Phenylthio migrations in rearrangements of 2,2-bisphenylthioethanols

Reactions of α- or γ-phenylthio substituted extended enolate anions derived from esters

“…eluting with dichloromethane gave the Eketo ester [86 mg, 39%, (42% based on recovered starting material)] as an oil, RdCH,Cl,) 0.36; v,,,&q. Methyl 2-Benzoyl-3-phenylthiopentanoate (49).-The ester ( B b ) (163 mg, 0.5 mmol) in ethanol (5 ml) was added to a stirred solution of sodium hydroxide (40 mg, 1.0 mmol) and thiophenol(220 mg, 0.2 ml, 2 mmol) in ethanol (20 ml). After 1.5 h the mixture was diluted with ether (50 ml) and brine (20 ml), washed with water (3 x 20 ml) and brine (2 x 10 ml), dried (MgSO,), and evaporated under reduced pressure.…”

Synthesis of α-phenylthio enones and esters of α-phenylthio alkenoic acids

“…134-137 "C/0.5 mmHg, of which only the Z-isomer, R,(CH,C12) 0.52 had been reported previously. 24 solution of mchloroperbenzoic acid (80% grade; 38 g, 0.17 mol) in dry ether (1 70 ml) was added slowly to a stirred, cooled (0 "C) solution of the sulphide (0.17 mol) in dry ether (500 ml) under a nitrogen atmosphere. The resultant suspension was stirred for a further 0.5 h at O"C, condensed, diluted with dichloromethane, and then washed with aqueous sodium thiosulphate (3 x 150 ml), aqueous sodium hydrogen carbonate (3 x 150 ml), and brine (2 x 100 ml), and dried (MgSO,).…”

“…-P h G SPh Ph+ (10) In other cases where the carbon skeleton is unsymmetrical, our regiospecific route24 to a-phenylthio ketones can be used: ketones (14) and (16) were made by this method, and ketone (18) has already been reported. 24 The ketone (18) was oxidised to its sulphoxide (19) and the Pummerer elimination route used to make the a-phenylthio enone (lb) in 89% yield as a 30: 1 mixture of Alkylation of the extended enolate from the cyclic apropylthio enone (22) has been reported" to give predominantly the a-product (23) in contrast to the formation of the a'-product (24) from the kinetic enolate. The best conditions for extended enolate formation were Bu'OK in Bu'OH, followed by HMPA and then MeI.…”

Rearrangements of 2-phenylthioethanols with alkenyl, alkynyl, ester, and other functionalised alkyl substituents at the migration origin: synthesis of γ-phenylthiocrotonate esters

“…(film) 1700 (C=O) and 1 630 cm-' ( C S ) ; G(CDC1,) 7.3 (5 H, br s, PhS), 5.19 and 5.29 (2 H, each d, J 0. 5 Hz, W H , ) , 2.73 and 3.12 (2 H, ABq, J 15 Hz, CHZCCI), 2.41 (3 H, s, MeCO), and 1.48 (3 H, s, PhSCMe).…”