Synthesis of branched deuterohydrocarbons, containing deuterium at a tertiary carbon atom

Ionic and Organometallic‐Catalyzed Organosilane Reductions

“…73). 221 In the same way, isopropenylcyclopropane gives an 80% yield of deuterated isopropylcyclopropane after 30 Preferential protonation of oxygen in comparison to carbon prevents 4-methylenetetrahydropyran from undergoing reduction to 4-methyltetrahydropyran even when held at 70 • for 10 hours in the presence of triethylsilane and a 20-fold excess of trifluoroacetic acid. 146 However, when the reaction conditions are changed so that a dichloromethane solution of the same substrate is treated with a mixture of four equivalents of triethylsilane and three equivalents of aluminum chloride in the presence of excess hydrogen chloride, a 40% yield of 4-methyltetrahydropyran product is obtained at room temperature after one hour (Eq.…”

“…77). 221 Under similar conditions, 2-methyl-2-butene gives 2-methylbutane-2-d 1 (90%) and 1-methylcyclopentene gives methylcyclopentane-1-d 1 (60%). 221…”

“…192 The use of deuterated organosilicon hydrides in conjunction with proton acids permits the synthesis of site-specific deuterium-labeled compounds. 59,126,221 Under such conditions, the deuterium atom in the final product is located at the charge center of the ultimate carbocation intermediate (Eq. 62).…”