistic studies shed some light on the
coupling step as well as the stereoselectivity control step.
Alkenes play an essential role in the realm of chemical synthesis
due to their enriched reactivity and abundance. 1,4-Dienes, an
important class of olefin compounds, are also common structural
motifs
found
in
bioactive
natural
products
and
pharmaceuticals.[1] Therefore, the development of catalytic,
selective methodologies for the stereoselective synthesis of 1,4-
dienes is of particular importance. During the last decade,
several
elegant
catalytic
methods,
represented
by
hydroallylation of alkynes,[2] hydroalkenylation of 1,3-dienes,[3]
and vinyl–allyl cross-couplings,[4] have been successfully
developed to yield 1,4-dienes with high efficiency. Nevertheless,
most of these methods are stereospecific, generally delivering
the thermodynamically stable trans-1,4-dienes as single
products; the other cis-isomers are typically inaccessible in
these catalytic circumstances. Particularly, stereodivergent
catalytic protocols that allow the construction of both Z and E
isomers from one set of substrates,[5] an attractive yet
challenging strategy in the synthesis of alkenes, remain elusive
in 1,4-diene synthesis.
Figure 1. Stereodivergent synthesis of E- and Z-1,4-dienes via
photoredox/nickel dual catalysis.
provide
a stereospecific route to skipped dienes. More
specifically, we expected a stereodivergent synthesis of both E-
and Z-isomers of 1,4-dienes by tuning the structures of
photocatalysts.[10] Herein, we describe the successful execution
of this idea and report a photoredox/nickel catalyzed cross-
electrophile coupling[11],[12] of allylic carbonates[4a, 13], and vinyl
triflates[14]
.
We began our investigations into this photocatalytic
stereodivergent protocol using allylic carbonate 1 and vinyl
triflate 2 as model substrates (Table 1). With the combination of
Ni(OAc)2•4H2O as a nickel catalyst, 2,2’-bipyridine as a ligand,
Recently, visible-light-induced photoredox catalysis has
emerged as
a versatile cross-coupling platform for the
development of new and valuable chemical transformations.[6] In
this vein, our laboratory has described the stereospecific
synthesis of trisubstituted alkenes via metallaphotoredox[7]
enabled three-component 1,2-alkylarylation of terminal
alkynes.[8] This transformation relies on the capacity of
synergistic photoredox and nickel catalysis to sequentially forge
C–C bonds over alkynes, and to tune the stereoselectivity of the
hantzsch ester (HE) as
diazabicyclo[2.2.2]octane (DABCO) as
a
stoichiometric reductant, 1,4-
base, we were
a
delighted to find that exposure of the reaction mixture to a 90 W
blue LED in the presence of Ru(bpy)3(PF6)2 afforded 86% yield
of the linear 1,4-diene product 3 with excellent E selectivity (E/Z
99:1) (entry 1). Several ruthenium-based catalysts, for example
Ru(phen)3Cl2•xH2O and Ru(bpy)3Cl2, all afforded trans-3 with
comparable yields (entries 1−3). No branch-selective diene
products were observed under this photocatalytic condition. We
found that the Z/E-selectivity depends on the triplet energy of the
photocatalyst. Switching to photocatalysts of increasing triplet
energy, such as Ir(ppy)2(dtbbpy)(PF6) (ET = 51.0 kcal/mol),
Ir(ppy)3 (ET = 53.6 kcal/mol), and 9-fluorenone (ET = 53.2
kcal/mol), led to the formation of linear 1,4-diene with Z-
selectivity (entries 4−6). The use of Ir(ppy)2(dtbbpy)(PF6)
delivered (Z)-3 in 80% yield (entry 4, Z/E 93:7). Finally, control
experiments indicated that there was no diene formation in the
absence of nickel catalyst, ligand, hantzsch ester, and visible
light (entries 7−10), while low efficiency (38% yield) was
observed
resulting alkene products via
a
photoinduced contra-
thermodynamic E®Z alkene isomerization[9]. Recently, we
questioned whether this synergistic catalysis pathway would
[*]
F. Song, F. Wang, X. Feng, Y. Zhang, Dr. Prof. L. Chu
State Key Laboratory for Modification of Chemical Fibers and
Polymer Materials, Center for Advanced Low-Dimension Materials,
College of Chemistry, Chemical Engineering and Biotechnology,
Donghua University, Shanghai 201620, China
E-mail: lingling.chu1@dhu.edu.cn
F.S. and F.W. contributed equally to this work.
[#]
[**]
The authors are grateful for financial support provided by the
National Natural Science Foundation of China (21702029) and the
Shanghai Sailing Program (17YF1400100).
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201909543
Angewandte Chemie International Edition
COMMUNICATION
Table 1. Optimization of reaction conditions.[a]
synthetic handles for further manipulations (Products 7, 10−12,
18−21, 61%−89% yields). Allylic carbonates bearing
heteroarenes, in the forms of pyridines, quinolines, and indoles,
were also viable substrates, yielding the corresponding skipped
dienes with moderate to good efficiency (Products 22−24,
45%−85% yields). Pleasingly, this dual catalytic strategy was
amenable to complex allylic carbonates derived from bioactive
molecules including ibuprofen, febuxostat, and indometacin,
generating the desired cross-coupling products with good
efficiency and selectivity (Products 25−27, 45%−89% yields).
Next, we examined the scope of vinyl triflate partners in this
photocatalytic system. As depicted in Scheme 1, cyclic vinyl
triflates efficiently coupled with allylic carbonate to furnish the
desired linear 1,4-dienes with moderate efficiency and excellent
E-selectivity in the presence of Ru(bpy)3(PF6)2 as photocatalyst
(Products 28−43, 47%−79% yields, E/Z > 96:4). We found that
installing substituents on the 4-positions of vinyl triflates had little
effect on the reaction efficiency, and a variety of functional
groups such as esters, ketals, and heteroatoms were well-
tolerated (Products 28−33); while adding substituents on the
alpha-positions of vinyl triflates slightly decreased the reaction
efficiency (Product 34, 64% yield). Besides the 6-membered
cyclic system, five-， seven- and eight-membered cyclic vinyl
triflates were also viable partners, generating the desired
products with moderate yields (Products 38−40, 55%−65%
yields，E/Z > 96:4). Furthermore, the reaction of acyclic vinyl
triflates, including those derived from aldehydes, afforded the
skipped dienes with synthetically useful yields and good
selectivity (Products 41−43, 47%−79% yields, E/Z > 91:9).
Finally, we explored the generality of substrate scope
regarding the Z-selectivity using the optimal condition as
indicated in Table 1, entry 4. As shown in Scheme 1, the
reaction of allylic carbonate 1 with an array of vinyl triflates
delivered the Z-skipped diene products with moderate yields and
good selectivity in the presence of Ir(ppy)2(dtbbpy)+ as
photocatalyst (Products 44−49, 46%−80% yields, Z/E > 91:9).
Furthermore, allylic carbonates incorporated with ortho-Me, -Cl,
and -F all proceeded well under the optimal conditions,
furnishing the desired 1,4-dienes with high Z-selectivity
(Products 50−52, 64%−69% yields, Z/E > 88:12). The presence
of ortho-substituent was found to be important for achieving high
Z-selectivity, while removing ortho-substituents resulted in a
comparable decrease in Z/E selectivity (Product 53, 70% yield,
Z/E = 85:15). We surmised that this phenomenon may be
attributed to the increased deconjugation in the product by
augmenting A1,3-strain.[16]
entry
photocatalysts
Ru(bpy)3(PF6)2
Ru(phen)3Cl2•xH2O
Ru(bpy)3Cl2•xH2O
Ir(ppy)2(dtbbpy)(PF6)
Ir(ppy)3
yield
86%
83%
76%
80%
55%
65%
E/Z
1
2
3
4
5
6
99:1
94:6
98:2
7:93
5:95
9:91
9-fluorenone
variations from the “standard” conditions
7b
w/o nickel catalyst
dark
0%
/
8b
0%
/
9b
w/o ligand
4%
E
10b
11b
12
w/o HE
0%
/
w/o DABCO
38%
89:11
w/o photocatalyst
69%
98:2
[a]Reaction conditions: photocatalyst (1 mol%), Ni(OAc)2•4H2O (15 mol%), 2,2’-
bipyridine (15 mol%), allylic carbonate 1 (0.1 mmol), vinyl triflate 2 (1.2 equiv.),
HE (1.5 equiv.), DABCO (1.0 equiv.), DMSO [0.05 M], 90 W Blue LED, 33-35
oC. Yields and Z/E ratios were determined by 1H NMR. [b]With Ru(bpy)3(PF6)2
in the absence of DABCO (entry 11). Interestingly, we found that
photocatalyst was not necessary for the formation of E-selective
1,4-diene, as there was 69% yield of trans-3 (E/Z = 98:2) in the
absence of photocatalyst (entry 12). We reasoned that
photoexcited HE was attributed to this reactivity in this case.[15]
While only the trans-diene product was observed in the absence
of photocatalyst, further indicating that photocatalyst controlled
the Z-selectivity in this stereodivergent strategy.
With the optimal conditions in hand, we next examined the
generality of the allylic carbonate component in this new
metallaphotoredox reductive coupling protocol. As described in
Scheme 1, a wide range of allylic carbonates incorporating
electron-rich and -poor aromatic substituents underwent the
desired cross-electrophile coupling under the optimal E-selective
conditions (entry 1 in Table 1), furnishing the E-selective skipped
dienes with good yields and excellent selectivity (Products 3−21,
61%−89% yields, up to 99:1 E/Z). Both linear and branched
allylic carbonates delivered the linear 1,4-dienes as single
To probe the possible reaction mechanism and understand
the selectivity control, we have performed
a series of
mechanistic studies (Scheme 2). First, exposure of trans-3 to
visible light in the presence of Ir(ppy)2(dtbbpy)(PF6) led to the
formation of cis-3 (quant, Z/E 94:6), while no isomerization was
observed in the absence of light or photocatalyst, suggesting
that Z-selectivity control could be attributed to a photocatalytic
E®Z isomerization process of alkene products (Scheme 2A).
Furthermore, Stern-Volmer fluorescent quenching studies
indicated that both the photoexcited state of *Ir(III) and *Ru(II)
were effectively quenched by HE, providing strong evidence for
electron transfer from HE to
regioisomers (Products
4 and 24, 82% and 85% yield,
respectively). The mild conditions allowed for the good
compatibility of many functional groups, including chlorides,
bromides, trifluoromethylates, and cyanides, providing useful
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10.1002/anie.201909543
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Scheme 1. Scope of substrates. Reaction conditions: photocatalyst (1 mol%), Ni(OAc)2•4H2O (15 mol%), 2,2’-bipyridine (15 mol%), allylic carbonates
(0.2 mmol), vinyl triflates (1.2 equiv.), HE (1.5 equiv.), DABCO (1.0 equiv.), DMSO [0.05M], 90 W Blue LED, 33-35 oC. Isolated yields. aWith linear
allylic carbonate; bWith 3 equiv. of vinyl triflate.
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10.1002/anie.201909543
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COMMUNICATION
transfer process with Ni(0) in this synergistic system (Scheme
2C).
A)
Ph
Ph
Ir(ppy)2(dtbbpy)+
Based on these experimental results, a plausible reaction
pathway has been depicted in Scheme 3. Vinyl triflate B would
undergo oxidative addition with Ni(0) A to produce (vinyl)Ni(II)
complex C. Meanwhile, single-electron reduction of allylic
carbonate D by Ni(0) species could generate allylic radical
ꢀꢁꢂꢃꢄꢅꢆꢇ
DMSO [0.05M]
cis-3
Z/E = 94:6
no catalyst: E only
Blue LED
standard:
trans-3
no light:
E only
species E, which then add to (vinyl)Ni(II)
C to furnish
B)
Me
Me
(allyl)(vinyl)Ni(III) species F.[4b] Ni(III) species F would undergo
facile reductive elimination to furnish the desired (E)-1,4-diene
product G as well as Ni(I) species H. Concurrently, single-
electron transfer from HE to the photoexcited *PCm II afforded
the reduced PCm-1 III. At this stage, single-electron transfer
between Ni(I) and PCm-1 would regenerate the ground state PCm
catalyst I and Ni(0) species A.[17] If photocatalysts with higher ET,
such as Ir(ppy)2(dtbbpy)+, were employed, the resulting (E)-1,4-
vinyl triflate 2
OBoc
Ph
standard condition
N
Ph
Ph
O
TEMPO (x equiv.)
Me Me
4
55
34%
54
x = 2: 40%
x = 5: 0%
70%
C)
i) Ni(COD)2, bpy
Me
Me
ii) Ru-cat, HE, DABCO, hv
OBoc
i) 23%
ii) 0%
iii) 0%
iii) HE, DABCO, hv
diene
G would further undergo a contra-thermodynamic,
N
Ph
Ph
O
TEMPO
photocatalytic E®Z isomerization in the presence of light,
furnishing (Z)-1,4-diene product J.[9] Additionally, we surmised
that photoexcited HE (E*red = –2.2 V vs SCE)[15e] would be
responsible for the single-electron reduction of Ni(I) in the
absence of photocatalyst[15b]. On the basis of literature reports[13b,
13d, 13f-h, 18] as well as the fact that 40% product was still observed
in the presence of 2 equiv. TEMPO (Scheme 2B), nevertheless,
another reaction pathway involving p-allyl-Ni (II) species might
also be operative in this transformation. Oxidative addition of
allylic carbonate to Ni(0) would give p-allyl-Ni (II) species K,
Me Me
(2.0 equiv.)
54
55
Scheme 2. Mechanistic studies.
OBoc
Ni(0)
R2
Ar
R1
Ar
E
Ar
D
Z-1,4-diene
J
TfO
NiIII
NiII
followed by SET reduction to afford p-allyl-Ni (I) L.[13g,
13h]
Ar
OTf
R1
C
Subsequent reaction of Ni(I) L with vinyl triflate would generate
the crucial Ni(III) F to enter the similar cycle shown above.
R1
F
Ir-cat, hv
isomerization
R2
R2
HE
*PCm II
In conclusion, we have developed
a
mild and
SET
stereodivergent cross-electrophile coupling reaction between
readily available allylic carbonates and vinyl triflates via visible-
light-induced photoredox/nickel dual catalysis. This dual catalytic
protocol allows for a direct and stereodivergent synthesis of both
(E)- and (Z)-selective skipped dienes from a single set of
substrates. The stereoselectivity of this cross-electrophile
coupling can be controlled by the nature of photocatalysts,
providing a practice and stereodivergent means to alkene
synthesis.
HE
vinyl
triflate
B
PCm
I
PCm-1
R2
R1
III
LnNi0
Ar
LnNiI
A
SET
X
allylic
carbonate
D
H
E-1,4-diene
G
HE*
HE
NiII
TfO
R1
X
NiIII
Ar
Ar
K
Keywords: photoredox catalysis • nickel catalysis • cross-
F
R2
electrophile coupling • 1,4-diene • stereodivergent
+ e
OTf
NiI
X
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COMMUNICATION
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10.1002/anie.201909543
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Fan Song,# Fang Wang, # Lei Guo,
Xiaoliang Feng, Yanyan Zhang, Lingling
Chu*
Page No. – Page No.
Visible-Light-Enabled
Stereodivergent Synthesis of (E)- and
(Z)-1,4-Dienes via Photoredox/Nickel
Dual Catalysis
A stereodivergent reductive coupling reaction between allylic carbonates and vinyl
triflates to yield both (E)- and (Z)-1,4-dienes has been achieved via visible light-
induced photoredox/nickel dual catalysis. The stereoselectivity of this cross-
electrophile coupling can be tuned by choosing an appropriate photocatalyst,
providing a practice and stereodivergent means to alkene synthesis.
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