期刊
CHEMICAL SCIENCE
卷 7, 期 2, 页码 1508-1513出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc04037j
关键词
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资金
- EPSRC [EP/J007455/1, EP/G036764/1]
- Syngenta
- SCI
- Royal Society
- EPSRC [EP/K03927X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [1100702, 981180, EP/K03927X/1, EP/J007455/1, 981192] Funding Source: researchfish
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)(2)C6H3)(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.
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