O,O‐Dialkylthiophosphonosulfenyl Bromides— A New Class of Reactive Organophosphorus Compounds

O,O-Dimethylthiophosphonosulfenyl bromide-silver triflate: a new powerful promoter system for the preactivation of thioglycosides

“…22 O,O-Dimethylthiophosphonosulfenyl bromide (1) was prepared as described in the literature. 19 A solution of Br 2 (0.51 g, 3.2 mmol) in CCl 4 (1.0 mL) was added to a stirred solution of 2 (1.0 g, 3.2 mmol) in CCl 4 (4.0 mL) at -25 • C, the mixture was stirred for 10 min. The solution was used as the promoter directly without purification.…”

“…1), prepared from tetramethyl thioperoxydiphosphate (2) and bromine, is a "soft" electrophilic reagent and easily binds to the "soft" sulfur atom. Since it was first synthesized by Michalski and co-workers, 19 DMTPSB has attested considerable interest in the field of organic chemistry, due to its easy preparation and low cost. However, DMTPSB has never been applied to the glycosylation reaction.…”

“…HRMS (ESI) calcd for C 55 H 50 NaO 15 [M + Na] + : 973.3042, found 973.3031. 6-tri-O-benzyl-a-D-glucopyranoside(19). Compound 1924 (18.1 mg, 91% yield as a semisolid) was prepared according to the general procedure for pre-activation glycosylation from donor 3 (15.0 mg, 21 mmol) and acceptor 12 (10.5 mg, 19 mmol) and purified by column chromatography (petroleum ether/ethyl acetate = 4 : 1).1 H NMR (300 MHz, CDCl 3 ): d 8.02 (d, 2H, J = 7.2 Hz), 7.93 (d, 2H, J = 7.2 Hz), 7.85 (d, 2H, J = 7.2 Hz), 7.74 This journal is © The Royal Society of Chemistry 2011 Org.…”

A new and efficient conversion of olefins into thiiranes using diethoxyoxophosphoranesulfenyl chloride

“…Our previous synthesis was based on diethoxythioxaphosphoranesufenyl bromide (EtO) 2 P(O)SBr 8. Although this compound can readily be prepared from diethylphosphorodithioic acid (EtO) 2 P(S)SH by reaction with elemental bromine [12], its stability is much lower than that of diethoxyoxophosphoranesulfenyl chloride 1. Also, sulfenyl bromide 8 reacts with alkenes to give a considerable amount of side products (alkane dibromides 9 and disulfide 10) together with addition products of the type 5 [13].…”

A General Synthesis of Thiophosphates Containing an α,β-Unsaturated Carbonyl Moiety

“…7-9 A mixture of (E) and (Z) diastereoisomers (75:25) is only obtained in the case of dienolate 7c, (E)/ (Z) ratio is the same as in starting ketone (Table 1, entry c). Then addition of phosphorus S-electrophiles O,O-dialkylchloro thiophosphonates (RO) 2 P(O)SCl 10 9 and O,Odialkylbromo dithiophosphonates (RO) 2 P(S)SBr 11, 12 10 to 7 and 8 afforded compounds 1-2 and 3-4 respectively (Scheme 2). Compounds 9 and 10 can be readily prepared from commercial materials and used without isolation.…”