title: Formamides as Lewis Base Catalysts in SN Reactions-Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers.
abstract: A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent functional group tolerance, scalability (>100 g) and waste-balance (E-factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one-pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac-Clopidogrel and S-Fendiline.
authors.affiliation: Universität des Saarlandes, Institut für Organische Chemie, Postfach 151150, 66041, Saarbrücken, Germany. peter.huy@uni-saarland.de.
authors.forename: Peter H
authors.identifier: 0000-0002-5099-5988
authors.initials: PH
authors.lastname: Huy
authors.affiliation: Universität des Saarlandes, Institut für Organische Chemie, Postfach 151150, 66041, Saarbrücken, Germany.|Universität zu Stuttgart, Institut für Organische Chemie, Pfaffenwaldring 55, 70569, Stuttgart, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Motsch
authors.affiliation: Universität des Saarlandes, Institut für Organische Chemie, Postfach 151150, 66041, Saarbrücken, Germany.
authors.forename: Sarah M
authors.initials: SM
authors.lastname: Kappler
keywords: green chemistry; halogenation; homogenous catalysis; nucleophilic substitution; organocatalysis