期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 19, 期 40, 页码 13547-13553出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201301280
关键词
asymmetric catalysis; cooperative catalysis; copper; density functional calculations; hydrogen bonds
资金
- CREST (JST)
- ACT-C (JST)
- MEXT through the Global COE grant [B01]
- Grants-in-Aid for Scientific Research [25105707, 24685015, 25620072] Funding Source: KAKEN
Catalyst-substrate hydrogen bonds in artificial catalysts usually occur in aprotic solvents, but not in protic solvents, in contrast to enzymatic catalysis. We report a case in which ligand-substrate hydrogen-bonding interactions cooperate with a transition-metal center in alcoholic solvents for enantioselective catalysis. Copper(I) complexes with prolinol-based hydroxy amino phosphane chiral ligands catalytically promoted the direct alkynylation of aldehydes with terminal alkynes in alcoholic solvents to afford nonracemic secondary propargylic alcohols with high enantioselectivities. Quantum-mechanical calculations of enantiodiscriminating transition states show the occurrence of a nonclassical sp(3)-CHO hydrogen bond as a secondary interaction between the ligand and substrate, which results in highly directional catalyst-substrate two-point hydrogen bonding.
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