119-43-7Relevant articles and documents
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Bowden
, p. 131 (1938)
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Deoxygenative α-alkylation and α-arylation of 1,2-dicarbonyls
Arman, Hadi D.,Dang, Hang T.,Haug, Graham C.,Jin, Shengfei,Larionov, Oleg V.,Nguyen, Viet D.
, p. 9101 - 9108 (2020/09/17)
Construction of C-C bonds at the α-carbon is a challenging but synthetically indispensable approach to α-branched carbonyl motifs that are widely represented among drugs, natural products, and synthetic intermediates. Here, we describe a simple approach to generation of boron enolates in the absence of strong bases that allows for introduction of both α-alkyl and α-aryl groups in a reaction of readily accessible 1,2-dicarbonyls and organoboranes. Obviation of unselective, strongly basic and nucleophilic reagents permits carrying out the reaction in the presence of electrophiles that intercept the intermediate boron enolates, resulting in two new α-C-C bonds in a tricomponent process. This journal is
Enantioselective Hydrogen Atom Transfer: Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases
Sandoval, Braddock A.,Meichan, Andrew J.,Hyster, Todd K.
supporting information, p. 11313 - 11316 (2017/08/30)
Flavin has long been known to function as a single electron reductant in biological settings, but this reactivity has rarely been observed with flavoproteins used in organic synthesis. Here we describe the discovery of an enantioselective radical dehalogenation pathway for α-bromoesters using flavin-dependent 'ene'-reductases. Mechanistic experiments support the role of flavin hydroquinone as a single electron reductant, flavin semiquinone as the hydrogen atom source, and the enzyme as the source of chirality.
