139016-79-8Relevant academic research and scientific papers
Ligand-Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis
Chen, Qing-An,Hu, Yan-Cheng,Ji, Ding-Wei,Kuai, Chang-Sheng,Liu, Heng,Zhao, Chao-Yang
, p. 19115 - 19120 (2020)
A method for the regiodivergent and stereoselective hydrosilylation of the basic industrial feedstock isoprene with unactivated silanes has been developed using earth-abundant iron catalysts. The manipulation of regioselectivity relies on fine modification of the coordination geometry of the iron center. While a bidentate pyridine imine ligand promoted the formation of allylic silanes through 4,1-addition, selectivity for the 3,4-adduct homoallylic silanes was observed with a tridentate nitrogen ligand. Experimental studies and analysis were carried out to elucidate the reaction mechanism and the factors enabling manipulation of the regioselectivity. This study contributes to the art of regioselectivity control in alkene hydrofunctionalization.
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.
