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Michael-Addition-Triggered Release of Substituents from Tertiary Amines
Toshiaki Wayama1, Hiroki Oguri1
1Department of Chemistry, Graduate School of Science, The University of Tokyo, Tokyo 113-0033, Japan.
Abstract:
A general and operationally simple method for removing substituents from tertiary amines via Michael-addition-triggered carbocation release is described. Using methyl propiolate, hexafluoroisopropyl alcohol (HFIP), and thioanisole, this reaction enables efficient, metal-free cleavage of challenging groups─including benzyl, p-methoxybenzyl (PMB), allyl, propargyl, diphenylmethyl, and tert-butyl. This carbocation-mediated platform offers predictable, broad-scope amine deprotection and provides a practical alternative to hydrogenolysis and other redox-based protocols.
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