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General Cyclopropane Assembly via Enantioselective Redox-Active Carbene Transfer to Aliphatic Olefins

preprint
submitted on 07.12.2018, 17:18 and posted on 10.12.2018, 19:44 by Marc Montesinos-Magraner, Matteo Costantini, Rodrigo Ramirez-Contreras, Michael E. Muratore, Magnus J. Johansson, Abraham Mendoza
Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates and reagents, even when targeting similar compounds. This limits the speed and chemical space available for discovery campaigns. Here we introduce a practical and versatile diazocompound, and we demonstrate its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. We found that the redox-active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect enabled the asymmetric cyclopropanation of a wide range of olefins including unactivated aliphatic alkenes, enabling the 3-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.

Funding

Automatized Catalysis and Single-Carbon Insertion

European Research Council

Find out more...

KAW2016.0153

History

Email Address of Submitting Author

abraham.mendoza@su.se

Institution

Stockholm University and AstraZeneca AB

Country

Sweden

ORCID For Submitting Author

0000-0001-9199-6736

Declaration of Conflict of Interest

A priority patent application has been filed (1850940-6), where A.M., M.M-M., M.C. and E.M.-C. are listed as inventors.

Version Notes

version 1.0

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