-Selective Iridium-catalyzed Cross-coupling of Allylic Carbonates and α-diazo Esters

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Apr 10

PMID 29629093

Citations 1

Authors

Bryce N Thomas

Patrick J Moon

Shengkang Yin

Alex Brown

Rylan J Lundgren

Affiliations

Soon will be listed here.

Abstract

A well-defined Ir-allyl complex catalyzes the -selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for -products typically observed in metal-mediated coupling reactions to enable the synthesis of ,-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 NEt.

Citing Articles

Synthesis of Isomerically Pure ()-Alkenes from Terminal Alkynes and Terminal Alkenes: Silver-Catalyzed Hydroalkylation of Alkynes.

Lee M, Goodstein M, Lalic G J Am Chem Soc. 2019; 141(43):17086-17091.

PMID: 31633923 PMC: 7304281. DOI: 10.1021/jacs.9b09336.

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