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Lewis Acid‐Mediated Decarboxylative Allylation of Enol Carbonates
Author(s) -
Dokai Yoichi,
Nishizawa Takuma,
Saito Kodai,
Yamada Tohru
Publication year - 2021
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.202100065
Subject(s) - chemistry , enol , lewis acids and bases , ketone , regioselectivity , organic chemistry , propargyl , carbon fixation , medicinal chemistry , catalysis , carbon dioxide
A homoallylic ketone can be transformed and functionalized by various synthetic reactions, and thus, is regarded as one of the representative building blocks in organic chemistry. An additional route to access homoallylic ketones, namely, a Lewis acid‐mediated decarboxylative allylation of cyclic enol carbonates, prepared by fixation of carbon dioxide onto propargyl alcohols, was developed in this work. The treatment of a cyclic enol carbonate with a Lewis acid in the presence of an allylsilane resulted in the formation of a homoallylic ketone. It was found that the title reaction proceeded well by the combined use of zirconium tetrachloride with allyltrimethylsilane. The allylation occurred with high regioselectivity and the corresponding homoallylic ketones were obtained in good‐to‐high yields. A reaction mechanism involving the decarboxylative formation of an oxyallyl cation equivalent is proposed.