期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 82, 期 1, 页码 57-75出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.6b02053
关键词
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资金
- NIH [P41 GM076267, T32 CA062948, P30 CA008748]
- William and Alice Goodwin
- Commonwealth Foundation for Cancer Research
- MSKCC Experimental Therapeutics Center
- U.S. NSF [CHE1058075, CHE1565669]
- National Science Foundation of China [NSFC 21133002]
- Shenzhen Peacock Program [JCYJ20140509093817689]
- Nanshan District [KC2014ZDZJ0026A]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1565669] Funding Source: National Science Foundation
Palladium-catalyzed oxidative cyclization of alkenols provides a convenient entry into cyclic ethers but typically proceeds with little or no diastereoselectivity for cyclization of trisubstituted olefins to form tetrahydrofurans due to the similar energies of competing 5-membered transition-state conformations. Herein, a new variant of this reaction has been developed in which a PdCl2/1,4-benzoquinone catalyst system coupled with introduction of a hydrogen bond acceptor in the substrate enhances both diastereoselectivity and reactivity. Cyclization occurs with 5-exo Markovnikov regioselectivity. Mechanistic and computational studies support an anti-oxypalladation pathway in which intramolecular hydrogen bonding increases the nucleophilicity of the alcohol and enforces conformational constraints that enhance diastereoselectivity. The cyclization is followed by a tandem redox-relay process that provides versatile side-chain functionalities for further derivatization.
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