期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 1, 页码 330-334出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201911651
关键词
catalysis; energy transfer; hydrogenation; organophotocatalysis; stereodivergence
资金
- WWU Munster
Enantiodivergent, catalytic reduction of activated alkenes relays stereochemical information encoded in the antipodal chiral catalysts to the pro-chiral substrate. Although powerful, the strategy remains vulnerable to costs and availability of sourcing both catalyst enantiomers. Herein, a stereodivergent hydrogenation of alpha,beta-unsaturated phosphonates is disclosed using a single enantiomer of the catalyst. This enables generation of the R- or S-configured beta-chiral phosphonate with equal and opposite selectivity. Enantiodivergence is regulated at the substrate level through the development of a facile E -> Z isomerisation. This has been enabled for the first time by selective energy transfer catalysis using anthracene as an inexpensive organic photosensitiser. Synthetically valuable in its own right, this process enables subsequent Rh-I-mediated stereospecific hydrogenation to generate both enantiomers of the product using only the S-catalyst (up to 99:1 and 3:97 e.r.). This strategy out-competes the selectivities observed with the E-substrate and the R-catalyst.
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