Asymmetric catalysis. Production of chiral diols by enantioselective catalytic intramolecular hydrosilation of olefins

Article abstract of DOI:10.1021/ja00032a028

Rhodium(I) chiral diphosphine complexes efficiently and rapidly catalyze the intramolecular hydrosilation of silyl ethers derived from allylic alcohols. The efficiency and rates of intramolecular hydrosilations were determined for a variety of silyl and olefin substituents. The catalysts were found to tolerate a wide variety of silyl substituents, although terminal alkyl olefin substituents were found to retard catalysis. Terminal aryl olefin substituents were found to be hydrosilated efficiently and at reasonable rates. One of the chiral catalysts is highly enantioselective for terminal aryl olefin substituents. Almost quantitative ee's are obtained. Moreover, the ee's are only slightly sensitive to aryl and olefin substituents, suggesting that this enantioselective catalysis can provide a wide range of chiral species. Oxidative cleavage of the hydrosilation products gives chiral diols.