A Cascade Approach to Captodative Trifluoromethylated Enamines or Vinylogous Guanidinium Salts: Aromatic Substituents as Switches of Reaction Direction

Abstract

β‐Halo‐β‐(trifluoromethyl)styrenes readily react with a variety of nitrogen nucleophiles bearing primary amino groups to afford either the captodative trifluoromethylated enamines or vinylogous guanidinium salts in a selective fashion depending on the electronic natures of the aromatic substituents.

Theoretical and experimental 15N NMR study of enamine–imine tautomerism of 4‐trifluoromethyl[b]benzo‐1,4‐diazepine system

“…As model systems for the enamine and/or azomethyne moieties bearing trifluoromethyl group, we have studied four captodative enamines 2a–d , two push‐pull enamines 4a , b , and three related azomethynes 3a–c (Scheme ). The 15 N NMR shifts for these acyclic compounds have been calculated herewith and compared with available experimental data …”

CF Bond Activation of Unactivated Aliphatic Fluorides: Synthesis of Fluoromethyl‐3,5‐diaryl‐2‐oxazolidinones by Desymmetrization of 2‐Aryl‐1,3‐difluoropropan‐2‐ols

“…CF bond cleavage in an unactivated aliphatic position under mild conditions is still a challenge,8 although the substitution of CH 2 F groups by phosphine groups using R 2 PLi was reported 30 years ago 8h. Very recently, we have been able to substitute all three fluorines and another β‐halogen substituent of β‐trifluoromethyl‐β‐halostyrenes with primary amines to form vinylogous guanidinium salts 9. As part of our research program related to the development of biologically relevant fluorine‐containing molecules,10, 11 we have been interested in 3,5‐diaryl‐2‐fluoromethyl‐oxazolidin‐2‐ones ( 1 ).…”

Basicity of the polydentate captodative aminoenones. Ab initio , DFT, and FTIR study

“…For this reason, different aspects of the chemistry of both captodative and push–pull aminoalkenes bearing trifluoroacetyl substituent as a strong EWG attract special attention during the last decade . In continuation of our recent research in this field, we have performed a comparative examination of basic properties of captodative and push–pull fluorine‐bearing aminoalkenes and their non‐fluorinated analogues (Table ).…”