Journal of the American Chemical Society
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remarkable Markovnikov selectivity and enantioselectivity to
form chiral tertiary boronic esters by hydroboration. Preliminary
study supports the transformation proceeds through hydroboration
over diboration of acyl imine pathway. The stable αꢀamino tertiary
boronic esters can be envisioned as not only important building
blocks for peptidomimetics, but also versatile chiral intermediates
in synthetic organic chemistry.
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Supporting Information
Full experimental details, characterization data, NMR spectra, or
cif files of 2aꢀv, 17ꢀ19, [Rh(nbd)((R)ꢀL1)]BF4, optimization data
and general procedure of hydroboration. This information is
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15. For examples of metalꢀcatalyzed asymmetric antiꢀMarkovnikov hydroboꢀ
ration, see: (a) Mazet, C.; Gérard, D. Chem. Commun. 2011, 47, 298. (b)
Corberán, R.; Mszar, N. W.; Hoveyda, A. H. Angew. Chem., Int. Ed.
2011, 50, 7079. (c) Zhang, L.; Zuo, Z.; Wan, X.; Huang, Z. J. Am. Chem.
Soc. 2014, 136, 15501. (d) Chen, J.; Xi, T.; Ren, X.; Cheng, B.; Guo, J.;
Lu, Z. Org. Chem. Front. 2014, 1, 1306. (e) Ding, J.; Rybak, T.; Hall, D.
G. Nat. Commun. 2014, 5, 5474.
Corresponding Author
Author Contributions
†N.H. and G.Z. contributed equally.
16. For other reports of chiral tertiary boronic esters, see: (a) Stymiest, J. L.;
Bagutski, V.; French, R. M.; Aggarwal, V. K. Nature 2008, 456, 778. (b)
Bagutski, V.; French, R. M.; Aggarwal, V. K. Angew. Chem. Int. Ed.
2010, 49, 5142. (c) Pulis, A. P.; Blair, D. J.; Torres, E.; Aggarwal, V. K.
J. Am. Chem. Soc. 2013, 135, 16054. (d) Chen, IꢀH.; Yin, L.; Itano, W.;
Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2009, 131, 11664.(e)
O’Brien, J. M.; Lee, K.ꢀs.; Hoveyda, A. H. J. Am. Chem. Soc. 2010, 132,
10630. (f) GuzmanꢀMartinez, A.; Hoveyda, A. H. J. Am. Chem. Soc.
2010, 132, 10634. (g) Feng, X. Yun, J. Chem. Eur. J. 2010, 16, 13609.
17. (a) Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114,
6671. (b) Evans, D. A.; Fu, G. C.; Anderson, B. A. J. Am. Chem. Soc.
1992, 114, 6679. (c) Rubina, M.; Rubin, M.; Gevorgyan, V. J. Am. Chem.
Soc. 2003, 125, 7198. (d) Smith, S. M.; Takacs, J. M. J. Am. Chem. Soc.
2010, 132, 1740. (e) Smith, S. M.; Hoang, G. L.; Pal, R.; Khaled, M. O.
B.; Pelter, L. S. W.; Zeng, X. C.; Takacs, J. M. Chem. Commun. 2012, 48,
12180.
18. CCDC 1036758 (2a) and 1036887 ([Rh((R)ꢀL1)(nbd)(H2O)]BF4) contain
the supplementary crystallographic data for this paper. These data can be
from the Cambridge Crystallographic Data Centre, 12 Union Road, Camꢀ
bridge CB21EZ, UK; fax: (+44)1223ꢀ336ꢀ033; or deposꢀ
was liked to be incorporated during crystallization.
Notes
The authors declare no competing financial interest.
Acknowledgments
This work is supported by NSFCꢀ21432007, 21272254, STCSMꢀ
13PJ1410900, the “Thousand Plan” Youth program.
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