Nucleophilic Fluoromethylation of Aldehydes with Fluorobis(phenylsulfonyl)methane: The Importance of Strong Li-O Coordination and Fluorine Substitution for C—C Bond Formation

摘要

Recently, the selective introduction of fluorinated moieties into organic molecules with α-fluorinated carbanions has attracted substantial interest in organic synthesis, owing to the increasingly important applications of selectively fluorinated organics in life and materials sciences. In particular, α-fluoro(phenylsulfonyl)methane (FSM) derivatives, such as difluoromethyl phenyl sulfone (PhSO2CF2H), fluoromethyl phenyl sulfone (PhSO2CH2F), and fluorobis(phenylsulfonyl)-methane (FBSM), have been extensively studied as excellent precursors of α-fluorinated carbanions for nucleophilic di-and monofluoromethylations. In this context, FBSM, a reagent independently reported by Shibata et al. and our group in 2006, has been widely recognized as a robust nucleophilic monofluoromethylating agent for many applications, including catalytic enantioselective monofluoromethylation reactions. However, although FBSM reacts with a great variety of electrbphiles, its nucleophilic addition reaction with aldehydes still remains a challenge.