A Convenient Method for the Transformation of Alcohols into Alkyl Trifluoromethyl Sulfides

Electrophilic S‐Trifluoromethylation of Cysteine Side Chains in α‐ and β‐Peptides: Isolation of Trifluoro‐methylated Sandostatin® (Octreotide) Derivatives

“…It has already been shown that these hypervalent iodine(III)ÀCF 3 reagents can be used for S-trifluoromethylation of cysteine esters (with or without N-protection) in high yields; the reaction is carried out in MeOH at dry-ice temperature in the absence of base [9]. Before invention of the reagents A and B, SCF 3 substituents were introduced into organic molecules by functional-group interconversions under rather drastic conditions [13], by direct transfer of the SCF 3 moiety [14], or by the delivery of CF 3 to a S-atom by a nucleophilic, or, more often, a radical reaction [15] [16]. The hitherto less common electrophilic S-trifluoromethylation with (trifluoromethyl)dibenzothio-, -seleno-, or -tellurophenium salts (Umemoto and Ishihara [17]) requires preformed sodium thiolates, and the product is accompanied by a considerable amount of disulfide.…”

“…Trifluoromethylation of 6. (14). Compound 6 (17.6 mg, 14.1 mmol) was dissolved in degassed MeOH (7.05 mm) and cooled to À 788.…”

1,1,1,4,5,5,5-Heptafluoro-4-(trifluoromethyl)-2,3-pentanedione, a potent reagent for the synthesis of cyclic ?5?5 phosphoranes

“…The phosphorus(III) compounds, PR 1 R 2 R 3 , 1 (R 1 ‫ס‬ CF 3 , R 2 ‫ס‬ R 3 ‫ס‬ Me (1a) [12], iPr (1b) [13], NEt 2 (1c) [14]; R 1 ‫ס‬ NCO, R 2 ‫ס‬ R 3 ‫ס‬ OMe (1d), OEt (1e) [15], R 2 -R 3 ‫ס‬ OCH 2 CH 2 O (1f), OCMe 2 CMe 2 O (1g) [16]; R 1 ‫ס‬ OSiMe 3 , R 2 ‫ס‬ R 3 ‫ס‬ OEt (1h) [17]; R 1 ‫ס‬ NEt 2 , R 2 ‫ס‬ R 3 ‫ס‬ OCH 2 CF 3 (1i) [18]; R 1 ‫ס‬ R 2 ‫ס‬ Et 2 N, R 3 ‫ס‬ OCH 2 CF 3 (1j) [19], OCH(CF 3 ) 2 (1k) [20], OCH 2 Ph (1l) [21], OC 6 F 5 (1m) [19]) were reacted with 1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2,3-pentanedione (2) to yield 1,3,2k 5 r 5 -dioxaphospholenes 3a-m, mainly colorless liquids but solids in the case of 3f, 3g, and 3m (Scheme 1). There was no interaction of the isocyanato group in 1d-g with the diketone observed, unlike the corresponding reaction with hexafluoracetone [9][10][11] ( Table 1).…”

“…[12], 1b [13], 1c [14], 1d and 1e [15], 1f and 1g [16], 1h [17], 1i [18], 1j [19], 1k [20], 1l [21], 1m [19], and 2 [6] were prepared according to literature procedures. 19 F, and 31 P NMR Data a of the Phosphoranes 3a-3m (J is given in Hz) General Method for the Synthesis of Phosphoranes 3a-3m (see Table 2 ) A stoichiometric amount of each phosphorus derivative 1 was added dropwise to a solution of compound 2 in 10 mL of diethyl ether at ‫01מ‬ЊC, stirred for 1 hour and then allowed to react at ambient temperature for 2 hours.…”

Regio- and Stereocontrolled Nucleophilic Trifluoromethylthiolation of Morita–Baylis–Hillman Carbonates

“…13,14 Transformation of alcohols into trifluoromethyl sulfides through phosphitylation and reaction with bis(trifluoromethyl) disulfide was also reported. 15 Various α-diazo compounds reacted with AgSCF 3 in copper-mediated trifluoromethylthiolations to form C(sp 3 )-SCF 3 bonds. 16 For a cheap and storable crystalline source of SCF 3 anion, Li and Zard reported the synthesis of O-octadecyl-S-trifluorothiolcarbonate, CF 3 SCO 2 C 18 H 37 , and reactions with gramines and α-bromoketones and -ester in the presence of KF and pyrrolidine.…”