Development of a Modified Bouveault–Blanc Reduction for the Selective Synthesis of α,α-Dideuterio Alcohols

Abstract

A modified Bouveault-Blanc reduction has been developed for the synthesis of α,α-dideuterio alcohols from carboxylic acid esters. Sodium dispersions are used as the electron donor in this electron transfer reaction, and ethanol-d is employed as the deuterium source. This reaction uses stable, cheap, and commercially available reagents, is operationally simple, and results in excellent deuterium incorporation across a broad range of aliphatic esters, which provides an attractive alternative to reactions mediated by expensive pyrophoric alkali metal deuterides.

Retracted Article: Synthesis of deuterated isopentyl pyrophosphates for chemo-enzymatic labelling methods: GC-EI-MS based 1,2-hydride shift in epicedrol biosynthesis

“…Further, the ester group is reduced with 2 H followed by the use of Bouveault-Blanc conditions 16 to obtain the corresponding alcohol, which when treated with TBDPSCl (tert-butyl-diphenylchlorosilane) gives protected-OH 7. The selective deprotection of the ketone of 7 is achieved in the presence of PPTS (pyridinium ptoluenesulfonate) in aqueous acetone.…”

40 Years of Hydrogen–Deuterium Exchange Adjacent to Heteroatoms: A Survey

“…The original approach for the synthesis of deuterated compounds involves classical transformations with deuterated reagents, 14,15 deuterated starting materials, 16,17 or deuterated solvents, with reductive deuteration being one such example. [18][19][20] However, these strategies can be time-consuming and/or cost-intensive. Indeed, deuterated reagents are expensive and should be ideally introduced at the end of a synthesis to reduce losses.…”

Selective C-N σ Bond Cleavage in Azetidinyl Amides under Transition Metal-Free Conditions

“…Previously, our group developed a more practical protocol for the synthesis of electride salts, using sodium dispersions and 15-crown-5 [28]. Sodium dispersion in oil is a bench-stable and commercially available reagent with a high specific surface area [28,29,30,31,32]. The derived electride has already been successfully applied in a chemoselective ammonia-free Birch reduction [28].…”