Projects per year
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.
Original language | English |
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Pages (from-to) | 463-468 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 137 |
Issue number | 1 |
Early online date | 24 Dec 2014 |
DOIs | |
Publication status | Published - 14 Jan 2015 |
Research Groups and Themes
- BCS and TECS CDTs
Fingerprint
Dive into the research topics of 'Reversible C-C bond activation enables stereocontrol in Rh-catalyzed carbonylative cycloadditions of aminocyclopropanes'. Together they form a unique fingerprint.Projects
- 2 Finished
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New enantioselective metal-catalysed C-N and C-C bond forming reactions
Bower, J. F. (Principal Investigator)
1/10/15 → 30/09/18
Project: Research
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3-month Core Capability for Chemistry Research
Crosby, J. (Principal Investigator)
1/01/13 → 1/04/13
Project: Research