期刊
NATURE CATALYSIS
卷 3, 期 4, 页码 401-410出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/s41929-020-0439-8
关键词
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资金
- National Natural Science Foundation of China [21722203, 21831002, 21702182, 2187308, 21801116]
- Shenzhen Special Funds [JCYJ20170412152435366, JCYJ20170307105638498]
- Shenzhen Nobel Prize Scientists Laboratory Project [C17783101]
- Fundamental Research Funds for the Central Universities [2019QNA3009]
In contrast with abundant methods for the asymmetric functionalization of alkyl radicals to generate stereogenic centres at reaction sites, catalytic enantioselective desymmetrizing functionalization of alkyl radicals for forging multiple stereocentres-including positions that are remote from the reaction sites-with both high enantio- and diastereoselectivity remains largely unexplored. The major challenge for such reactions is the high reactivity of open-shell alkyl radicals. Here, we describe a strategy to address this challenge: the use of Cu(ii) phosphate to immediately associate with the in situ-generated reactive alkyl radical species, creating a compact and confined chiral microenvironment for effective stereocontrol. With this strategy, we have developed a general and efficient catalytic enantioselective desymmetrizing functionalization of alkene-tethered 1,3-diols. It provides various tetrahydrofurans and analogues bearing multiple stereocentres with remarkably high levels of enantio- and diastereocontrol. Density functional theory calculations and mechanistic experiments revealed a reaction mechanism involving an enantiodetermining outer-sphere C-O bond formation step.
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