10.1002/anie.201813222
Angewandte Chemie International Edition
COMMUNICATION
[3]
[4]
For selected reviews, see: a) G. C. Fu, ACS Cent. Sci. 2017, 3, 692; b)
M. R. Netherton, G. C. Fu, Adv. Synth. Catal. 2004, 346, 1525; c) R.
Jana, T. P. Pathak, M. S. Sigman, Chem. Rev. 2011, 111, 1417; d) X.
Hu, Chem. Sci. 2011, 2, 1867; e) J. Choi, G. C. Fu, Science 2017, 356,
eaaf7230.
octenes (equimolar amounts of the four linear octene-isomers)
on 10 mmol scale, the reaction produced enantiopured terminal
alkylation product (3a) in an effective fashion (Scheme 1a).
Moreover, diphenylamides are attractive carboxylic acid
derivatives and can be easily converted into other useful
functional groups without erosion of enantiomeric excess.[6e] For
example, reduction of 3n and 4i with LiAlH4 cleaved the amide
group to deliver free primary alcohol 5n and 5i in 97% ee and
91% ee, respectively (Scheme 1b).
For Ni-catalyzed asymmetric Kumada reactions using racemic sec-alkyl
Grignard reagents, see: a) Y. Kiso, K. Tamao, N. Miyake, K. Yamamoto,
M. Kumada, Tetrahedron Lett. 1974, 15, 3; b) T. Hayashi, M. Tajika, K.
Tamao, M. Kumada, J. Am. Chem. Soc. 1976, 98, 3718; c) T. Hayashi,
M. Konishi, M. Fukushima, T. Mise, M. Kagotani, M. Tajika, M. Kumada,
J. Am. Chem. Soc. 1982, 104, 180; d) G. Consiglio, F. Morandini, O.
Piccolo, Tetrahedron 1983, 39, 2699; e) S. Pellet-Rostaing, C. Saluzzo,
R. Ter Halle, J. Breuzard, L. Vial, F. Le Guyader, M. Lemaire,
Tetrahedron: Asymmetry 2001, 12, 1983; For Pd-catalyzed asymmetric
Kumada reaction using racemic sec-alkyl Grignard reagents, see: f) H.
Horibe, Y. Fukuda, K. Kondo, H. Okuno, Y. Murakami, T. Aoyama,
Tetrahedron 2004, 60, 10701; For Ni-catalyzed asymmetric Kumada
reactions using racemic alkyl halides, see: g) S. Lou, G. C. Fu, J. Am.
Chem. Soc. 2010, 132, 1264; For Co-catalyzed asymmetric Kumada
reaction using racemic alkyl halides, see: h) J. Mao, F. Liu, M. Wang, L.
Wu, B. Zheng, S. Liu, J. Zhong, Q. Bian, P. J. Walsh, J. Am. Chem.
Soc. 2014, 136, 17662.
a
Regioconvergent and large scale conversion of isomeric mixtures of olefins
Me
Me
O
O
Me
standard
conditions
Ph
Ph
+
Me
Me
N
Me
N
Me
Me
Me
Ph Br
Ph nOct
2a
(1.5 equiv)
3a
91% yield, 97% ee
10 mmol (1:1:1:1)
petroleum-derived feedstocks
b
Reduction of N,N-diphenylamide
O
O
Et
LiAlH4
LiAlH4
Ph
Et
HO
HO
Ph
Ph
N
N
Ph
nOct
PMP
()4
THF, r.t.
84% yield
THF, r.t.
88% yield
Ph
PMP
()4
Ph nOct
3n 98% ee
5n 97% ee
4i 92% ee
5i 92% ee
[5]
For Ni-catalyzed asymmetric Negishi reactions using racemic alkyl
halides, see: a) F. O. Arp, G. C. Fu, J. Am. Chem. Soc. 2005, 127,
10482; b) C. Fischer, G. C. Fu, J. Am. Chem. Soc. 2005, 127, 4594; c)
S. W. Smith, G. C. Fu, J. Am. Chem. Soc. 2008, 130, 12645; d) S. Son,
G. C. Fu, J. Am. Chem. Soc. 2008, 130, 2756; e) P. M. Lundin, J.
Esquivias, G. C. Fu, Angew. Chem. Int. Ed. 2009, 48, 154; f) X. Lin, J.
Sun, Y. Xi, D. Lin, Organometallics 2011, 30, 3284; g) J. Choi, G. C. Fu,
J. Am. Chem. Soc. 2012, 134, 9102; h) J. T. Binder, C. J. Cordier, G. C.
Fu, J. Am. Chem. Soc. 2012, 134, 17003; i) A. J. Oelke, J. Sun, G. C.
Fu, J. Am. Chem. Soc. 2012, 134, 2966; j) H.-Q. Do, E. R. R.
Chandrashekar, G. C. Fu, J. Am. Chem. Soc. 2013, 135, 16288; k) Y.
Liang, G. C. Fu, J. Am. Chem. Soc. 2014, 136, 5520; l) J. Choi, P.
Martín-Gago, G. C. Fu, J. Am. Chem. Soc. 2014, 136, 12161; m) N. D.
Schley, G. C. Fu, J. Am. Chem. Soc. 2014, 136, 16588; n) Y. Liang, G.
C. Fu, Angew. Chem. Int. Ed. 2015, 127, 9047; o) J. Schmidt, J. Choi,
A. T. Liu, M. Slusarczyk, G. C. Fu, Science 2016, 354, 1265; For Ni-
catalyzed asymmetric Negishi reaction using racemic alkylzinc reagent,
see: p) C. J. Cordier, R. J. Lundgren, G. C. Fu, J. Am. Chem. Soc.
2013, 135, 10946.
Scheme 1. Regioconvergent and derivatization experiments.
In summary, we have developed
a
NiH-catalyzed
asymmetric remote hydroalkylation process from two readily
accessed starting materials, unactivated alkenes and racemic α-
bromo amides. With
a chiral nickel-pyrox-based catalyst,
excellent regio- and enantioselectivity were observed with broad
substrate scope. This mild, enantioconvergent reaction provides
rapid access to a variety of enantioriched α-alkylalkanoic amides
in good yields and ee. Furthermore, the practical value of this
transformation is highlighted by the regioconvergent and
enantioconvergent conversion of petroleum-derived isomeric
mixtures of olefins feedstocks into
a single region- and
stereoisomer of the product. The further development and
application of this reaction as well as mechanistic investigations
are currently in progress.
[6]
For Ni-catalyzed asymmetric Suzuki-Miyaura reactions using racemic
alkyl halides, see: a) B. Saito, G. C. Fu, J. Am. Chem. Soc. 2008, 130,
6694; b) P. M. Lundin, G. C. Fu, J. Am. Chem. Soc. 2010, 132, 11027;
c) N. A. Owston, G. C. Fu, J. Am. Chem. Soc. 2010, 132, 11908; d) Z.
Lu, A. Wilsily, G. C. Fu, J. Am. Chem. Soc. 2011, 133, 8154; e) L. L.
Zultanski, G. C. Fu, J. Am. Chem. Soc. 2011, 133, 15362; f) A. Wilsily,
F. Tramutola, N. A. Owston, G. C. Fu, J. Am. Chem. Soc. 2012, 134,
5794; f) H. Cong, G. C. Fu, J. Am. Chem. Soc. 2014, 136, 3788.
For Ni-catalyzed asymmetric other cross-coupling reactions using
racemic reagents, see: a) S. Lou, G. C. Fu, J. Am. Chem. Soc. 2010,
132, 5010; b) Z. Zuo, H. Cong, W. Li, J. Choi, G. C. Fu, D. W. C.
MacMillan, J. Am. Chem. Soc. 2016, 138, 1832; c) A. H. Cherney, N. T.
Kadunce, S. E. Reisman. J. Am. Chem. Soc. 2013, 135, 7442; d) A. H.
Cherney, S. E. Reisman. J. Am. Chem. Soc. 2014, 136, 14365; e) N. T.
Kadunce, S. E. Reisman. J. Am. Chem. Soc. 2015, 137, 10480; f) J. L.
Hofstra, A. H. Cherney, C. M. Ordner, S. E. Reisman. J. Am. Chem.
Soc. 2018, 140, 139.
Acknowledgements
Support was provided by “1000-Youth Talents Plan”, NSFC
(21602101, 21772087, 21822105). We thank Professor Yi-Ming
Wang (University of Pittsburgh) for helpful suggestions in the
preparation of the manuscript.
[7]
Keywords: nickel • C–H activation • isomerization • alkylation •
enantioselectivity
[8]
[9]
For selected reviews on C–H activation, see: a) W. R. Gutekunst, P. S.
Baran, Chem. Soc. Rev. 2011, 40, 1976; b) L. McMurray, F. O’Hara, M.
J. Gaunt, Chem. Soc. Rev. 2011, 40, 1885; c) M. C. White, Science
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For reviews on remote functionalization through alkene isomerization,
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