Iridium-catalyzed Z-retentive asymmetric allylic substitution reactions.

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Date: Jan. 22, 2021
From: Science(Vol. 371, Issue 6527)
Publisher: American Association for the Advancement of Science
Document Type: Article
Length: 4,108 words
Lexile Measure: 1620L

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Abstract :

Z-Olefins are challenging synthetic targets owing to their relative thermodynamic instability. Transition metal-catalyzed asymmetric allylic substitution reactions are well known for installing stereocenters adjacent to branched or E-linear olefins. However, analogous reactions for the synthesis of optically active Z-olefin products are rare. Here we report iridium-catalyzed asymmetric allylic substitution reactions that retain Z-olefin geometries while establishing an adjacent quaternary stereocenter. The formation of transient anti-n-allyl-iridium intermediates and their capture by external nucleophiles before isomerization to the thermodynamically more stable syn-[pi]-allyl-iridium counterparts have been observed. These results provide a promising method for preparing chiral Z-olefinic compounds.

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Gale Document Number: GALE|A652011490