65248-43-3Relevant articles and documents
Ketone Synthesis from Benzyldiboronates and Esters: Leveraging α-Boryl Carbanions for Carbon-Carbon Bond Formation
Lee, Boran,Chirik, Paul J.
, p. 2429 - 2437 (2020/03/03)
An alkoxide-promoted method for the synthesis of ketones from readily available esters and benzyldiboronates is described. The synthetic method is compatible with a host of sterically differentiated alkyl groups, alkenes, acidic protons α to carbonyl groups, tertiary amides, and aryl rings having common organic functional groups. With esters bearing α-stereocenters, high enantiomeric excess was maintained during ketone formation, establishing minimal competing racemization by deprotonation. Monitoring the reaction between benzyldiboronate and LiOtBu in THF at 23 °C allowed for the identification of products arising from deborylation to form an α-boryl carbanion, deprotonation, and alkoxide addition to form an "-ate" complex. Addition of 4-trifluoromethylbenzoate to this mixture established the α-boryl carbanion as the intermediate responsible for C-C bond formation and ultimately ketone synthesis. Elucidation of the role of this intermediate leveraged additional bond-forming chemistry and enabled the one-pot synthesis of ketones with α-halogen atoms and quaternary centers with four-different carbon substituents.
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.
Silicon-(thio)urea Lewis acid catalysis
Hrdina, Radim,Mueller, Christian E.,Wende, Raffael C.,Lippert, Katharina M.,Benassi, Mario,Spengler, Bernhard,Schreiner, Peter R.
, p. 7624 - 7627 (2011/06/26)
We present a new class of catalysts based on the combination of N,N′-diaryl(thio)ureas and weak silicon Lewis acids (e.g., SiCl 4). Such silicon-(thio)urea catalysts effectively catalyze the stereospecific rearrangement of epoxides to quaternary carbaldehydes.