期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 34, 页码 13759-13768出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c05769
关键词
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资金
- National Institutes of Health [R35 GM118190, R35 GM128779]
- NSF [DGE 1752814]
- College of Chemistry CheXray (NIH Shared Instrumentation Grant) [S10-RR027172]
- NIH [S10OD024998]
In this study, the copper-catalyzed silylation of propargylic difluorides was successfully used to generate axially chiral, tetrasubstituted monofluoroallenes with good yields and high enantioselectivities. A novel mechanistically distinct reaction was developed, which involves enantiodiscrimination between enantiotopic fluorides to set an axial stereocenter. The effects of the C1-symmetric Josiphos-derived ligand on reactivity and enantioselectivity were investigated, showing that enantioselective beta-fluoride elimination can be achieved in alkenyl copper species.
Herein we report the copper-catalyzed silylation of propargylic difluorides to generate axially chiral, tetrasubstituted monofluoroallenes in both good yields (27 examples >80%) and enantioselectivities (82-98% ee). Compared to previously reported synthetic routes to axially chiral allenes (ACAs) from prochiral substrates, a mechanistically distinct reaction has been developed: the enantiodiscrimination between enantiotopic fluorides to set an axial stereocenter. DFT calculations and vibrational circular dichroism (VCD) suggest that beta-fluoride elimination from an alkenyl copper intermediate likely proceeds through a syn-beta-fluoride elimination pathway rather than an anti-elimination pathway. The effects of the C1-symmetric Josiphos-derived ligand on reactivity and enantioselectivity were investigated. Not only does this report showcase that alkenyl copper species (like their alkyl counterparts) can undergo can undergo beta-fluoride elimination, but this elimination can be achieved in an enantioselective fashion.
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