A novel protocol for a significantly improved, practical, and chemoselective ammonia-free Birch reduction mediated by bench-stable sodium dispersions and recoverable 15-crown-5 ether is reported. A broad range of aromatic and heteroaromatic compounds is reduced with excellent yields.
The first general reductive deuteration of nitriles under single-electron transfer conditions has been developed for the synthesis of α,α-dideuterio amines. This practical and cost-efficient protocol requires only bench stable and commercially available sodium dispersions and EtOD- d and allows for the reductive deuteration of a variety of nitriles in excellent yields and deuterium incorporations.
A transition-metal-free single electron transfer reaction has been developed for the synthesis of [D]-alkenes from terminal alkynes using sodium dispersions as the electron donor and EtOD- d as the deuterium source. Both reagents are cost-effective and bench-stable. This practical method exhibits remarkable terminal alkyne selectivity and exclusive alkene selectivity. Excellent deuterium incorporations and yields were achieved across a broad range of terminal alkynes without olefin isomerization. Of note, this reaction is highly solvent dependent. n-Hexane provides unique enhancement to this reductive deuteration process.
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.
Functionalization of amide bond via the cleavage of a non-carbonyl, C-N σ bond remains under-investigated. In this work, a transition-metal-free single-electron transfer reaction has been developed for the C-N σ bond cleavage of N-acylazetidines using the electride derived from sodium dispersions and 15-crown-5. Of note, less strained cyclic amides and acyclic amides are stable under the reaction conditions, which features the excellent chemoselectivity of the reaction. This method is amenable to a range of unhindered and sterically encumbered azetidinyl amides.
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