Activation of the Si-B linkage: copper-catalyzed addition of nucleophilic silicon to imines

Devendra J Vyas; Roland Fröhlich; Martin Oestreich

doi:10.1021/ol200509c

Activation of the Si-B linkage: copper-catalyzed addition of nucleophilic silicon to imines

Org Lett. 2011 Apr 15;13(8):2094-7. doi: 10.1021/ol200509c. Epub 2011 Mar 18.

Authors

Devendra J Vyas¹, Roland Fröhlich, Martin Oestreich

Affiliation

¹ Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.

PMID: 21417305
DOI: 10.1021/ol200509c

Abstract

Activation of the Si-B bond through copper-catalyzed transmetalation quickly developed into a practical method to generate Cu-Si reagents. These silicon nucleophiles cleanly add to aldehyde-derived imine electrophiles to form α-silylated amines in protic media, and no carbon-to-nitrogen Brook-type rearrangement of the intermediate anion is observed. Aside from electron-withdrawing groups at the imine nitrogen atom, for example, SO(2)Tol and P(O)Ph(2), previously delicate nitrogen substituents such as phenyl or benzhydryl are tolerated. The same protocol also allows the unprecedented addition to representative ketone-derived imines.