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Transition-Metal-Free Formylation of Allylzinc Reagents Leading to α-Quaternary Aldehydes
Ryosuke Haraguchi1, Akinori Kusakabe1, Nakaba Mizutani1
1Department of Applied Chemistry, Institute of Science and Engineering , Chuo University , 1-13-27 Kasuga , Bunkyo-ku , Tokyo 112-8551 , Japan.
Abstract:
The first example of formylation of allylzinc reagents using S-phenyl thioformate is presented. The reaction proceeded under mild conditions without any transition-metal catalyst, forming quaternary carbon centers with reactive functionalities, such as formyl and vinyl groups. Moreover, Barbier-type formylation of an allylic bromide with a sterically demanding thioformate was achieved. As a preliminary result, asymmetric formylation was conducted using a menthol-derived chiral thioformate.
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