Asymmetric catalysis. Production of chiral diols by enantioselective catalytic intramolecular hydrosilation of olefins
作者:Steven H. Bergens、Pedro Noheda、John Whelan、B. Bosnich
DOI:10.1021/ja00032a028
日期:1992.3
Rhodium(I) chiral diphosphine complexes efficiently and rapidly catalyze the intramolecular hydrosilation of silylethers derived fromallylicalcohols. The efficiency and rates of intramolecular hydrosilations were determined for a variety of silyl and olefin substituents. The catalysts were found to tolerate a widevariety of silyl substituents, although terminal alkyl olefin substituents were found to
Photoinduced electron transfer reactions of 2,7-diarylocta-1,7-dienes 1 or 2,8-Diarylnona-1,8-dienes 2 resulted in bicyloalkanes 3 or 5 and cycloalkenes 4 or 6. A mechanism involving cyclic 1,4-cation radicals 7•+ or 8•+ has been proposed based on the trapping experiments with oxygen.