Communication
ChemComm
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5 For kinetic resolutions to allylic alcohols, see: (a) Y. Naruse, T. Esaki
and H. Yamamoto, Tetrahedron, 1988, 44, 4747; (b) A. Gayet,
S. Bertilsson and P. G. Andersson, Org. Lett., 2002, 4, 3777;
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sensitive functional groups are compatible with the method,
delivering the products in essentially quantitative yield.
Preliminary mechanistic investigations point to a hydride
mechanism similar to the one recently elucidated for a palla-
dium hydride complex. Current efforts are directed toward the
synthesis of enantiopure variants of the iridium complex for
application in enantioselective reactions.
This work was supported by the University of Geneva and the
Swiss National Foundation (Project PP00P2_133482). Roche is
also acknowledged for support through an unrestricted grant.
Dr Luqing Lin is warmly thanked for technical assistance.
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6 D. J. Vyas, E. Larionov, C. Besnard, L. Guenee and C. Mazet, J. Am.
Chem. Soc., 2013, 135, 6177.
7 The origins of the reduction product 4a are not clear at the moment.
8 (a) P. Wipf and W. Xu, J. Org. Chem., 1993, 58, 825; (b) P. Wipf and
W. Xu, J. Org. Chem., 1993, 58, 5880; (c) P. Wipf, W. Xu, H. Takahashi,
H. Jahn and P. D. G. Coish, Pure Appl. Chem., 1997, 69, 639.
9 For other isomerization reaction with Schwartz reagent, see:
(a) N. Chinkov, A. Levin and I. Marek, Angew. Chem., Int. Ed., 2006,
45, 465; (b) N. Chinkov, A. Levin and I. Marek, Synlett, 2006, 501.
10 H. Li and C. Mazet, Org. Lett., 2013, 15, 6170.
Notes and references
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´
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D. Gerard, C. Besnard and C. Mazet, Eur. J. Inorg. Chem., 2012, 3320.
12 Although the catalyst is air-stable and the reaction can be set on a
bench-top, at these very low loadings the use of perfectly anhydrous
substrates and solvent is preferable. The iridium complexes
with BArF anion are usually hygroscopic and are best kept in a
desiccator.
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13 (a) A. C. Albeniz, P. Espinet, R. Lopez-Fernandez and A. Sen, J. Am.
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14 When optically (R)-1a (94% ee) was subjected to the typical reaction
conditions (4.0 mol% [Ir], 100 1C, 4 h), 2a was obtained in racemic
form. This result is similar to the one obtained with 3 and rules out
the possibility of a stereospecific process.
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Trans. 1, 2000, 1749; ( j) I. Kamare, M. L. Tommasino and M. Lemaire,
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15 M. Portnoy and D. Milstein, Organometallics, 1994, 13, 600.
16 CCDC 999031 for complex 5. The structure in Scheme 3 was generated
with CYLview: Legault, C. Y. CYLview, version 1.0.561b; Universite de
Tetrahedron Lett., 2006, 47, 5919; (m) E. Ertu¨rk, M. Gollu¨ and
A. S. Demir, Tetrahedron, 2010, 66, 2373; (n) M. W. C. Robinson,
K. S. Pillinger, L. Mabbett, D. A. Timms and A. E. Graham, Tetrahedron,
2010, 66, 8377. For stereoselective variants, see: (o) K. Maruoka, T. Ooi
and H. Yamamoto, J. Am. Chem. Soc., 1989, 111, 6431; (p) K. Suda, 17 For additional experimental details, see ref. 6.
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