Nickel-Catalyzed Hydroarylation of in Situ Generated 1,3-Dienes with Arylboronic Acids Using a Secondary Homoallyl Carbonate as a Surrogate for the 1,3-Diene and Hydride Source

Article abstract of DOI:10.1021/acs.orglett.9b04634

The nickel-catalyzed hydroarylation of 1,3-dienes with arylboronic acids using a secondary homoallyl carbonate as a surrogate for the 1,3-diene and hydride source has been developed. The synthetic strategy allowed an efficient access to a wide array of hydroarylation products in high yields with high functional group compatibility without the use of an external hydride source. Mechanistic experiments indicated that the alkene-directed oxidative addition and subsequent β-hydride elimination would be a critical process in this transformation.

Full text of DOI:10.1021/acs.orglett.9b04634

pubs.acs.org/OrgLett
Letter
Nickel-Catalyzed Hydroarylation of in Situ Generated 1,3-Dienes
with Arylboronic Acids Using a Secondary Homoallyl Carbonate as a
Surrogate for the 1,3-Diene and Hydride Source
Takashi Hamaguchi, Yoshiyuki Takahashi, Hiroaki Tsuji,* and Motoi Kawatsura*
Cite This: https://dx.doi.org/10.1021/acs.orglett.9b04634
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: The nickel-catalyzed hydroarylation of 1,3-dienes
with arylboronic acids using a secondary homoallyl carbonate as a
surrogate for the 1,3-diene and hydride source has been developed.
The synthetic strategy allowed an efficient access to a wide array of
hydroarylation products in high yields with high functional group
compatibility without the use of an external hydride source.
Mechanistic experiments indicated that the alkene-directed
oxidative addition and subsequent β-hydride elimination would
be a critical process in this transformation.
Scheme 1. Transition-Metal-Catalyzed Hydroarylation of
1,3-Dienes
he transition-metal-catalyzed hydrofunctionalization of
Tcarbon−carbon multiple bonds represents an attractive
strategy for the formation of carbon−carbon and carbon−
heteroatom bonds in organic synthesis.1 The catalytic
hydrofunctionalization of 1,3-dienes is among the most
significant transformations due to its high utility in the
construction of complex organic molecules.2−9 In particular,
catalytic hydroarylation of 1,3-dienes offers efficient and
straightforward access to the alkenyl arenes and has received
significant attention from organic chemists. The hydroarylation
has been achieved by the transition-metal-catalyzed reactions
involving a metal hydride species generated by the aromatic
C−H bond activation (Scheme 1a)10 and the reaction with
alcohols as an external hydride source (Scheme 1b).11,12
A
carbodicarbene−Rh(I) pincer complex is also known to be an
active π-acidic catalyst in the hydroarylation of conjugated
dienes (Scheme 1c).13 However, these reported methods rely
on the use of special arenes (e.g., electron-rich arenes,
heteroarenes, and benzamides) and the external hydride
source. Therefore, developing a novel approach for realizing
the highly efficient catalytic hydroarylation of 1,3-dienes with a
broad scope of substrates is highly desirable.
The substrate-directed chemical reaction, especially using
metal catalysts, has been recognized as a powerful tool in the
field of synthetic organic chemistry.14 Among these reactions,
the transition-metal-catalyzed alkene-directed transformations
have received much attention, and several attractive reactions
have been established.15 Sigman and co-workers reported that
the palladium-catalyzed reaction of homoallyl tosylates with
arylboronic acids afforded the hydroarylation products
(Scheme 1d).16 In this reaction, the alkene-directed oxidative
addition of a C−O bond to Pd(0) followed by β-hydride
elimination produces 1,3-dienes that subsequently react with
Received: December 24, 2019
https://dx.doi.org/10.1021/acs.orglett.9b04634
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

Organic Letters
pubs.acs.org/OrgLett
Letter
arylboronic acids in the presence of a palladium hydride
species, providing the hydroarylation products. Although this
reaction would provide a new path for the hydroarylation of
1,3-dienes, the catalyst system seems to be immature with
respect to the substrate scope and reaction yield. This research
precedent stimulated us to develop a new catalyst system for
the hydroarylation of 1,3-dienes, which covers a broad scope of
arenes without the use of an external hydride source. We now
report the nickel-catalyzed hydroarylation of 1,3-dienes with
arylboronic acids using secondary homoallyl carbonates as a
surrogate for the 1,3-diene and hydride source (Scheme 1e).
We began our investigation with the optimization of the
reaction conditions (Table 1). Recently, Krische and co-
the transformation, giving the desired hydroarylation product
3aa in 89% yield (Table 1, entry 3). In sharp contrast, the
reaction with P(p-CF3C6H4)3 failed to give the desired product
3aa (Table 1, entry 4). In addition, the use of sterically
congested monophosphine ligands such as P(o-tol)3, P(o-
MeOC6H4)3, PCy3, Pt-Bu3, and XPhos retarded the reaction
(Table 1, entries 5−9). We also evaluated the effect of the
bisphosphine ligands in the nickel catalyst system. DPPPent
and DPEphos were not effective for the reaction, yielding 3aa
in low yields (Table 1, entries 10 and 11). The reaction in the
presence of Xantphos led to a decrease in the yield of 3aa
(Table 1, entry 12). When bipyridine- and phenanthroline-
derived ligands were employed in the reaction as the ligands,
the desired product 3aa was formed in low yields (Table 1,
entries 13 and 14). The ligand screening indicated that the use
of a triarylphosphine bearing an electron-donating group at the
para position on the phenyl ring is essential to proceed the
transformation. To improve the yield of 3aa, the reaction of 1a
with 2a was performed using the Ni(cod)2/P(p-MeOC6H4)3
system for 36 h. Fortunately, the reaction proceeded
quantitatively to give the desired product 3aa in 94% isolated
yield (Table 1, entry 15).
With the optimized reaction conditions in hand, we
examined the reaction of various homoallyl carbonates 1
with phenylboronic acid (2a) (Scheme 2). The reaction could
be conducted on a 3 mmol scale to give the desired
hydroarylation product 3aa in 93% yield. The reaction of
homoallyl carbonates 1b−e bearing electron-donating (Me,
MeO) and -withdrawing (CF3, CO2Me) substituents at the
para position on the phenyl rings smoothly proceeded to
provide the corresponding hydroarylation products 3ba−ea in
83−93% yields. Homoallyl carbonates 1f and 1g having 4-
fluorophenyl and biphenyl groups underwent the reaction to
give the desired products 3fa and 3ga in 87% and 89% yield,
respectively. Both electron-donating and -withdrawing sub-
stituents at the meta and ortho positions on their phenyl rings
were compatible with the reaction, giving the corresponding
hydroarylation products 3ha−ma in 71−91% yields. The other
substituents, such as piperonyl (1n), 2-naphthyl (1o), and 6-
methoxy-2-naphthyl (1p) groups, were well tolerated during
the nickel catalysis. Our nickel catalyst system can be also
applicable to the transformation of homoally carbonates 1q
and 1r having pyridine rings, affording the hydroarylation
product 3qa and 3ra in 65% and 93% yield, respectively.
Unfortunately, other heterocyclic rings such as furan and
thiophene were not tolerated during the reaction, resulting in
the complex mixture of unassigned products. In addition,
although the reaction of homoally carbonates bearing aliphatic
substituents (R = cyclohexyl) proceeded under the reaction
conditions, we could not isolate the desired products as a pure
form (89% conv, 42% NMR yield). We confirmed that the
reaction of homoally carbonates 1s and 1t did not take place
under the optimized reaction conditions. In the reactions with
1e, 1i, 1o, and 1q, we confirmed the formation of a trace
amount of the corresponding 1,4-hydroarylation products by
1H NMR analyses of the crude mixture.
a
Table 1. Optimization of Reaction Conditions
b
b
entry
L
conv (%)
yield (%)
1
2
3
4
5
6
7
8
PPh3
P(p-tol)3
72
90
94
<1
<1
25
32
16
<1
26
56
73
59
36
>99
53
c
81
89
c
P(p-MeOC6H4)3
P(p-CF3C6H4)3
P(o-tol)3
P(o-MeOC6H4)3
PCy3
P-t-Bu3
XPhos
DPPPent
DPEphos
<1
<1
13
19
2
9
<1
5
10
11
12
13
14
20
57
15
6
Xantphos
4,4′-di-t-Bu-2,2′-bpy
1,10-phenanthroline
P(p-MeOC6H4)3
d
e
f
15
>99 (94)
a
Reaction conditions: 1a (0.25 mmol), 2a (0.375 mmol), Ni(cod)2
(0.025 mmol), L (0.05 mmol), K2CO3 (0.375 mmol) in CH3CN (0.2
1
M) at 60 °C for 18 h. E/Z ratios were determined by H NMR
b
analyses of crude mixture. The conversions and yields were
1
determined by H NMR analysis using phenanthrene as an internal
c
standard. A trace amount of the 1,4-hydroarylation product was
d
observed by the 1H NMR analysis of the crude mixture. The reaction
e
1
time was prolonged to 36 h. The yield was determined by H NMR
f
analysis using CH2Br2 as an internal standard. Isolated yield as a
mixture with a trace amount of Z isomer.
workers reported an intriguing result in which a homoallyl
carbonate was converted into the hydroarylation product in the
presence of a nickel catalyst via in situ formation of a 1,3-diene
(single example).17 Based on this result, we chose secondary
homoallyl carbonate 1a, which is readily prepared by the
reaction of benzaldehyde with allylorganometallic reagents,18
and Ni(cod)2 as a catalyst. The reaction of homoallyl
carbonate 1a with phenylboronic acid (2a) was carried out
in the presence of 10 mol % Ni(cod)2, 20 mol % PPh3, and 1.5
equiv of K2CO3 in CH3CN at 60 °C for 18 h. We confirmed
that hydroarylation product 3aa was formed in 53% yield
(Table 1, entry 1). Motivated by this initial result, we
examined the screening of monophoshine ligands (Table 1,
entries 2−9). The use of P(p-tol)3 as the ligand improved the
yield of 3aa to 81% (Table 1, entry 2). A combination of
Ni(cod)2 and P(p-MeOC6H4)3 was found to be effective for
We next investigated the scope of arylboronic acids 2 in the
reaction of homoallyl carbonate 1a (Scheme 3). Both electron-
rich and -poor phenylboronic acids 2b−f underwent the
reaction to afford the hydroarylation products 3ab−af in high
yields. Functionalized phenylboronic acids bearing acetyl and
terminal alkene groups also participated in the reaction,
providing the desired hydroarylation products 3ag and 3ah in
B
https://dx.doi.org/10.1021/acs.orglett.9b04634
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
pubs.acs.org/OrgLett
Letter
a
a
Scheme 2. Scope of Secondary Homoallyl Carbonates
Scheme 3. Scope of Arylboronic Acids
a
Reaction conditions: 1a (0.25 mmol), 2 (0.375 mmol), Ni(cod)2
(0.025 mmol), P(p-MeOC6H4)3 (0.05 mmol), K2CO3 (0.375 mmol)
in CH3CN (0.2 M) at 60 °C for 36 h. E/Z ratios were determined by
1H NMR analyses of the crude mixture and are shown in parentheses.
b
Trace amounts of the corresponding 1,4-hydroarylation products
c
1
were observed by H NMR analyses of the crude mixture. Yield of
the corresponding alcohol. See the Supporting Information for details.
d
20 mol % of Ni(cod)2 and 40 mol % of P(p-MeOC6H4)3 were used.
e
f
As a mixture with a trace amount of inseparable impurity. A trace
a
Reaction conditions: 1 (0.25 mmol), 2a (0.375 mmol), Ni(cod)2
(0.025 mmol), P(p-MeOC6H4)3 (0.05 mmol), K2CO3 (0.375 mmol)
in CH3CN (0.2 M) at 60 °C for 36 h. E/Z ratios were determined by
1H NMR analyses of the crude mixture and are shown in parentheses.
amount of Z isomer was observed by GC−MS analysis.
Scheme 4. Control Experiments
b
c
3 mmol scale. Trace amounts of the corresponding 1,4-hydro-
1
arylation products were observed by H NMR analyses of the crude
mixture.
89% and 61% yield, respectively. Meta- and ortho-substituted
phenyl boronic acids 2i−k also worked well in the reaction
system, giving the desired products 3ai−ak in high yields. The
use of phenylboronic acid 2l bearing a trifluoromethyl group at
the ortho position led to a slight decrease of the reaction
efficiency. When the reaction 1-naphthalenylboronic acid 2m
was subjected to the reaction conditions, the desired product
3am was obtained in 96% yield. Heterocyclic rings such as
furan, thiophene, and carbazole were compatible with the
nickel catalyst system, providing the corresponding hydro-
arylation products 3an−ap in 61−92% yields. In the reactions
with 2d, 2k, 2m, and 2p, we confirmed the formation of a trace
amount of the corresponding 1,4-hydroarylation products by
1H NMR and GC−MS analyses.
The reaction of bishomoallyl carbonate 4 with phenylboronic
acid (2a) was carried out under the optimized reaction
conditions, giving the olefin isomerization product 6 in 35%
yield. We could not observe the formation of hydroarylation
products by the reaction of the isomerized product 6 with 2a
probably due to the inert nature of homoallyl carbonate
To identify the role of the alkene group on the substrate, we
examined several control experiments as shown in Scheme 4.
C
https://dx.doi.org/10.1021/acs.orglett.9b04634
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
pubs.acs.org/OrgLett
Letter
bearing a disubstituted alkene group in the nickel catalyst
system (see Scheme 2, substrates 1s and 1t). The reaction of
carbonate 5 having three methylene units also afforded the
alkene-isomerized product 7 in 69% yield (Scheme 4a).19
When the reaction of secondary alkyl carbonate 8 with 2a was
performed under the optimized reaction conditions, no
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.9b04634.
■
sı
Experimental details and procedures; experimental
details for control experiments; NMR spectra (PDF)
1
products were observed by H NMR and GC−MS analyses
of the reaction mixture (Scheme 4b). These results indicated
that the alkene group of the homoalyll carbonates plays a key
role for the present nickel catalyzed hydroarylation as a
directing group.
Based on the results of the control experiments and the
reaction mechanism of the palladium-catalyzed reaction of
homoallyl tosylates with arylboronic acids reported by Sigman
and co-workers,16 we proposed a plausible catalytic cycle for
the present nickel catalysis (Scheme 5). Initially, the alkene-
AUTHOR INFORMATION
Corresponding Authors
■
Hiroaki Tsuji − Department of Chemistry, College of
Humanities & Sciences, Nihon University, Tokyo 156-8550,
Japan; orcid.org/0000-0002-8899-3435; Email: tsuji@
chs.nihon-u.ac.jp
Motoi Kawatsura − Department of Chemistry, College of
Humanities & Sciences, Nihon University, Tokyo 156-8550,
Japan; orcid.org/0000-0002-8341-6866;
Email: kawatsur@chs.nihon-u.ac.jp
Scheme 5. Plausible Reaction Mechanism
Authors
Takashi Hamaguchi − Department of Chemistry, College of
Humanities & Sciences, Nihon University, Tokyo 156-8550,
Japan
Yoshiyuki Takahashi − Department of Chemistry, College of
Humanities & Sciences, Nihon University, Tokyo 156-8550,
Japan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.9b04634
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by a Grant-in-Aid for Scientific
Research (C) from the Japan Society for the Promotion of
Science (17K05794). We thank Mr. Yusuke Miyazaki for IR
and HRMS measurements.
directed oxidative addition of a C−O bond of homoallyl
carbonate 1a to nickel(0) species would occur to generate
secondary alkylnickel intermediate I. Subsequent β-hydride
elimination would produce nickel hydride intermediate II
stabilized by the coordination of the diene ligand derived from
the homoallyl carbonate. Insertion of the terminal alkene
moiety of the diene ligand to a Ni−H bond seems to take place
due to the formation of the π-allylnickel intermediate III.20
Transmetalation between the intermediate III and borate
species followed by the reductive elimination from inter-
mediate IV would produce the desired coupling product 3aa
along with the regeneration of nickel(0) species.21
In conclusion, we have developed the nickel-catalyzed
hydroarylation of 1,3-dienes with arylboronic acids in which
secondary homoallyl carbonates would act as a surrogate for
the 1,3-diene and hydride source. The nickel catalyst system
enabled the straightforward access to a series of alkenyl arenes
in high yields using readily accessible secondary homoallyl
carbonates and arylboronic acids. The development of the
hydrofunctionalization using this methodology and the de-
tailed mechanistic study are currently underway in our
laboratory.
REFERENCES
■
(1) For recent reviews, see: (a) de Mendoza, P.; Echavarren, A. M.
Synthesis of Arenes and Heteroarenes by Hydroarylation Reactions
Catalyzed by Electrophilic Metal Complexes. Pure Appl. Chem. 2010,
82, 801−820. (b) Huang, L.; Arndt, M.; Gooßen, K.; Heydt, H.;
Gooßen, L. J. Late Transition Metal-Catalyzed Hydroamination and
Hydroamidation. Chem. Rev. 2015, 115, 2596−2697. (c) Dong, Z.;
Ren, Z.; Thompson, S. J.; Xu, Y.; Dong, G. Transition-Metal-
Catalyzed C-H Alkylation Using Alkenes. Chem. Rev. 2017, 117,
́
9333−9403. (d) Bezzenine-Lafollee, S.; Gil, R.; Prim, D.;
Hannedouche, J. First-Row Late Transition Metals for Catalytic
Alkene Hydrofunctionalisation: Recent Advances in C-N, C-O and C-
P Bond Formation. Molecules 2017, 22, 1901−1929. (e) Holmes, M.;
Schwartz, L. A.; Krische, M. J. Intermolecular Metal-Catalyzed
Reductive Coupling of Dienes, Allenes, and Enynes with Carbonyl
Compounds and Imines. Chem. Rev. 2018, 118, 6026−6052.
̈
(2) For selected examples for the hydroamination, see: (a) Lober,
O.; Kawatsura, M.; Hartwig, J. F. Palladium-Catalyzed Hydro-
amination of 1,3-Dienes: A Colorimetric Assay and Enantioselective
Additions. J. Am. Chem. Soc. 2001, 123, 4366−4367. (b) Pawlas, J.;
Nakao, Y.; Kawatsura, M.; Hartwig, J. F. A General Nickel-Catalyzed
Hydroamination of 1,3-Dienes by Alkylamines: Catalyst Selection,
Scope, and Mechanism. J. Am. Chem. Soc. 2002, 124, 3669−3679.
(c) Qin, H.; Yamagiwa, N.; Matsunaga, S.; Shibasaki, M. Bismuth-
Catalyzed Intermolecular Hydroamination of 1,3-Dienes with
Carbamates, Sulfonamides, and Carboxamides. J. Am. Chem. Soc.
D
https://dx.doi.org/10.1021/acs.orglett.9b04634
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
pubs.acs.org/OrgLett
Letter
2006, 128, 1611−1614. (d) Brouwer, C.; He, C. Efficient Gold-
Catalyzed Hydroamination of 1,3-Dienes. Angew. Chem., Int. Ed.
2006, 45, 1744−1747. (e) Goldfogel, M. J.; Roberts, C. C.; Meek, S. J.
Intermolecular Hydroamination of 1,3-Dienes Catalyzed by Bis-
(phosphine)carbodicarbene-Rhodium Complexes. J. Am. Chem. Soc.
2014, 136, 6227−6230. (f) Yang, X.-H.; Dong, V. M. Rhodium-
Catalyzed Hydrofunctionalization: Enantioselective Coupling of
Indolines and 1,3-Dienes. J. Am. Chem. Soc. 2017, 139, 1774−1777.
(g) Tran, G.; Shao, W.; Mazet, C. Ni-Catalyzed Enantioselective
Intermolecular Hydroamination of Branched 1,3-Dienes Using
Primary Aliphatic Amines. J. Am. Chem. Soc. 2019, 141, 14814−
14822.
(3) For recent examples of hydroalkoxylation, see the following and
pertinent references cited therein. (a) Bigot, S.; El Alami, M. S. I.;
Mifleur, A.; Castanet, Y.; Suisse, I.; Mortreux, A.; Sauthier, M. Nickel-
Catalysed Hydroalkoxylation Reaction of 1,3-Butadiene: Ligand
Controlled Selectivity for the Efficient and Atom-Economical
Synthesis of Alkylbutenyl Ethers. Chem. - Eur. J. 2013, 19, 9785−
9788. (b) Tran, G.; Mazet, C. Ni-Catalyzed Regioselective Hydro-
alkoxylation of Branched 1,3- Dienes. Org. Lett. 2019, 21, 9124−9127.
(4) For recent examples of hydrothiolation, see: (a) Yang, X.-H.;
Davison, R. T.; Dong, V. M. Catalytic Hydrothiolation: Regio- and
Enantioselective Coupling of Thiols and Dienes. J. Am. Chem. Soc.
2018, 140, 10443−10446. (b) Yang, X.-H.; Davison, R. T.; Nie, S.-Z.;
Cruz, F. A.; McGinnis, T. M.; Dong, V. M. Catalytic Hydrothiolation:
Counterion-Controlled Regioselectivity. J. Am. Chem. Soc. 2019, 141,
3006−3013.
(b) Saini, V.; O’Dair, M.; Sigman, M. S. Synthesis of Highly
Functionalized Tri- and Tetrasubstituted Alkenes via Pd-Catalyzed
1,2-Hydrovinylation of Terminal 1,3-Dienes. J. Am. Chem. Soc. 2015,
137, 608−611. (c) Timsina, Y. N.; Sharma, R. K.; RajanBabu, T. V.
Cobalt-Catalysed Asymmetric Hydrovinylation of 1,3-Dienes. Chem.
Sci. 2015, 6, 3994−4008.
(9) For recent example of hydroacylation, see the folllowing and
pertinent references cited therein. Chen, Q.-A.; Kim, D. K.; Dong, V.
M. J. Am. Chem. Soc. 2014, 136, 3772−3775.
(10) (a) Nakao, Y.; Kashihara, N.; Kanyiva, K. S.; Hiyama, T.
Nickel-Catalyzed Alkenylation and Alkylation of Fluoroarenes via
Activation of C-H Bond over C-F Bond. J. Am. Chem. Soc. 2008, 130,
16170−16171. (b) Lee, W.-C.; Shih, W.-C.; Wang, T.-H.; Liu, Y.;
Yap, G. P. A.; Ong, T.-G. Nickel Promoted Switchable Hydro-
heteroarylation of Cyclodienes via C-H Bond Activation of
Heteroarenes. Tetrahedron 2015, 71, 4460−4464. (c) Nagamoto,
M.; Yorimitsu, H.; Nishimura, T. Iridium-Catalyzed Hydroarylation of
Conjugated Dienes via D-Allyliridium Intermediates. Org. Lett. 2018,
20, 828−831.
(11) (a) Liao, L.; Sigman, M. S. Palladium-Catalyzed Hydroarylation
of 1,3-Dienes with Boronic Esters via Reductive Formation of π-Allyl
Palladium Intermediates under Oxidative Conditions. J. Am. Chem.
Soc. 2010, 132, 10209−10211. (b) Xiao, L.-J.; Cheng, L.; Feng, W.-
M.; Li, M.-L.; Xie, J.-H.; Zhou, Q.-L. Nickel(0)-Catalyzed Hydro-
arylation of Styrenes and 1,3-Dienes with Organoboron Compounds.
Angew. Chem., Int. Ed. 2018, 57, 461−464.
(12) Meek and co-workers reported the hydroarylation of 1,3-dienes
with indoles catalyzed by Rh-H species using a carbodicarben ligand
as the hydride source; see: Marcum, J. S.; Roberts, C. C.; Manan, R.
S.; Cervarich, T. N.; Meek, S. J. J. Am. Chem. Soc. 2017, 139, 15580−
15583.
(5) For recent examples of hydrophosphorylation, see the following
and pertinent references cited therein. Nie, S.-Z.; Davison, R. T.;
Dong, V. M. Enantioselective Coupling of Dienes and Phosphine
Oxides. J. Am. Chem. Soc. 2018, 140, 16450−16454.
(6) For recent examples of hydroboration, see: (a) Ely, R. J.;
Morken, J. P. Regio- and Stereoselective Ni-Catalyzed 1,4-Hydro-
boration of 1,3-Dienes: Access to Stereodefined (Z)-Allylboron
Reagents and Derived Allylic Alcohols. J. Am. Chem. Soc. 2010, 132,
2534−2535. (b) Liu, Y.; Fiorito, D.; Mazet, C. Copper-Catalyzed
Enantioselective 1,2-Borylation of 1,3-Dienes. Chem. Sci. 2018, 9,
5284−5288. (c) Fiorito, D.; Mazet, C. Ir-Catalyzed Selective
Hydroboration of 2-Substituted 1,3-Dienes: A General Method to
Access Homoallylic Boronates. ACS Catal. 2018, 8, 9382−9387.
(d) Duvvuri, K.; Dewese, K. R.; Parsutkar, M. M.; Jing, S. M.; Mehta,
M. M.; Gallucci, J. C.; RajanBabu, T. V. Cationic Co(I)-Intermediates
for Hydrofunctionalization Reactions: Regio- and Enantioselective
Cobalt-Catalyzed 1,2-Hydroboration of 1,3-Dienes. J. Am. Chem. Soc.
2019, 141, 7365−7375. See also pertinent references cited therein.
(7) For selected examples of hydroalkylation, see: (a) Shibahara, F.;
Bower, J. F.; Krische, M. J. Ruthenium-Catalyzed C-C Bond Forming
Transfer Hydrogenation: Carbonyl Allylation from the Alcohol or
Aldehyde Oxidation Level Employing Acyclic 1,3-Dienes as
Surrogates to Preformed Allyl Metal Reagents. J. Am. Chem. Soc.
2008, 130, 6338−6339. (b) Zbieg, J. R.; Yamaguchi, E.; McInturff, E.
L.; Krische, M. J. Enantioselective C-H Crotylation of Primary
Alcohols via Hydrohydroxyalkylation of Butadiene. Science 2012, 336,
324−327. (c) Adamson, N. J.; Wilbur, K. C. E.; Malcolmson, S. J.
Enantioselective Intermolecular Pd-Catalyzed Hydroalkylation of
Acyclic 1,3-Dienes with Activated Pronucleophiles. J. Am. Chem.
Soc. 2018, 140, 2761−2764. (d) Cheng, L.; Li, M.-M.; Xiao, L.-J.; Xie,
J.-H.; Zhou, Q.-L. Nickel(0)-Catalyzed Hydroalkylation of 1,3-Dienes
with Simple Ketones. J. Am. Chem. Soc. 2018, 140, 11627−11630.
(e) Li, C.; Liu, R. Y.; Jesikiewicz, L. T.; Yang, Y.; Liu, P.; Buchwald, S.
L. CuH-Catalyzed Enantioselective Ketone Allylation with 1,3-
Dienes: Scope, Mechanism, and Applications. J. Am. Chem. Soc.
2019, 141, 5062−5070. (f) Lv, L.; Zhu, D.; Qiu, Z.; Li, J.; Li, C.-J.
Nickel-Catalyzed Regioselective Hydrobenzylation of 1,3-Dieneswith
Hydrazones. ACS Catal. 2019, 9, 9199−9205.
(13) (a) Roberts, C. C.; Matías, D. M.; Goldfogel, M. J.; Meek, S. J.
Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed
Hydroarylation of Dienes. J. Am. Chem. Soc. 2015, 137, 6488−6491.
́
(b) Gu, L.; Wolf, L. M.; Zielinski, A.; Thiel, W.; Alcarazo, M. z-
Dicationic Chelating Phosphines: Synthesis and Application to the
Hydroarylation of Dienes. J. Am. Chem. Soc. 2017, 139, 4948−4953.
(14) (a) Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Substrate-
Directable Chemical Reactions. Chem. Rev. 1993, 93, 1307−1370.
(b) Sawano, T.; Yamamoto, H. Substrate-Directed Catalytic Selective
Chemical Reactions. J. Org. Chem. 2018, 83, 4889−4904. (c) Bhadra,
S.; Yamamoto, H. Substrate Directed Asymmetric Reactions. Chem.
Rev. 2018, 118, 3391−3446.
(15) For a review, see: Johnson, J. B.; Rovis, T. More than
Bystanders: The Effect of Olefins on Transition-Metal-Catalyzed
Cross-Coupling Reactions. Angew. Chem., Int. Ed. 2008, 47, 840−871.
(16) (a) Stokes, B. J.; Opra, S. M.; Sigman, M. S. Palladium-
Catalyzed Allylic Cross-Coupling Reactions of Primary and Secondary
Homoallylic Electrophiles. J. Am. Chem. Soc. 2012, 134, 11408−
11411. (b) Stokes, B. J.; Bischoff, A. J.; Sigman, M. S. Pd(quinox)-
Catalyzed Allylic Relay Suzuki Reactions of Secondary Homostyrenyl
Tosylates via Alkene-Assisted Oxidative Addition. Chem. Sci. 2014, 5,
2336−2339.
(17) Guo, Y.-A.; Liang, T.; Kim, S. W.; Xiao, H.; Krische, M. J.
Nickel-Catalyzed Cross-Coupling of Vinyl Dioxanones to Form
Enantiomerically Enriched Cyclopropanes. J. Am. Chem. Soc. 2017,
139, 6847−6850.
(18) For selected reviews, see: (a) Denmark, S. E.; Fu, J. Catalytic
Enantioselective Addition of Allylic Organometallic Reagents to
Aldehydes and Ketones. Chem. Rev. 2003, 103, 2763−2793. (b) Yus,
́
M.; Gonzalez, J. C.; Foubelo, F. Catalytic Enantioselective Allylation
of Carbonyl Compounds and Imines. Chem. Rev. 2011, 111, 7774−
7854.
(19) (a) Lim, H. J.; Smith, C. R.; RajanBabu, T. V. Facile Pd(II)-
and Ni(II)-Catalyzed Isomerization of Terminal Alkenes into 2-
Alkenes. J. Org. Chem. 2009, 74, 4565−4572. (b) Weber, F.; Schmidt,
(8) For selected examples of hydrovinylation, see: (a) Zhang, A.;
RajanBabu, T. V. Hydrovinylation of 1,3-Dienes: A New Protocol, an
Asymmetric Variation, and a Potential Solution to the Exocyclic Side
Chain Stereochemistry Problem. J. Am. Chem. Soc. 2006, 128, 54−55.
̈
A.; Rose, P.; Fischer, M.; Burghaus, O.; Hilt, G. Double-Bond
Isomerization: Highly Reactive Nickel Catalyst Applied in the
Synthesis of the Pheromone (9Z,12Z)-Tetradeca-9,12-dienyl Acetate.
E
https://dx.doi.org/10.1021/acs.orglett.9b04634
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
pubs.acs.org/OrgLett
Letter
Org. Lett. 2015, 17, 2952−2955. (c) Weber, F.; Steinlandt, P. S.;
Ballmann, M.; Hilt, G. Structure-Dependent Nickel-Catalysed Trans-
position of N-Allylamides to E- or Z-Enamides. Synthesis 2016, 49,
440−450.
(20) (a) Lappert, M. F.; Nile, T. A.; Takahashi, S. Homogeneous
catalysis: II. Ziegler systems as catalysts for hydrosilylation. J.
Organomet. Chem. 1974, 72, 425−439. (b) Takimoto, M.; Hiraga,
Y.; Sato, Y.; Mori, M. Nickel-Catalyzed Regio- and Stereoselective
Synthesis of Homoallylic Alcohol Derivatives from Dienes and
Aldehydes. Tetrahedron Lett. 1998, 39, 4543−4546. (c) Sawaki, R.;
Sato, Y.; Mori, M. Ligand-Controlled Highly Stereoselective
Syntheses of E- and Z-Allylsilanes from Dienes and Aldehydes
Using Nickel Complex. Org. Lett. 2004, 6, 1131−1133.
(21) (a) Kobayashi, Y.; Mizojiri, R.; Ikeda, E. Nickel-Catalyzed
Coupling Reaction of 1,3-Disubstituted Secondary Allylic Carbonates
and Lithium Aryl- and Alkenylborates. J. Org. Chem. 1996, 61, 5391−
5399. (b) Kobayashi, Y.; Tokoro, Y.; Watatani, K. Preparation of
Functionalized Zinc Borates and their Coupling Reaction with Allylic
Acetates. Tetrahedron Lett. 1998, 39, 7537−7540. (c) Srinivas, H. D.;
Zhou, Q.; Watson, M. P. Enantiospecific, Nickel-Catalyzed Cross-
Couplings of Allylic Pivalates and Arylboroxines. Org. Lett. 2014, 16,
3596−3599. (d) Cobb, K. M.; Rabb-Lynch, J. M.; Hoerrner, M. E.;
Manders, A.; Zhou, Q.; Watson, M. P. Stereospecific, Nickel-
Catalyzed Suzuki-Miyaura Cross-Coupling of Allylic Pivalates To
Deliver Quaternary Stereocenters. Org. Lett. 2017, 19, 4355−4358.
F
https://dx.doi.org/10.1021/acs.orglett.9b04634
Org. Lett. XXXX, XXX, XXX−XXX