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Reversible C-C bond activation enables stereocontrol in Rh-catalyzed carbonylative cycloadditions of aminocyclopropanes

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)463-468
Number of pages6
JournalJournal of the American Chemical Society
Volume137
Issue number1
Early online date24 Dec 2014
DOIs
DateAccepted/In press - 24 Dec 2014
DateE-pub ahead of print - 24 Dec 2014
DatePublished (current) - 14 Jan 2015

Abstract

Upon exposure to neutral or cationic Rh(I)-catalyst systems, amino-substituted cyclopropanes undergo carbonylative cycloaddition with tethered alkenes to provide stereochemically complex N-heterocyclic scaffolds. These processes rely upon the generation and trapping of rhodacyclopentanone intermediates, which arise by regioselective, Cbz-directed insertion of Rh and CO into one of the two proximal aminocyclopropane C-C bonds. For cyclizations using cationic Rh(I)-systems, synthetic and mechanistic studies indicate that rhodacyclopentanone formation is reversible and that the alkene insertion step determines product diastereoselectivity. This regime facilitates high levels of stereocontrol with respect to substituents on the alkene tether. The option of generating rhodacyclopentanones dynamically provides a new facet to a growing area of catalysis and may find use as a (stereo)control strategy in other processes.

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