Projects per year
Abstract
Pd-catalyzed cyclizations of oxime esters with pendant alkenes are subject to an unusual ligand controlled mechanistic divergence. Pd-systems modified with electron deficient phosphines (e.g. P(3,5-(CF3)2C6H3)3) promote efficient aza-Heck cyclization, wherein C–N bond formation occurs via alkene imino-palladation. Conversely, electron rich ligands, such as P(t-Bu)3, cause deviation to a SET pathway and, in these cases, C–N bond formation occurs via cyclization of an iminyl radical. A series of mechanistic experiments differentiate the two pathways and the scope of the hybrid organometallic radical cyclization is outlined. This study represents a rare example in Pd-catalysis where selection between dichotomous mechanistic manifolds is facilitated solely by choice of phosphine ligand.
Original language | English |
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Pages (from-to) | 1508-1513 |
Number of pages | 6 |
Journal | Chemical Science |
Volume | 7 |
Issue number | 2 |
Early online date | 1 Dec 2015 |
DOIs | |
Publication status | Published - 1 Feb 2016 |
Research Groups and Themes
- BCS and TECS CDTs
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Dive into the research topics of 'Dichotomous mechanistic behaviour in Narasaka-Heck cyclizations: electron rich Pd-catalysts generate iminyl radicals'. Together they form a unique fingerprint.Projects
- 2 Finished
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3-month Core Capability for Chemistry Research
Crosby, J. (Principal Investigator)
1/01/13 → 1/04/13
Project: Research
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New Transition Metal Catalysed Methods for Alkyl C-N Bond Formation
Bower, J. F. (Principal Investigator)
3/11/11 → 3/11/13
Project: Research