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Relevant academic research and scientific papers

Regio- and Stereochemistry on the Electrophilic Trapping of Allylic Samariums Generated by Reductive Cleavage of Allylic Ethers with (C5Me5)2Sm(thf)n

The C-O bond of allylic benzyl ethers was selectively cleaved with Cp*2Sm(thf)n to give allylic samarium complexes in good yields. Facility of their bond fission has been found to be comparable to that of the corresponding propargylic ethers intermolecularly, but lower intramolecularly. Regio-and stereochemistry on the electrophilic trapping of the allylic complexes thus generated remarkably depended on the nature of the electrophiles. They reacted with carbonyl compounds exclusively from the most substituted terminus of the allylic moieties to yield blanched homoallylic alcohols with anti diasteroselectivity. On the other hand, trapping with silyl chlorides produced linear allylic silanes. Here, a plausible mechanism to account for the difference is proposed.

First Practical Hydrozincation of Dienes Catalyzed by Cp2TiCl2. Generation of Allylzinc Reagent and Its Reaction with Carbonyl Compounds

The first practical hydrozincation of butadiene and 2-alkylbutadienes has been achieved by a combination reagent including ZnI2, LiH, and Cp2TiCl2 in a ratio of 1:2.2:0.1 to yield the corresponding allylzinc reagents in THF, which, in turn, react with a variety of carbonyl compounds.

SYNTHESIS OF HOMOALLYL ALCOHOLS BY THE REACTION OF ?-ALLYLDICYCLOPENTADIENYLTITANIUM(III) WITH CARBONYL COMPOUNDS

Reaction of ?-allyldicyclopentadienyltitanium(III) complexes, preformed or formed in situ, with aldehydes or ketones proceeds with regiospecificity, high stereoselectivity and chemospecificity, affording, under mild conditions, the corresponding homoallyl alcohols after hydrolysis in excellent yields.