95841-50-2

Upstream product

• 108-98-5 thiophenol 
• 1066-54-2 trimethylsilylacetylene 
• 2973-86-6 lithium thiophenoxide 
• 138426-64-9 trans-1-(tributylstannyl)-2-(trimethylsilyl)epoxyethane 
• 114693-79-7 2,3-bis(trimethylsilyl)oxirane 
• 41309-43-7 (2-bromovinyl)trimethylsilane 
• 70737-20-1 (cis-2-bromo-vinyl)-trimethyl-silane 
• 1007-27-8 (phenylthio)trimethylstannane 

Downstream Products

• 82494-92-6 1-(phenylthio)-cis-bicyclo<3.3.0>oct-3-en-2-one 
• 82494-93-7 1-(phenylthio)-7,7-dimethyl-cis-bicyclo<3.3.0>oct-3-en-2-one 
• 19372-00-0 1-(trimethylsilyl)-2-phenylethene 

Relevant academic research and scientific papers

Synthesis and Configurational Assignment of Vinyl Sulfoximines and Sulfonimidamides

Vinyl sulfones and sulfonamides are valued for their use as electrophilic warheads in covalent protein inhibitors. Conversely, the S(VI) aza-isosteres thereof, vinyl sulfoximines and sulfonimidamides, are far less studied and have yet to be applied to the field of protein bioconjugation. Herein, we report a range of different synthetic methodologies for constructing vinyl sulfoximine and vinyl sulfonimidamide architectures that allows access to new areas of electrophilic chemical space. We demonstrate how late-stage functionalization can be applied to these motifs to incorporate alkyne tags, generating fully functionalized probes for future chemical biology applications. Finally, we establish a workflow for determining the absolute configuration of enantioenriched vinyl sulfoximines and sulfonimidamides by comparing experimentally and computationally determined electronic circular dichroism spectra, enabling access to configurationally assigned enantiomeric pairs by separation.

Rhodium(I) and iridium(I) complexes containing bidentate phosphine-imidazolyl donor ligands as catalysts for the hydroamination and hydrothiolation of alkynes

A series of novel cationic and neutral rhodium and iridium complexes containing bidentate phosphine-imidazolyl donor ligands of the general formulae [M(ImP)(COD)]BPh4 (M = Rh, ImP = ImP2, 3; ImP1a, 4a; ImP1b, 4b and M = Ir, ImP = ImP2, 5; ImP1a, 6a and ImP1b, 6b), [Ir(ImP)(CO)2]BPh 4 (ImP = ImP2, 7; ImP1a, 8a and ImP1b, 8b), [Rh(ImP1b)(CO) 2]BPh4 (10b) and [M(ImP)(CO)Cl] (M = Rh, ImP = ImP2, 11; ImP1b, 12 and M = Ir, ImP = ImP2, 13; ImP1b, 14) where COD = 1,5-cyclooctadiene, ImP2 = 1-methyl-2-[(2-(diphenylphosphino)ethyl]imidazole, 1; ImP1a = 1-methyl-2-[(diphenylphosphino)methyl]imidazole, 2a and ImP1b = 2-[(diisopropylphosphino)methyl]-1-methylimidazole, 2b were successfully synthesised. The solid state structures of 3, 6a, 11 and 12 were determined by single crystal X-ray diffraction analysis. A number of these complexes are effective as catalysts for the intramolecular hydroamination of 4-pentyn-1-amine to 2-methyl-1-pyrroline. The cationic complexes are significantly more effective than analogous neutral complexes. The cationic iridium complex 8b, containing the phosphine-imidazolyl ligand with the bulky isopropyl groups on the phosphorus donor, is more efficient than analogous complexes with the phenyl substituents on the phosphorus donor atom, 7 and 8a. The complexes 7-8b are also moderately effective in catalysing the addition of thiophenol to a range of terminal alkynes. In contrast to the hydroamination reaction, placement of the isopropyl group on the phosphorus donor leads to a decrease in the reactivity of the resulting metal complexes as catalysts for the hydrothiolation reaction.

Regio- and stereospecific cleavage of stannylepoxides with lithium phenylsulfide

Unsubstituted and α or β C-substituted epoxystannanes react with lithium phenylsulfide to give regio- and stereodefined α-phenylthio-β-hydroxystannanes resulting from α-opening with inversion of configuration. On the other hand, α- or β-trans-silyl epoxys

Regio- and stereospecific cleavage of α,β-epoxysilanes with lithium phenylsulfide

Trimethyl- or dimethylphenylsilylepoxides react with lithium phenylsulfide to give regio- and stereodefined vinyl sulfides resulting from α-ring opening and Peterson elimination. When the epoxide bears the bulky tert-butyldiphenylsilyl group the reaction

Synthesis of Triafulvalene Precursors by 'Carbene-Dimerization' of 1-Halogeno-1-lithiocyclopropanes

Bi(cyclopropylidenes) 7a, 7c, and 7e are available in a simple one-pot reaction by treating 1,1-dibromocyclopropanes 5 at -95° with BuLi and CuCl2. Attempts towards triafulvalene precursors with good leaving groups are reported. The most promising attempt makes use of 2,2′-bis(phenylthio)-3.3′-bis(trimethylsilyl)-1.1′- bi(cyclopropylidene) (7c) which has been oxidized to give the bis(phenylsulfonyl) derivative 7g. So far, F--induced elimination experiments with 7g failed.

PALLADIUM-CATALYZED REACTIONS OF TRIALKYLSTANNYL PHENYL SULFIDES WITH ALKENYL BROMIDES. A NEW DIASTEREOSELECTIVE SYNTHESIS OF (E)-1-ALKENYL PHENYL SULFIDES

The reaction of easily available stereoisomeric mixtures of 1-alkenyl bromides with molar excesses of trialkylstannyl phenyl sulfides takes place readily in the presence of Pd(PPh3)4 to afford diastereoselectively (E)-1-alkenyl phenyl sulfides in excellent yields.

Et3B Induced Radical Addition of Thiols to Acetylenes

Thiols added easily to acetylenic compounds in the presence of Et3B to give alkenyl sulfides in good yields.The reaction of acetylenes with 3-methyl-2-buten-1-thiol gave dihydrothiophene derivatives in one pot.

Silicon in Synthesis. 21. Reagents for Thiophenyl-Functionalized Cyclopentenone Annulations and the Total Synthesis of (+/-)-Hirsutene

1-(Trimethylsilyl)-1-(phenylthio)ethylene (1) reacts with cyclic α,β-unsaturated acid chlorides to give β-mercaptophenyl-substituted cyclopentenones, whereas 1-(trimethylsilyl)-2-(phenylthio)ethylene (2) under similar conditions results in thiophenyl migr