Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
1
Scheme 2 shows a plausible reaction mechanism. It is known that
silyl copper species (A) is generated upon the reaction of PhMe2Si–
B(pin) with copper complexes.8 Thus, A is the key catalyst species
involved in the catalytic cycles (step 0). Then, A is subsequently
added across a sterically less hindered C-C double bond of 1,3-diene
(2), yielding an allylcopper intermediates B or B’ (step 1). Next, B’
would react with a nitrile (1) at the -position to provide C via 6-
membered ring transition state (step 2), as proposed in the allylation
of nitriles.14 Donating ability of monodentate phosphines facilitates
the nucleophilic attack step. Finally, the -bond metathesis of C with
PhMe2Si–B(pin) produces an imine (D) and regenerates the active
DOI: 10.1039/D0CC01803A
2871. (c) M. Jeganmohan and C.-H. Cheng, Chem. Commun., 2008,
3101–3117. (d) S. Yu and S. Ma, Angew. Chem. Int. Ed., 2012, 51,
3074–3112.
(a) N. Herrmann, D. Vogelsang, A. Behr and T. Seidensticker,
ChemCatChem, 2018, 10, 5342–5365. (b) Y. Xiong, Y. Sun and G.
Zhang, Tetrahedron Lett., 2018, 59, 347–355.
2
3
(a) E. W. Colvin, in Silicon in Organic Synthesis, Butterworths, London,
1981, pp 44–82. (b) E. W. Colvin, in Silicon Reagents in Organic
Synthesis, Academic, London, 1988, pp 7–19. (c) E. Langkopf and D.
Schinzer, Chem. Rev., 1995, 95, 1375–1408. (d) T. A. Blumenkopf and
L. E. Overman, Chem. Rev., 1986, 86, 857–873. (e) I. Fleming, J.
Dunogues and R. Smithers, Org. React., 1989, 37, 57–575.
T. Fujihara and Y. Tsuji, Synthesis, 2018, 50, 1737–1749.
(a) Y. Tani, T. Fujihara, J. Terao and Y. Tsuji, J. Am. Chem. Soc., 2014,
136, 2332–2333. (b) T. Fujihara, A. Sawada, T. Yamaguchi, Y. Tani, J.
Terao and Y. Tsuji, Angew. Chem. Int. Ed., 2017, 56, 1539–1543. (c) Y.
Tani, T. Yamaguchi, T. Fujihara, J. Terao and Y. Tsuji, Chem. Lett., 2015,
44, 271–273.
4
5
catalyst species
A (step 4). Acidic work-up provides the
corresponding ketone (3).
Scheme 2 Possible Catalytic Cycle
6
7
8
9
Z.-T. He, X.-Q. Tang, L.-B. Xie, M. Chen, P. Tian and G.-Q. Lin, Angew.
Chem. Int. Ed., 2015, 54, 14815–14818.
O
R2
J. Rae, K. Yeung, J. J. W. McDouall and D. J. Procter, Angew. Chem. Int.
Ed., 2016, 55, 1102–1107.
R
R1
SiMe2Ph
C. Kleeberg, M. S. Cheung, Z. Lin and T. B. Marder, J. Am. Chem. Soc.,
2011, 133, 19060–190603.
3
H3O+
G. J. P. Perry, T. Jia and D. J. Procter, ACS Catal., 2020, 10, 1485–1499,
and references sited therein.
AcO-Cu-L
B(pin)
PhMe2Si-B(pin)
10 (a) J.-J. Feng and M. Oestreich, Angew. Chem. Int. Ed. 2019, 58,
8211−8215. (b) T. Jia, M. J. Smith, A. P. Pulis, G. J. Perry and D. J.
Procter, ACS Catal., 2019, 9, 6744−6750. (c) T. Jia, Q. He, R. E. Ruscoe,
A. Pulis and D. J. Procter, Angew. Chem. Int. Ed., 2018, 57, 11305–
11309. (d) K. B. Smith and M. K. Brown, J. Am. Chem. Soc., 2017, 139,
7721–7724. (e) S. R. Sardini and M. K. Brown, J. Am. Chem. Soc., 2017,
139, 9823–9826. (f) Y. Huang, K. B. Smith and M. K. Brown, Angew.
Chem. Int. Ed., 2017, 56, 13314−13318. (g) L. Jiang, P. Cao, M. Wang,
B. Chen, B. Wang and J. Liao, Angew. Chem. Int. Ed., 2016, 55, 13854-
13858. (h) X. Li, F. Meng, S. Torker, Y. Shi and A. H. Hoveyda, Angew.
Chem. Int. Ed., 2016, 55, 9997-10002. (i) K. Kubota, Y. Watanabe, K.
Hayama and H. Ito, J. Am. Chem. Soc., 2016, 138, 4338−4341. (j) K.
Semba, M. Shinomiya, T. Fujihara, J. Terao and Y. Tsuji, Chem. Eur. J.,
2013, 19, 7125–7133. (k) Y. Sasaki, C. Zhong, M. Sawamura and H. Ito,
J. Am. Chem. Soc., 2010, 132, 1226–1227.
11 (a) 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, 18825−18835. (b) C. Li,
K. Shin, R. Y. Liu and S. L. Buchwald, Angew. Chem. Int. Ed., 2019, 58,
17074−17080. (c) C. Li, R. Y. Liu, L. T. Jesikiewicz, Y. Yang, P. Liu, and S.
L. Buchwald, J. Am. Chem. Soc., 2019, 141, 5062−5070. (d) B. Fu, X.
Yuan, Y. Li, Y. Wang, Q. Zhang, T. Xiong and Q. Zhang, Org. Lett., 2019,
21, 3576−3580. (e) D. Li, Y. Park, W. Yoon, H. Yun and J. Yun, Org. Lett.,
2019, 21, 9699−9703. (f) Y.-Y. Gui, N. Hu, X.-W. Chen, L. Liao, T. Ju, J.-
H. Ye, Z. Zhang, J. Li and D.-G. Yu, J. Am. Chem. Soc., 2017, 139,
17011−17014.
N
R2
step 0
R
AcO-B(pin)
R2
R1
SiMe2Ph
Me2PhSi-Cu-L
D
R1
2a
A
step 1
step 3
PhMe2Si-B(pin)
Cu- R2
L
Cu-L
R2
Cu-L
N
R2
R
R1
SiMe2Ph
R1
SiMe2Ph
B
B'
R1
SiMe2Ph
C
step 2
R-CN
1
In conclusion, three-component coupling reactions using
nitriles, 1,3-dienes, and silylboranes were reported for the first
time. The desires reactions proceeded smoothly in the presence
of copper catalysts. The corresponding ,-unsaturated ketones
with a (dimethylphenylsilyl)methyl moiety at the -position
were obtained in good to high yields with high regioselectivity.
Further studies to clarify reaction mechanism and application to
enantioselective reactions are now in progress.
12 R. C. Larock, Comprehensive Organic Transformation, 2nd Ed., Wiley-
VCH, New York, 1999.
13 (a) A. Cope, H. Holmes and O. House, Org. React., 1957, 9, 107−331.
(b) S. Arseniyadis, K. S. Kyler and D. S. Watt, Org. React., 1984, 31,
1−71. (c) F. Dénès, A. Pérez-Luna and F. Chemla, Chem. Rev., 2010,
110, 2366–2447.
This work was supported by JSPS KAKENHI Grant Number
17H03096 in Grant-in-Aid for Scientific Research (B) from MEXT,
Japan (YT). TF acknowledged JSPS KAKENHI Grant Number
18H04257 in Precisely Designed Catalysts with Customized
Scaffolding from MEXT, Japan and Tokuyama Science
Foundation for financial support.
14 G. Courtois and L. Miginiac, J. Organomet. Chem., 1974, 69, 1–44.
15 (a) M. Hayashi, S. Bachman, S. Hashimoto, C. C. Eichman and B. M.
Stoltz, J. Am. Chem. Soc., 2016, 138, 8997−9000 (b) L. Zhao and X. Lu,
Angew. Chem. Int. Ed. 2002, 41, 4343–4345. (c) B. Skillinghaug, C.
Sköld, J. Rydfjord, F. Svensson, M. Behrends, J. Sävmarker, P. J. R.
Sjöberg and M. Larhed, J. Org. Chem., 2014, 79, 12018−12032. (d) M.
Xiong, X. Xie and Y. Liu, Org. Lett., 2017, 19, 3398–3401. (e) J. H. Kim
and S.-G. Lee, Org. Lett., 2011, 13, 1350–1353.
16 S. Zhang, J. del Pozo, F. Romiti, Y. Mu, S. Torker and A. H. Hoveyda,
Science, 2019, 364, 45−54.
17 See ESI for detail.
Conflicts of interest
There are no conflicts to declare.
18 A. Boreux, K. Indukuri, F. Gagosz and O. Riant, ACS Catal., 2017, 7,
8200–8204
19 A. Sawada, T. Fujihara and Y. Tsuji, Adv. Synth. Catal., 2018, 360,
2621–2625.
Notes and references
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins