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The rhodium(II)-catalyzed reaction of N-bis(trimethylsilylmethyl)diazoamides: steric, electronic and conformational effects

✍ Scribed by Andrew G.H Wee; Sammy C Duncan

Publisher: Elsevier Science
Year: 2002
Tongue: French
Weight: 121 KB
Volume: 43
Category: Article
ISSN: 0040-4039
DOI: 10.1016/s0040-4039(02)01273-x

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✦ Synopsis

The N-bis(trimethysilyl)methyl (N-BTMSM) group is effective for conformational control about the amide N C(O) bond in tertiary diazoamides; metallocarbenoid C-H insertion reaction occurs only at the other N-'alkyl' unit. In C a -unbranched diazoamides, the inherent electronic effects of the N-'alkyl' group influence the regioselectivity of the reaction. The N-BTMSM group also influences the conformational preference about the amide N-C a bond in C a -branched systems which, in turn, affects the regioselectivity of the reaction; substituent electronic effects are subtle and play subordinate roles. A transition state model to explain the results is proposed.

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