Ligand Exchange in Mixed Organocuprate(I) π-Complexes
摘要:
pi-Complexes of mixed organocuprate(I) reagents with alpha,beta-unsaturated carbonyl compounds can undergo ligand exchange to give the corresponding homocuprate-olefin pi-complexes. The mechanism of this metathesis, which has profound implications for synthetic applications, involves a second order reaction of the Mixed cuprate with the mixed cuprate-olefin pi-complex.
Ligand Exchange in Mixed Organocuprate(I) π-Complexes
摘要:
pi-Complexes of mixed organocuprate(I) reagents with alpha,beta-unsaturated carbonyl compounds can undergo ligand exchange to give the corresponding homocuprate-olefin pi-complexes. The mechanism of this metathesis, which has profound implications for synthetic applications, involves a second order reaction of the Mixed cuprate with the mixed cuprate-olefin pi-complex.
Minimization of Organocuprate Complexity through Self-Organization: Remarkable Orientation Effect in Mixed Cuprate π Complexes
作者:Steven H. Bertz、Richard A. Hardin、Michael D. Murphy、Craig A. Ogle、Joshua D. Richter、Andy A. Thomas
DOI:10.1002/anie.201107060
日期:2012.3.12
where to go: A powerful orientation effect has been observed in complexes of mixedorganocuprates [RTRNTCuLi] and substrates with CC, CN, and CS double bonds (see scheme; Th=thienyl). The preferred geometry of the intermediate complex sets up the facile addition of RT to the double bond, rather than addition of the “dummyligand”, RNT.
他们“知道”去哪里:一个强大的取向效应在混合有机铜[R的复合物中观察到Ť ř NT CuLi]和底物使用C C,C N,和C š双键(参见方案; TH =噻吩基)。中间配合物的优选几何形状建立了将R T容易地添加到双键中,而不是添加了“虚拟配体” R NT。