Nickel-catalyzed allyl-allyl coupling reactions between 1,3-dienes and allylboronates

Article abstract of DOI:10.1039/d0cc02697b

A regiospecific allyl-allyl coupling reaction between 1,3-dienes and allylboronates has been demonstrated under nickel catalysis. Salient features of this method include the earth-abundant metal catalyst, excellent regioselectivity and good functional group tolerance. Notably, even congested allyl substrates can also be applied to this protocol, thus allowing for the rapid preparation of a series of valuable 1,5-dienes. This journal is

Full text of DOI:10.1039/d0cc02697b

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: D. Ji, G. He, W.
Zhang, C. Zhao, Y. Hu and Q. Chen, Chem. Commun., 2020, DOI: 10.1039/D0CC02697B.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 5
ChemComm
View Article Online
DOI: 10.1039/D0CC02697B
COMMUNICATION
Nickel-catalyzed allyl-allyl coupling reactions between 1,3-dienes
and allylboronates
Ding-Wei Ji,a,b Gu-Cheng He,a Wei-Song Zhang,a Chao-Yang Zhao,a Yan-Cheng Hu,a Qing-An Chen*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A regiospecific allyl-allyl coupling reaction between 1,3-dienes and complexity.5,6 Despite the fact that reductive allyl–allyl cross-
allylboronates has been demonstrated under nickel catalysis. coupling of allenes or alkynes have been developed by
Salient features of this method include the earth-abundant metal Hoveyda,7 Tsuji,8 Zhang9 and our group,10 the direct utilization
catalyst, excellent regioselectivity and good functional group of 1,3-dienes in allyl–allyl coupling for the synthesis of 1,5-
tolerance. Notably, even congested allyl substrates can also be dienes was rarely realized. Very recently, Meek and co-workers
applied to this protocol, thus allowing for the rapid preparation of reported
a
seminal work on the rhodium-catalyzed
a series of valuable 1,5-dienes.
hydroallylation of 1,3-dienes with allyltrifluoroborates.11 Due
to undesired alkene isomerization, a mixture of 1,5- and 1,4-
dienes were obtained in most cases (Scheme 1b). In light of
excellent performance of nickel catalyst in 1,3-diene
hydrofunctionalization,12 we envisioned that the relatively
cheap and earth-abundant nickel could also serve as an
attractive alternative to noble rhodium catalyst in
hydroallylation of 1,3-dienes. As an extension of our studies on
catalytic functionalization of dienes,13 herein we report this
regiospecific reductive allyl-allyl cross-coupling between 1,4-
dienes and allylboronates under nickel-hydride catalysis
(Scheme 1c).
Owing to the diverse reactivity of the allyl and vinyl groups,
1,5-diene fragments and their derivatives often serve as useful
building blocks in organic synthesis.1 Besides, 1,5-diene unit
itself is widely found in biologically active molecules and
natural products.2 Therefore, their synthesis has attracted
considerable attention over the past decades and some
efficient strategies have been established.3 Among them,
transition metal-catalyzed cross-coupling between allyl
electrophiles and allyl nucleophiles represents one of the
simplest and most straightforward tools.4 However, two
inherent challenges limit the applications of this classic
strategy (Scheme 1a). First, the requirement for pre-
installation of
a leaving group onto the starting allyl
electrophiles may diminish the synthetic economy. Second,
several difficulties such as the poor regioselective control of
products or the competing formation of side product 1,3-
dienes derived from β-hydride elimination may arise when
utilizing internal allyl electrophiles as the coupling partners.4l,4o
In this context, developing a general and regioselective allyl-
allyl coupling reaction to access 1,5-dienes from non-activated
precursors is still highly demanded.
As 1,3-dienes are easily accessible and versatile synthons in
organic synthesis, the employment of 1,3-dienes as greener
allyl precusors via the catalytic hydrofunctionalization is
becoming an attractive way for the buildup of molecular
a. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian116023,
P. R. China, E-mail: qachen@dicp.ac.cn, Web: http://www.lbcs.dicp.ac.cn
b. University of Chinese Academy of Sciences, Beijing 100049, P. R. China
Scheme 1. Transition metal-catalyzed allyl−allyl coupling reactions
Electronic
Supplemen tary
Information
(E SI)
available:
See
DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 5
COMMUNICATION
Journal Name
We initiated our research with 1-phenyl-1,3-butadiene 1a transformed into product 3o in an excellent yield.ViHewetAertircolecOyncllinice
DOI: 10.1039/D0CC02697B
and allylB(pin) 2a as the model substrates (Table 1). Pleasingly, substrates 3p-3r were also compatible in current protocol and
the expected 1,5-diene 3a was observed as sole product in the afforded the products in 21-60% yields.
presence of Ni(COD)2 (5 mol%) and PPh3 (10 mol%) in MeOH at
80 ºC (entry 1). The evaluation of solvent suggested that the
Table 2. Hydroallylation of 1,3-diene
yield of 3a could be improved to 58% when the reaction was
performed in ethanol (entries 2-5). After examining various
ligands, we obtained an increased yield of 3a with P(nBu)3
(entries 6-11). While lowering or raising temperature resulted
in decreased yields (entries 12-13), increasing the reaction
concentration successfully led to 3a in an excellent yield (93%,
entry 14).
Table 1. Optimization for hydroallylation of 1,3-diene
entry
1
ligand (x mol%)
PPh3 (10)
PPh3 (10)
PPh3 (10)
PPh3 (10)
PPh3 (10)
PCy 3 (10)
P(tBu)3 (10)
P(nBu)3 (10)
dppp (5)
solvent
MeOH
EtOH
nPrOH
iPrOH
tBuOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
yield (%)b
50
58
2
3
51
4
55
5
45
6
22
7
trace
83
8
9
2
10
11
12c
13d
14e
15f
dppb (5)
50
dppf (5)
5
P(nBu)3 (10)
P(nBu)3 (10)
P(nBu)3 (10)
P(nBu)3 (10)
42
74
93 (85)g
75
aReaction conditions: 1a (0.20 mmol), 1b (0.40 mmol), Ni(COD)2 (5 mol%),
Ligand (5-10 mol%), solvent (0.4 M), 80 ºC, 18 h. bDetermined by GC-FID
with 1,3,5-trimethoxybenzene as the internal standard. c60 ºC. d100 ºC.
eEtOH (0.8 M), fEtOH (0.2 M). gIsolated yield.
With the optimal reaction conditions in hand, we shifted our
attention to explore the substrate scope of this nickel-
catalyzed allyl-allyl coupling reaction. As shown in Table 2, we
generally obtained various 1,5-dienes in good yields and
selectivities. The 1,3-dienes with alkyl substituents on phenyl
ring such as methyl, ethyl and butyl all gave desirable products
in good to excellent yields (3b-3d, 3j, 3k). The strong electron-
donating substrates (e.g. OMe, NMe2) were comparatively
sluggish in this reaction (3e and 3f). A fluoro group was also
well tolerated, delivering the 1,5-diene 3g in 80% yield.
Electron-withdrawing Ph and CF3 groups exhibited higher
reactivity and offered good yields of 1,5-dienes even at lower
temperature (3h, 3i and 3l). Notably, ortho-substituted
substrates 1m and 1n also proceeded smoothly, regardless of
their steric hindrance, generating the corresponding products
in 83% and 85% yield, respectively. On replacing the phenyl
group with 1-naphthalenyl group, the substrate was
The transition-metal catalyzed allyl–allyl couplings with
congested allylboronates is a challenging task and very limited
works have been successfully realized.4j,4o Satisfactorily,
although linear substrate 2b was unreactive under current
reaction conditions, the prenylative product 3s could be
obtained in an acceptable yield with branched prenyl-B(pin)
(Table 3). Moreover, geranyl-B(pin) 2d also reacted well with
1a and gave the product 3t in 42% yield. These results
complement the Rh-catalyzed hydroallylation method for the
synthesis of 1,5-dienes.11
2 | J. Name., 2012, 00, 1-3
This journal is © The RoyalSociety of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 5
ChemComm
Journal Name
COMMUNICATION
Table 3. The scope of allylborons
View Article Online
DOI: 10.1039/D0CC02697B
Scheme 3. Deuterium-Labeling and Control Experiments
While further studies are warranted, we tentatively
proposed the following mechanism on the basis of literature
and our own observations (Figure 1).11,12f First, the oxidative
To further verify the synthetic utility of this protocol, a scale- addition of the ethanol with a nickel(0) precursor A gives Ni(II)-
up reaction (5.0 mmol) was performed, delivering 1,5-diene hydride species B, which then undergoes migratory insertion
product 3a in 88% yield (762 mg, Scheme 2). Besides, further with 1,3-diene 1 to afford allyl-Ni (II) intermediate C or C' in a
synthetic transformation of 3a with phenyl acrylate under reversible pathway. Through the transmetalation between
cross olefin-metathesis conditions furnished the unsaturated allyl-Ni (II) intermediate and allyl-B(pin) 2, bis(allyl)Ni species D
ester 4 in 37% yield. Moreover, the hydroboration/oxidation is produced. Finally, reductive elimination of D leads to
reactions of 3a could proceed efficiently to give the alcohol 5 terminal 1,5-diene product 3 and regenerates the nickel(0). It
in a good yield (82%).
should be noted that the existence of allyl-Ni (II) intermediate C
/C' were supported by the observation of 6 via a reductive
elimination step. Therefore, current mechanism was preferred
over the reported transmetalation-alkene insertion pathway in
previous Rh-catalyzed reactions.11
Scheme 2. Scale-up synthesis and transformations of 1,5-diene 3a
To gain some insights into the mechanism, a deuterium-
labeling experiment with 1-phenyl-1,3-butadiene 1a and allyl-
B(pin) 2a was conducted with EtOH-d6. As depicted in Scheme
3a, while 0.37 deuterium was incorporated into the methyl
group of 1,5-diene product, 0.64 deuterium was also
exchanged into terminal CH2 of the recovered diene 1a. This
observation supports a reversible process of the migratory
insertion between the 1,4-diene and the Ni-hydride. In the
absence of 2a, hydroalkoxylative product 6 could also be
obtained in 21% NMR yield under the standard reaction
condition. However, the reaction between 6 and 2a under
standard condition could not deliver 1,5-diene 3a (Scheme 3b),
thus excluding the possibility that 6 is an intermediate of the
process.
Figure 1. Proposed mechanism for Ni-catalyzed hydroallylation
In summary,
reaction between 1,3-dienes and allyl-B(pin) was achieved via
hydroallylative protocol. This strategy exhibited good
a nickel-catalyzed allyl–allyl cross-coupling
a
functional group tolerance, exclusive regioselectivity and high
reactivity, thus complementing a facile route to access 1,5-
dienes. Further studies on expanding the scope of unsaturated
substrates, detailed mechanism as well as the asymmetric
version are now in progress in our laboratory.
This journal is © The Royal Society of Chemistry 20xx
J . Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
122; (f) G. J. P. Perry, T. Jia and D. J. Procter, ACS Catal.,
Conflicts of interest
There are no conflicts to declare.
View Article Online
2020, 10, 1485.
DOI: 10.1039/D0CC02697B
6. (a) N. J. Adamson, E. Hull and S. J. Malcolmson, J. Am. Chem.
Soc., 2017, 139, 7180; (b) Y. Y. Gui, N. Hu, X. W. Chen, L. L.
Liao, T. Ju, J. H. Ye, Z. Zhang, J. Li and D. G. Yu, J. Am. Chem.
Soc., 2017, 139, 17011; (c) J. S. Marcum, C. C. Roberts, R. S.
Manan, T. N. Cervarich and S. J. Meek, J. Am. Chem. Soc.,
2017, 139, 15580; (d) X. H. Yang and V. M. Dong, J. Am.
Chem. Soc., 2017, 139, 1774; (e) X. H. Yang, A. Lu and V. M.
Dong, J. Am. Chem. Soc., 2017, 139, 14049; (f) N. J.
Adamson, K. C. E. Wilbur and S. J. Malcolmson, J. Am. Chem.
Soc., 2018, 140, 2761; (g) S. Z. Nie, R. T. Davison and V. M.
Dong, J. Am. Chem. Soc., 2018, 140, 16450; (h) X. H. Yang, R.
T. Davison and V. M. Dong, J. Am. Chem. Soc., 2018, 140,
10443; (i) X. W. Chen, L. Zhu, Y. Y. Gui, K. Jing, Y. X. Jiang, Z.
Y. Bo, Y. Lan, J. Li and D. G. Yu, J. Am. Chem. Soc., 2019, 141,
18825; (j) G. Wang, L. Gao, H. Chen, X. Liu, J. Cao, S. Chen, X.
Cheng and S. Li, Angew. Chem. Int. Ed., 2019, 58, 1694; (k) X.
H. Yang, R. T. Davison, S. Z. Nie, F. A. Cruz, T. M. McGinnis
and V. M. Dong, J. Am. Chem. Soc., 2019, 141, 3006.
7. (a) F. K. Meng, K. P. McGrath and A. H. Hoveyda, Nature,
2014, 513, 367; (b) Y. Sun, Y. Zhou, Y. Shi, J. Del Pozo, S.
Torker and A. H. Hoveyda, J. Am. Chem. Soc., 2019, 141,
12087.
8. K. Semba, N. Bessho, T. Fujihara, J. Terao and Y. Tsuji,
Angew. Chem. Int. Ed., 2014, 53, 9007.
9. G. Xu, B. Fu, H. Zhao, Y. Li, G. Zhang, Y. Wang, T. Xiong and Q.
Zhang, Chem. Sci., 2019, 10, 1802.
10. D.-W. Ji, Y.-C. Hu, H. Zheng, C.-Y. Zhao, Q.-A. Chen and
Vy M. Dong, Chem. Sci., 2019, 10, 6311.
Acknowledgements
Financial support from Dalian Institute of Chemical Physics
(DICPI201902), the National Natural Science Foundation of
China (21702204), Liaoning Revitalization Talents Program
(XLYC1807181), and the "Thousand Youth Talents Plan" is
acknowledged.
Notes and references
1. (a) H.-Y. Lee, Acc. Chem. Res., 2015, 48, 2308; (b) J. Adrian, S.
Roth and C. B. W. Stark, ChemCatChem, 2016, 8, 1679; (c) P.
K. Dornan, D. Lee and R. H. Grubbs, J. Am. Chem. Soc., 2016,
138, 6372; (d) Y. R. Gao, D. Y. Wang and Y. Q. Wang, Org.
Lett., 2017, 19, 3516; (e) B. Schmidt, M. H. Petersen and D.
Braun, J. Org. Chem., 2018, 83, 1627.
2. (a) E. Breitmaier, Terpenes: Flavors, Fragrances, Pharmaca,
Pheromones, Wiley-VCH, Weinheim, Germany, 2006; (b) L.
Chuang, C. H. Wen, Y. R. Lee, Y. L. Lin, L. R. Hsu, S. Y. Wang
and F. H. Chu, J. Nat. Prod., 2018, 81, 1162; (c) A. C. Huang,
Y. J. Hong, A. D. Bond, D. J. Tantillo and A. Osbourn, Angew.
Chem. Int. Ed., 2018, 57, 1291.
3. (a) Y. Sumida, S. Hayashi, K. Hirano, H. Yorimitsu and K.
Oshima, Org. Lett., 2008, 10, 1629; (b) F. Ding, R. William, F.
Wang and X.-W. Liu, Chem. Commun., 2012, 48, 8709; (c) J.
Y. Hamilton, D. Sarlah and E. M. Carreira, J. Am. Chem. Soc.,
2014, 136, 3006; (d) Q. Yuan, K. Yao, D. Liu and W. Zhang,
Chem. Commun., 2015, 51, 11834; (e) M. Ellwart, I. S.
Makarov, F. Achrainer, H. Zipse and P. Knochel, Angew.
Chem. Int. Ed., 2016, 55, 10502; (f) H. Wang, S. Qiu, S. Wang
and H. Zhai, ACS Catal., 2018, 8, 11960.
4. (a) P. Srihari, A. P. Singh, A. K. Basak and J. S. Yadav,
Tetrahedron Lett., 2007, 48, 5999; (b) P. Zhang, L. A. Brozek
and J. P. Morken, J. Am. Chem. Soc., 2010, 132, 10686; (c) L.
A. Brozek, M. J. Ardolino and J. P. Morken, J. Am. Chem. Soc.,
2011, 133, 16778; (d) T. Chatterjee, R. Dey and B. C. Ranu,
New J. Chem., 2011, 35, 1103; (e) A. Jimenez-Aquino, E. F.
Flegeau, U. Schneider and S. Kobayashi, Chem. Commun.,
2011, 47, 9456; (f) P. Zhang, H. Le, R. E. Kyne and J. P.
Morken, J. Am. Chem. Soc., 2011, 133, 9716; (g) M. B. Li, Y.
Wang and S. K. Tian, Angew. Chem. Int. Ed., 2012, 51, 2968;
(h) V. Hornillos, M. Perez, M. Fananas-Mastral and B. L.
Feringa, J. Am. Chem. Soc., 2013, 135, 2140; (i) H. Le, R. E.
Kyne, L. A. Brozek and J. P. Morken, Org. Lett., 2013, 15,
1432; (j) M. J. Ardolino and J. P. Morken, J. Am. Chem. Soc.,
2014, 136, 7092; (k) J. Y. Hamilton, N. Hauser, D. Sarlah and
E. M. Carreira, Angew. Chem. Int. Ed., 2014, 53, 10759; (l) H.
Le, A. Batten and J. P. Morken, Org. Lett., 2014, 16, 2096; (m)
Y. Yasuda, H. Ohmiya and M. Sawamura, Angew. Chem. Int.
Ed., 2016, 55, 10816; (n) X. B. Wang, X. M. Wang, Z. B. Han,
Z. Wang and K. L. Ding, Angew. Chem. Int. Ed., 2017, 56,
1116; (o) Y. Zheng, B.-B. Yue, K. Wei and Y.-R. Yang, Org.
Lett., 2018, 20, 8035.
11. J. S. Marcum, T. N. Cervarich, R. S. Manan, C. C. Roberts
and S. J. Meek, ACS Catal., 2019, 9, 5881.
12. (a) J. Pawlas, Y. Nakao, M. Kawatsura and J. F. Hartwig, J.
Am. Chem. Soc., 2002, 124, 3669; (b) N. Saito, A. Kobayashi
and Y. Sato, Angew. Chem. Int. Ed., 2012, 51, 1228; (c) A.
Koepfer, B. Sam, B. Breit and M. J. Krische, Chem. Sci., 2013,
4, 1876; (d) X. Lian, W. Chen, L. Dang, Y. Li and C. Y. Ho,
Angew. Chem. Int. Ed., 2017, 56, 9048; (e) L. Cheng, M. M. Li,
L. J. Xiao, J. H. Xie and Q. L. Zhou, J. Am. Chem. Soc., 2018,
140, 11627; (f) L. J. Xiao, L. Cheng, W. M. Feng, M. L. Li, J. H.
Xie and Q. L. Zhou, Angew. Chem. Int. Ed., 2018, 57, 461; (g)
B. Chen, Y. Zhang, R. Wu, D. Fang, X. Chen, S. Wang, Y. Zhao,
P. Hu, K.-Q. Zhao, B.-Q. Wang and P. Cao, ACS Catal., 2019,
9, 11788; (h) Y. G. Chen, B. Shuai, X. T. Xu, Y. Q. Li, Q. L. Yang,
H. Qiu, K. Zhang, P. Fang and T. S. Mei, J. Am. Chem. Soc.,
2019, 141, 3395; (i) J. Long, P. Wang, W. Wang, Y. Li and G.
Yin, iScience, 2019, 22, 369; (j) L. Lv, D. Zhu, Z. Qiu, J. Li and
C.-J. Li, ACS Catal., 2019, 9, 9199; (k) X.-Y. Lv, C. Fan, L.-J.
Xiao, J.-H. Xie and Q.-L. Zhou, CCS Chem., 2019, 1, 328; (l) G.
Tran and C. Mazet, Org. Lett., 2019, 21, 9124; (m) G. Tran,
W. Shao and C. Mazet, J. Am. Chem. Soc., 2019, 141, 14814;
(n) Y.-L. Li, W.-D. Li, Z.-Y. Gu, J. Chen and J.-B. Xia, ACS Catal.,
2020, 10, 1528.
13. (a) Y. C. Hu, D. W. Ji, C. Y. Zhao, H. Zheng and Q. A. Chen,
Angew. Chem. Int. Ed., 2019, 58, 5438; (b) J. Yang, D. W. Ji, Y.
C. Hu, X. T. Min, X. G. Zhou and Q. A. Chen, Chem. Sci., 2019,
10, 9560; (c) Y. Li, Y. C. Hu, H. Zheng, D. W. Ji, Y. F. Cong and
Q. A. Chen, Eur. J. Org. Chem., 2019, 6510; (d) Y. Li, Y. C. Hu,
D. W. Ji, W. S. Zhang, G. C. He, Y. F. Cong and Q. A. Chen,
Chin. J. Catal., 2020, DOI: 10.1016/S1872-2067(20)63575-6.
5. (a) N. Herrmann, D. Vogelsang, A. Behr and T. Seidensticker,
ChemCatChem, 2018, 10, 5342; (b) M. Holmes, L. A.
Schwartz and M. J. Krische, Chem. Rev., 2018, 118, 6026; (c)
Y. Xiong, Y. W. Sun and G. Z. Zhang, Tetrahedron Lett., 2018,
59, 347; (d) N. J. Adamson and S. J. Malcolmson, ACS Catal.,
2020, 10, 1060; (e) X. Wu and L. Z. Gong, Synthesis, 2019, 51,
4 | J. Name., 2012, 00, 1-3
This journal is © The RoyalSociety of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 5 of 5
ChemComm
Journal Name
COMMUNICATION
View Article Online
DOI: 10.1039/D0CC02697B
Graphical Abstracts (Table of Contents Entry)
A nickel-hydride catalysis has been developed to facilitate
the allyl–allyl cross-coupling reactions between 1,3-dienes
and allyl-B(pin) in excellent regioselectivity.
This journal is © The Royal Society of Chemistry 20xx
J . Name., 2013, 00, 1-3 | 5
Please do not adjust margins