期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 41, 页码 14694-14702出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201907375
关键词
allylic substitution; DFT calculations; enantioselectivity; inner-sphere pathway; palladium
资金
- National Natural Science Foundation of China [21503143]
- Natural Science Foundation of Tianjin [16JCQNJC05600]
- CERCA Program/Generalitat de Catalunya
- ICREA
- Spanish MINECO [CTQ2017-88920-P]
- AGAUR [2017-SGR-232]
- MINECO
A recently reported palladium-catalyzed allylic substitution of vinyl-substituted cyclic carbonates (VCCs) with aryl amines represents a rare example of a regio- and enantioselective synthesis of alpha,alpha-disubstituted allylic N-aryl amines. However, the underlying reasons for this unusual selectivity profile remain elusive. In the present work, density functional theory (DFT) calculations in combination with mechanistic control experiments were performed to elucidate in detail this allylic amination manifold and the origin of the regio- and enantioselectivity. The combined data show that after oxidative addition of the VCC to Pd-0, the nucleophilic attack via an originally proposed outer-sphere pathway gives, however, the opposite regioisomer compared to the experimental results. Instead, nucleophilic attack of the amine reagent via a unique type of chelation-assisted, inner-sphere pathway accounts for the experimentally observed branched regioselectivity and high enantio-control.
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