139016-92-5Relevant academic research and scientific papers
Stereoselective synthesis of silacyclohexanols by silicon tethered Type II ene cyclisation
Robertson, Jeremy,O'Connor, Garry,Sardharwala, Tsarina,Middleton, Donald S.
, p. 8309 - 8320 (2007/10/03)
Vinyl silane precursors for intramolecular ene reaction were prepared either by sequential organometallic substitution of appropriate silyl halides or by ring opening of oxasilacyclopentanes with 2-propenyllithium. The oxasilacyclopentane intermediates were prepared by free-radical cyclisation, intramolecular hydrosilylation, or intramolecular Diels-Alder reaction. Treatment of the ene precursors with methylaluminium dichloride resulted in the formation of silacyclohexanols with high stereoselectivity. (C) 2000 Elsevier Science Ltd.
Oxasilacyclopentanes as intermediates for silicon tethered ene cyclisations
Robertson, Jeremy,Middleton, Donald S.,O'Connor, Garry,Sardharwala, Tsarina
, p. 669 - 672 (2007/10/03)
Oxasilacyclopentanes 3, generated by either free-radical cyclisation, intramolecular hydrosilylation, or silicon tethered Diels-Alder reaction, may be efficiently opened with 2-propenyl-lithium and the product alcohols oxidised to prepare precursors 2 for silicon tethered ene cyclisation. Efficient and highly stereoselective ene reactions have been achieved with these precursors.
Asymmetric catalysis. Production of chiral diols by enantioselective catalytic intramolecular hydrosilation of olefins
Bergens, Steven H.,Noheda, Pedro,Whelan, John,Bosnich
, p. 2121 - 2128 (2007/10/02)
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.
