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Journal Name
COMMUNICATION
Notes and references
†
Present address: Department of BaDsiOcI: S10c.i1e0n3c9e/C, 7GCCra0d2u81a6tDe
School of Art and Sciences, The University of Tokyo, Tokyo
153-8902.
1
2
The Chemistry of Organocopper Compounds (Eds.: Z.
Rappoport and I. Marek), Wiley, Chichester, 2009.
S. Díez-González and S. P. Nolan, Acc. Chem. Res. 2008, 41
,
349–358. (b) C. Deutsch, N. Krause and B. H.Lipshutz, Chem.
Rev., 2008, 108, 2916–2927; (c) S. Rendler and M. Oestreich,
Angew. Chem., Int. Ed., 2007, 46, 498–504; (d) B. H. Lipshutz,
Synlett, 2009, 509–524; (e) J. Abraham, G. Lalic, J. P. Sadighi,
Chem. Rev. 2016, 116, 8318–8372.
3
4
N. P. Mankad, D. S. Laitar and J. P. Sadighi, Organometallics,
2004, 23, 3369–3371
Scheme 2 Stoichiometric reactions relevant to mechanism.
Semihydrogenation, see; (a) K. Semba, T. Xu, T. Fujihara, J.
Terao and Y. Tsuji, Adv. Synth. Catal., 2012, 354, 1542–1550;
(b) A. M. Whittaker and G. Lalic, Org. Lett., 2013, 15, 1112–
1115; (c) G.-H. Wang, H.-Y. Bin, M. Sun, S.-W. Chen, J.-H. Liu,
and C.-M. Zhong, Tetrahedron, 2014, 70, 2175–2179; (d) J. F.
Daeuble, C. McGettigan and J. M. Stryker, Tetrahedron Lett.,
1990, 31, 2397–2400.
A possible catalytic cycle is shown in Scheme 3. First, the
reaction of copper chloride complex
copper t-butoxide (step 1). Copper hydride (Cu–H) species
is generated in situ by the reaction of HSi(OMe)3 with
2).3,8a Next,
from the less hindered site, giving (Z)-
intermediate (step 3). Then, the addition of
A with LiOtBu affords
B
C
(step
B
5
Hydroaminations, see; (a) S.-L. Shi, Z.-L. Wong and S. L.
Buchwald, Nature, 532, 353-356; (b) S. Zhu, N. Niljianskul and
C
adds across a terminal double bond of an allene 1
S. L. Buchwald, Nature Chem., 2016,
8
, 144–150; (c) S.-L. Shi
, 38–44; (d) J. A.
D
-allylcopper
to the C–C
and S. L. Buchwald, Nature Chem., 2015,
7
D
Bandar, M. T. Pirnot and S. L. Buchwald, J. Am. Chem. Soc.,
2015, 137, 14812–14818; (e) D. Niu and S. L. Buchwald, J. Am.
Chem. Soc., 2015, 137, 9716–9721; (f) Y. Yang, S.-L. Shi, D. Niu,
P. Liu and S. L. Buchwald, Science, 2015, 349, 62–66; (g) N.
Niljianskul, S. Zhu and S. L. Buchwald, Angew. Chem. Int. Ed.,
2015, 54, 1638–1641; (h) S. Zhu and and S. L. Buchwald, J. Am.
Chem. Soc., 2013, 135, 15913–15916; (i) S. Zhu, N. Niljianskul
and S. L. Buchwald, J. Am. Chem. Soc., 2013, 135, 15746–
15749; (j) D. Nishikawa, K. Hirano and M. Miura, J. Am. Chem.
Soc., 2015, 137, 15620–15623; (k) Y. Miki, K. Hirano, T. Satoh
and M. Miura, Org. Lett. 2014, 16, 1498–1501; (l) Y. Miki, K.
Hirano, T. Satoh and M. Miura, Angew. Chem. Int. Ed., 2013,
52, 10830–10834.
Hydroborations, see; (a) K. Semba, M. Shinomiya, T. Fujihara,
J. Terao, Y. Tsuji, Chem. Eur. J., 2013, 18, 7125–7132; (b) K.
Semba, T. Fujihara, J. Terao and Y. Tsuji, Chem. Eur. J., 2012,
18, 4179–4184; (c) B. H. Lipshutz, Ž. V. Bošković and D. H. Aue,
Angew. Chem. Int. Ed., 2008, 47, 10183–10186; (d) Y. Zi and J.
F. Hartwig, J. Am. Chem. Soc., 2016, 138, 6703–6706.
(a) J. S. Bandar, E. Ascic and S. L. Buchwald, J. Am. Chem. Soc.,
2016, 138, 5821–5824; (b) E. Ascic and S. L. Buchwald, J. Am.
Chem. Soc., 2015, 137, 4666–4669.
double bond of
isomerization17 of
provides 3 (step 5) and regenerates A.
2
affords
E, with concomitant E/Z
D
(step 4). Subsequent elimination from
E
6
7
8
(a) T. Fujihara, T. Xu, K. Semba, J. Terao and Y. Tsuji, Angew.
Chem. Int. Ed., 2011, 50, 523–527; (b) Y. Tani, K. Kuga, T.
Fujihara, J. Terao and Y. Tsuji, Chem. Commun., 2015, 51
13020–13023.
,
Scheme 3 Possible Reaction Mechanism.
9
(a) M. R. Uehling, R. P. Rucker and G. Lalic, J. Am. Chem. Soc.
2014, 136, 1424–1427; (b) A. M. Suess, M. R. Uehling, W.
Kaminsky and G. Lalic, J. Am. Chem. Soc., 2015, 137, 7747–
7753.
In conclusion, we have developed
a
Cu-catalyzed
hydroallylation of allenes using a hydrosilane and allyl chlorides.
The reaction afforded (E)-1,5-dienes in good to high yields with
good to high selectivity. Further studies on the reaction
mechanism and applications including enantioselective
reactions are now in progress.
10 Y.-M. Wang, N. C. Bruno, A. L. Placeres, S. Zhu and S. L.
Buchwald, J. Am. Chem. Soc., 2015, 137, 10524–10527.
11 Selected examples for the use of 1,5-dienes in organic
synthesis: (a) R. J. Felix, D. Weber, O. Gutierrez, D. J. Tantillo
and M. R. Gagné, Nat. Chem., 2012, 4, 405–409; (b) J. A.
Feducia and M. R. Gagné, J. Am. Chem. Soc., 2008, 130, 592–
599; (c) Y.-J. Zhao, S.-S. Chng and T.-P. Loh, J. Am. Chem. Soc.,
2007, 129, 492–493; (d) T. J. Donohoe and S. Butterworth,
Angew. Chem. Int. Ed., 2003, 42, 948–951; (e) R. C. Brown and
J. F. Keily, Angew. Chem. Int. Ed., 2001, 40, 4496–4498.
This work was supported by JSPS KAKENHI Grant Number
25708017 in Grant-in-Aid for Young Scientists (A) and Grant
Number JP16H01020 in Precisely Designed Catalysts with
Customized Scaffolding from MEXT, Japan.
12 (a) Y. Yamamoto and K. Maruyama, J. Am. Chem. Soc., 1978,
100, 6282–6284; (b) B. M. Trost and E. Keinan, Tetrahedron
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