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General Cyclopropane Assembly by Enantioselective Transfer of a Redox‐Active Carbene to Aliphatic Olefins
Author(s) -
MontesinosMagraner Marc,
Costantini Matteo,
RamírezContreras Rodrigo,
Muratore Michael E.,
Johansson Magnus J.,
Mendoza Abraham
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201814123
Subject(s) - cyclopropane , cyclopropanation , enantioselective synthesis , geminal , chemistry , carbene , combinatorial chemistry , reactivity (psychology) , redox , organic chemistry , chemical space , selectivity , reagent , catalysis , drug discovery , medicine , ring (chemistry) , biochemistry , alternative medicine , pathology
Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates, and reagents, even when targeting similar compounds. This approach slows down discovery and limits available chemical space. Introduced herein is a practical and versatile diazocompound and its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. The redox‐active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect allowed the asymmetric cyclopropanation of various olefins, including unfunctionalized aliphatic alkenes, that enables the three‐step total synthesis of (−)‐dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally differentiated diazocompounds are viable and advantageous equivalents of single‐carbon chirons.