Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of Alkenyl Isocyanates with Tolanes

Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2 + 2 + 2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enant...

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Published in:Organic letters 2009-11, Vol.11 (21), p.4934-4937
Main Authors: Oinen, Mark Emil, Yu, Robert T, Rovis, Tomislav
Format: Article
Language:English
Subjects:
Alkenes - chemistry
Catalysis
Cyclization
Isocyanates - chemistry
Ligands
Molecular Structure
Nicotinic Acids - chemistry
Rhodium - chemistry
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description Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2 + 2 + 2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enantioselectivity is the result of a change in composition of a proposed rhodium(III) intermediate on the catalytic cycle. The net result is a rational probe of a short-lived rhodium(III) intermediate and gives insight that may have applications in many rhodium-catalyzed reactions.
doi_str_mv 10.1021/ol9020805
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subjects Alkenes - chemistry
Catalysis
Cyclization
Isocyanates - chemistry
Ligands
Molecular Structure
Nicotinic Acids - chemistry
Rhodium - chemistry
title Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of Alkenyl Isocyanates with Tolanes
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