Nacsa, Eric D.; MacMillan, David W. C. published the artcile< Spin-Center Shift-Enabled Direct Enantioselective α-Benzylation of Aldehydes with Alcohols>, Formula: C7H6FNO2, the main research area is chiral aldehyde enantioselective preparation; aldehyde alc enantioselective benzylation photoredox organocatalyst photocatalyst.
Nature routinely engages alcs. as leaving groups, as DNA biosynthesis relies on the removal of water from ribonucleoside diphosphates by a radical-mediated “”spin-center shift”” (SCS) mechanism. Alcs., however, remain underused as alkylating agents in synthetic chem. due to their low reactivity in two-electron pathways. We report herein an enantioselective α-benzylation of aldehydes using alcs. as alkylating agents based on the mechanistic principle of spin-center shift. This strategy harnesses the dual activation modes of photoredox and organocatalysis, engaging the alc. by SCS and capturing the resulting benzylic radical with a catalytically generated enamine. Mechanistic studies provide evidence for SCS as a key elementary step, identify the origins of competing reactions, and enable improvements in chemoselectivity by rational photocatalyst design.
Journal of the American Chemical Society published new progress about Alcohols Role: RCT (Reactant), RACT (Reactant or Reagent). 876919-08-3 belongs to class pyridine-derivatives, and the molecular formula is C7H6FNO2, Formula: C7H6FNO2.