Pyrolysis of benzenediazonium bis(trifluoromethanesulfonyl)methide

Synthetic Methods for Compounds Having CF3–S Units on Carbon by Trifluoromethylation, Trifluoromethylthiolation, Triflylation, and Related Reactions

“…An oxygen phenylation product, and not a carbon phenylation product, was obtained (eq b, Scheme 85). 342 Halonium ylides could be prepared from bis(triflyl)methane (Scheme 86). Chen and Zhu reported the synthesis of phenyliodonium bis(triflyl)methide by the reaction of bis-(triflyl)methane and diacetoxyiodobenzene in good yield (eq a, Scheme 86).…”

“…443 Yamamoto and co-workers reported the pyrolysis of benzenediazonium bis(triflyl)methide in acetonitrile to give a novel acetonitrileinserted compound, PhNH(Me)CC(SO 2 CF 3 ) 2 , quantitatively (eq c, Scheme 122). 342 In this reaction, bis(triflyl)methide anion reacted with an ammonium ion intermediate, which was generated by the nucleophilic attack of the nitrogen atom in acetonitrile until the phenyl cation formed. The last method for the synthesis of vinyl triflone is the oxidation reaction (Scheme 123).…”

“…Surprisingly, Yamamoto and co-workers could not repeat this reaction. An oxygen phenylation product, and not a carbon phenylation product, was obtained (eq b, Scheme ) …”

Synthesis of superacidic carbon acid and its derivatives

“…This type of salts was obtained by the reaction of dry KCH(SO 2 R f ) 2 with arenediazonium chloride in water [40]. Although expected C-arylation reaction via pyrolysis of PhN 2 + Tf 2 CH -19a under neat conditions had been reported [41], Yamamoto pointed out that only O-arylation product 20a was given (Scheme 16) [42]. There is only one example for acylation reaction of Tf 2 CH 2 3a with acyl chloride (Scheme 18) [44].…”

Weakly Nucleophilic Conjugate Bases of Superacids as Powerful Nucleophiles in Vinylic Bimolecular Nucleophilic Substitutions of Simple β-Alkylvinyl(aryl)-λ3-bromanes

“…The unique structure of ( Z )-ylide 8a was identified by 1 H, 13 C, and 19 F NMR and MS spectral analyses, especially by (1) two peaks with 1:1 intensity at −75.6 and −80.5 ppm in the 19 F NMR spectrum, indicating the presence of different kinds of CF 3 groups, and (2) a small vicinal coupling constant of 5.6 Hz between the vinylic protons and a sharp singlet peak at 4.25 ppm assigned to the hydrogen atom attached to the ylidic CS bond in the 1 H NMR spectrum (see Scheme S4). Potassium bis(nonaflyl)methanide also afforded ( Z )-ylide 8d selectively in high yield (entry 4). The presence of a sterically demanding β- tert -butyl group in ( E )-alkenyl(phenyl)-λ 3 -iodanes completely inhibits the S N 2 displacement with halide anions but instead results in syn β-elimination, yielding a terminal alkyne; however, tert -butylvinyl-λ 3 -bromane 3c did undergo the S N 2V reaction with bis(sulfonyl)methanide anions and afforded ( Z )-sulfinates 8c and 8f , albeit in moderate yields.…”