Cine-Silylative Ring-Opening of α-Methyl Azacycles Enabled by the Silylium-Induced C-N Bond Cleavage

Article abstract of DOI:10.1021/jacs.0c05241

Described herein is the development of a borane-catalyzed cine-silylative ring-opening of α-methyl azacycles. This transformation involves four-step cascade processes: (i) exo-dehydrogenation of alicyclic amine, (ii) hydrosilylation of the resultant enamine, (iii) silylium-induced cis-β-amino elimination to open the ring skeleton, and (iv) hydrosilylation of the terminal olefin. The present borane catalysis also works efficiently for the C-N bond cleavage of acyclic tertiary amines. On the basis of experimental and computational studies, the silicon atom was elucidated to play a pivotal role in the β-amino elimination step.

Full text of DOI:10.1021/jacs.0c05241

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Communication
cine-Silylative Ring-Opening of #-Methyl Azacycles
Enabled by the Silylium-Induced C-N Bond Cleavage
Jianbo Zhang, and Sukbok Chang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c05241 • Publication Date (Web): 05 Jul 2020
Downloaded from pubs.acs.org on July 6, 2020
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cine-Silylative Ring-Opening of -Methyl Azacycles Enabled by the
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