Synthesis and Diels–Alder reactions of α-fluoro- and α-trifluoromethylacrylonitriles

Selective synthesis of α-trifluoromethyl-β-aryl enamines or vinylogous guanidinium salts by treatment of β-halo-β-trifluoromethylstyrenes with secondary amines under different conditions

“…5 Also, the ease of b-halogen atom substitution by C-, S-and O-nucleophiles in b-chloro-and b-bromob-(trifluoromethyl)styrenes or b-bromo-b-fluorostyrenes was demonstrated in a series of publications. Treatment of these compounds with copper cyanide, sodium 4-methylphenylsulfinate, alkylthiolates, arylthiolates and alkoxides resulted in a number of novel convenient approaches to a-fluoro-and a-trifluoromethylacrylonitriles, 6 a-fluoro-b-arylvinyl sulfones, 7 trifluoromethyl(vinylsulfides), 8 and alkoxy-b-(trifluoromethyl)styrenes. 9 Having such encouraging results, we decided to continue our investigations on the synthetic utility of b-halo-b-(trifluoromethyl)styrenes examining their reactions with N-nucleophiles.…”

Recent progress in the use of fluoroorganic compounds in pericyclic reactions

“…67 The a-fluorinated derivatives of 42 are not useful as dienophiles as a result of inseparable product mixtures (Scheme 21).…”

A molecular electron density theory study of Diels‐Alder reaction between Danishefsky's diene and (2E)‐3‐phenyl‐2‐(trifluoromethyl) acrylonitrile

“…Recently 2‐methoxy‐6‐phenyl‐4‐oxo‐1 (trifluoromethyl) cyclohexanecarbonitrile ( 6 and 7 ), only one regioisomer of the corresponding nitriles as a 2:1 mixture of diasteremers 6 and 7 , through a regioselective DA reaction of Danishefsky's diene (DD 4 ) toward (2E)‐3‐phenyl‐2‐(trifluoromethyl) acrylonitrile (EPTA 5 ), was synthesized with a moderate yield of 88% (Scheme ) . Due to high nucleophilic nature of DD 4 , it is a very reactive reagent in DA reactions.…”

“…In the present theoretical study, an MEDT study of the DA reaction between DD 4 and EPTA 5 was performed at the DFT‐M06‐2X/6‐31G(d,p) level in order to characterize the regioselectivity and stereoselectivity and mechanism of the reaction. The comparison between the results of this work with those obtained by the experiment reported in a previous study showed very good agreement.…”