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.

An efficient one-pot sequential hydrogen isotope exchange (HIE)/ reductive deuteration approach was developed for the preparation of α,β-deuterated alcohols using ketones as the precursors. The HIE step can also be used for the synthesis of α-deuterated ketones. This method has been applied in the synthesis of four deuterated drug and MS internal standards.Letter pubs.acs.org/OrgLett

We report the first highly chemoselective synthesis of α,α-dideuterio alcohols with exquisite incorporation of deuterium (>98% [D2]) using pentafluorophenyl esters as ketyl radical precursors, SmI2 as a mild reducing agent, and D2O as the deuterium source. This system tolerates a variety of functional groups, offering rapid entry to valuable α,α-dideuterated alcohol building blocks. More generally, this report introduces pentafluorophenyl esters as the most reactive O-ketyl precursors reported to date.

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A practical and scalable single electron transfer reduction mediated by sodium dispersions has been developed for the reduction and reductive deuteration of tertiary amides. The chemoselectivity of this method highly depends on the nature of the proton donor. The challenging reduction via C-N bond cleavage has been achieved using Na/EtOH, affording alcohol products, while the use of Na/NaOH/HO leads to the formation of amines via selective C-O scission. Sodium dispersions with high specific surface areas are crucial to obtain high yields and good chemoselectivity. This new method tolerates a range of tertiary amides. Moreover, the corresponding reductive deuterations mediated by Na/EtOD- d and Na/NaOH/DO afford useful α,α-dideuterio alcohols and α,α-dideuterio amines with an excellent deuterium content.