Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 21, Pages 7230-+Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja9026852
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- NIH [GM068640]
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Herein, we provide crystallographic and computational evidence that Hashimoto's Rh-2(S-PTTL)(4) catalyst adopts a chiral crown conformation with a reactive chiral face and an unreactive achiral face. In Rh-2(S-PTTL)(4), all four tert-butyl groups are aligned on the same face of the catalyst, and each C-(t-Bu) bond is roughly parallel. to the central Rh-Rh bond. This orients the four phthalimido groups on the opposite face of the catalyst. Also described is an enantioselective and diastereoselective protocol for intermolecular Rh-2(S-PTTL)(4)-catalyzed cyclopropanation using alpha-alkyl-alpha-diazoesters. Intermotecular cyclopropanation is selective over two competing intramolecular pathways: C-H insertion and B-hydride elimination. On the basis of density functional theory calculations and the Davies-Singleton model, for cyclopropanation, a model for asymmetric induction is proposed.
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