Journal
ACS CATALYSIS
Volume 6, Issue 1, Pages 262-271Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.5b01891
Keywords
Rh-catalysis; asymmetric dearomatization; C-H activation; DFT calculation; reaction mechanism; enantioselectivity
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Funding
- National Basic Research Program of China (973 Program) [2015CB856600]
- National Natural Science Foundation of China [21332009, 21302209, 21421091]
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Comprehensive DFT calculations have been performed to pursue deeper understandings on the mechanism of Rh-catalyzed asymmetric dearomatization of 2-naphthols initiated with C-H activation, which was developed by our group recently. A refined reaction mechanism is described here to account for the experimentally observed high enantio- and regioselectivity. Although the C-H activation was suggested to be involved in the turnover-limiting step, the enantioselectivity of the reaction was found to be determined during the migratory insertion of the alkyne. Different from the originally proposed mechanism, the final dearomatized product is afforded via a [1,3']-reductive elimination directly from the eight-membered rhodacyclic intermediate generated from the migratory insertion step. In addition, the pi-pi interaction between the phenyl substituent on the alkyne and 2-naphthol might partially contribute to the high regioselectivity when unsymmetrical alkynes were employed as the substrates.
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