Issue 48, 2021

Stereodivergent synthesis via iridium-catalyzed asymmetric double allylic alkylation of cyanoacetate

Abstract

Methods that enable the rapid construction of multiple C–C bonds using a single catalyst with high diastereo- and enantio-control are particularly valuable in organic synthesis. Here, we report an Ir-catalyzed double allylic alkylation reaction in which bisnucleophilic cyanoacetate reacted successionally with electrophilic π-allyl-Ir species, producing various pseudo-C2-symmetrical cyanoacetate derivatives in high yield with excellent stereocontrol. More challenging sequential allylic alkylation/allylic alkylation with two distinct allylic carbonates that can deliver the corresponding products bearing three contiguous tertiary–quaternary–tertiary stereocenters was also developed by using a modified catalytic system, which is revealed to be associated with the quasi-dynamic kinetic resolution of the initially formed diastereomeric monoallylation intermediates. Notably, stereodivergence for this sequential process depending on a single iridium catalyst was successfully realized, and up to six stereoisomers could be predictably prepared by combining the appropriate enantiomer of the chiral ligand for the iridium catalyst and adjusting the adding sequence of two distinct allylic precursors.

Graphical abstract: Stereodivergent synthesis via iridium-catalyzed asymmetric double allylic alkylation of cyanoacetate

Supplementary files

Article information

Article type
Edge Article
Submitted
04 noy 2021
Accepted
19 noy 2021
First published
20 noy 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 15882-15891

Stereodivergent synthesis via iridium-catalyzed asymmetric double allylic alkylation of cyanoacetate

C. Shen, X. Cheng, L. Wei, R. Wang and C. Wang, Chem. Sci., 2021, 12, 15882 DOI: 10.1039/D1SC06115A

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