期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 76, 期 22, 页码 9246-9252出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo201447e
关键词
-
资金
- Swedish Research Council [621-2009-4736, 622-2009-371]
- Wenner-Gren Foundations
Density functional theory calculations are used to study the reaction mechanism and origins of C2 selectivity in a copper(I)-catalyzed amidation of indoles. It is shown that concerted metalation-deprotonation is not able to reproduce the observed regioselectivity. Instead, an unprecedented mechanism based on a four-center reductive elimination is proposed to be responsible for the reaction outcome. This mechanism has a lower reaction barrier and is able to reproduce the experimentally observed selectivity. A possible alternative mechanism involving a Cu(II) species instead of Cu(III) is presented, but it is shown that higher energy barriers are associated with this mechanism. An important technical detail is that addition of dispersion effects to the B3LYP results is necessary to reproduce the observed selectivity, although not important for the overall mechanistic proposal.
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