866807-65-0Relevant articles and documents
The bis(trimethylsilyl)methyl group as an effective N-protecting group and site-selective control element in rhodium(II)-catalyzed reaction of diazoamides
Wee, Andrew G. H.,Duncan, Sammy C.
, p. 8372 - 8380 (2007/10/03)
The intramolecular rhodium(II)-carbenoid-mediated C-H insertion reaction of structurally varied N-bis(trimethylsilyl)methyl,N-substituted diazoamides is studied. It has been found that in tertiary diazoamides the N- bis(trimethylsilyl)methyl (N-BTMSM) group is effective for conformational control about the amide N-C(O) bond; C-H insertion occurs at the other N-substituent. In Cα-branched diazoamides, the N-BTMSM is found also to exert its influence on the conformational preference about the N-C α bond, which affects the regioselectivity of the C-H insertion in these systems. In unbranched diazoamides, inherent electronic effects of the N-substituent affect the regio- and chemoselectivity of the reaction; however, in branched diazoamides, electronic effects of the N-substituent and the α-substituent at the carbenoid carbon are subtle, but important in the deciding the eventual outcome of the reaction.
