Co-catalyzed autoxidation of alkene in the presence of silane. The effect of the structure of silanes on the efficiency of the reaction and on the product distribution

• Published in: Tetrahedron Vol. 61; no. 42; pp. 9961 - 9968
• Main Authors: Wu, Jin-Ming, Kunikawa, Shigeki, Tokuyasu, Takahiro, Masuyama, Araki, Nojima, Masatomo, Kim, Hye-Sook, Wataya, Yusuke
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 17-10-2005
• Subjects: Antimalarial activity; Co-catalyzed autoxidation; Silyl peroxide; Yingzhaosu A analogue; Antimalarial activity; Yingzhaosu A analogue; Silyl peroxide; Co-catalyzed autoxidation
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2005.08.025

A systematic investigation of the structural effect of silanes on the Co-catalyzed reductive oxygenation of alkene in the presence of silane (Mukaiyama–Isayama reaction) showed that the efficiency of the reaction decreases with the increase of the steric bulk of the silanes. A similar trend was observed for the metal-exchange reaction between Co(III)–alkylperoxo complex and silane, too. The peroxidation of (
S)-limonene, followed by deprotection of the derived silyl peroxides, provides a mixture of the corresponding monocyclic hydroperoxide
24
and the bicyclic one
25
, the ratio being a marked function of the steric bulk of silanes.
Graphical Abstract