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Issue 1, 2018

Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters

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Abstract

A well-defined Ir–allyl complex catalyzes the Z-selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E-products typically observed in metal-mediated coupling reactions to enable the synthesis of Z,E-dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir–carbene and Ir–allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E–H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt3.

Graphical abstract: Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters

Supplementary files

Article information


Submitted
02 Oct 2017
Accepted
23 Oct 2017
First published
24 Oct 2017

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 238-244
Article type
Edge Article

Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters

B. N. Thomas, P. J. Moon, S. Yin, A. Brown and R. J. Lundgren, Chem. Sci., 2018, 9, 238 DOI: 10.1039/C7SC04283C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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