TY - JOUR
T1 - Ozone Oxidation of Silylalkene
T2 - Mechanistic Study and Application for the Synthesis of Silacarboxylic Acid Derivatives
AU - Igawa, Kazunobu
AU - Kawasaki, Yuuya
AU - Nozaki, Sora
AU - Kokan, Naoto
AU - Tomooka, Katsuhiko
N1 - Funding Information:
This research was supported by JSPS KAKENHI grants JP17H06235 and JP18H04419 in Middle Molecular Strategy, Integrated Research Consortium on Chemical Sciences, the Cooperative Research Program of “Network Joint Research Center for Materials and Devices,” Ube Industries Foundation, and Kakihara Science Technology Foundation. The authors thank N. Mitsuda for technical assistance and T. Nishi and S. Yano (Kyushu Univ.) for assistance in the HRMS measurements.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/3/20
Y1 - 2020/3/20
N2 - The addition-type ozone oxidation of silylalkenes is a highly efficient reaction to provide synthetically versatile α-silylperoxy carbonyl compounds. To gain insight into the reaction mechanism, we performed a computational study, which revealed that the reaction proceeds via [1,2]-Brook rearrangement-type silyl migration of primary ozonide. In sharp contrast to the addition-type reactions, the ozone oxidation of α-alkoxysilylalkenes proceeds in a cleavage-type manner to afford excellent yields of silacarboxylic acid esters via the 1,3-cycloelimination of primary ozonide prior to 1,2-silyl migration.
AB - The addition-type ozone oxidation of silylalkenes is a highly efficient reaction to provide synthetically versatile α-silylperoxy carbonyl compounds. To gain insight into the reaction mechanism, we performed a computational study, which revealed that the reaction proceeds via [1,2]-Brook rearrangement-type silyl migration of primary ozonide. In sharp contrast to the addition-type reactions, the ozone oxidation of α-alkoxysilylalkenes proceeds in a cleavage-type manner to afford excellent yields of silacarboxylic acid esters via the 1,3-cycloelimination of primary ozonide prior to 1,2-silyl migration.
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U2 - 10.1021/acs.joc.9b03350
DO - 10.1021/acs.joc.9b03350
M3 - Article
C2 - 32141746
AN - SCOPUS:85081664186
SN - 0022-3263
VL - 85
SP - 4165
EP - 4171
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 6
ER -