37053-16-0

Upstream product

• 10181-73-4 (phenylsulfinyl)cyclopentane 
• 108-98-5 thiophenol 
• 120-92-3 cyclopentanone 
• 64741-03-3 ((1R,2R)-2-chlorocyclopentyl)(phenyl)sulfane 
• 930-29-0 1-chlorocyclopent-1-ene 
• 57774-95-5 5-(phenylthio)-1-pentanol 
• 28075-49-2 1-cyclopentenyl triflate 
• 882-33-7 diphenyldisulfane 
• 931-59-9 benzenesulfenyl chloride 
• 99965-75-0 5-(phenylthio)-1-pentyl mesylate 
• 99965-77-2 6-chloro-6-(phenylthio)hexanenitrile 
• 99965-76-1 6-(phenylthio)hexanenitrile 
• 19744-72-0 cyclopentyl phenyl sulfide 
• 930-69-8 sodium thiophenolate 

Downstream Products

• 71650-86-7 C₁₇H₁₆S 
• 103409-58-1 3-(2-Phenylsulfanyl-cyclopentyl)-cyclohexanone 
• 85895-43-8 (2-bromocyclopent-1-en-1-yl)(phenyl)sulfane 
• 85895-42-7 5-bromo-1-(phenylthio)cyclopent-1-ene 
• 85894-95-7 3-(α,α'-dicarbethoxy methyl)-2-phenylthiocyclopentene 
• 71624-76-5 (+/-)-1-acetoxy-2-phenylthio-2-cyclopentene 
• 71634-04-3 (5-Vinyl-cyclopent-1-enylsulfanyl)-benzene 
• 71634-03-2 (5-Butyl-cyclopent-1-enylsulfanyl)-benzene 
• 71634-01-0 C₁₇H₁₆S 

Relevant academic research and scientific papers

General Synthesis of Alkenyl Sulfides by Palladium-Catalyzed Thioetherification of Alkenyl Halides and Tosylates

The cross-coupling reaction of alkenyl bromides with thiols catalyzed by palladium complexes derived from inexpensive dppf ligand is reported. These reactions occur under low catalyst loading and in high yields and display wide scope, including the coupling of bulky thiols and trisubstituted bromoolefins, and functional group tolerance. In addition, the thioetherification of less reactive chloroalkenes and, for the first time, alkenyl tosylates was accomplished using a catalyst generated from CyPFtBu alkylbisphosphine ligand.

Ruthenium-catalyzed reaction of alkenyl triflates with zinc thiolates

A ruthenium complex coordinated with 3,4,7,8-tetramethyl-1,10- phenanthroline catalyzed the reaction of alkenyl triflates with zinc dithiolates to give alkenyl sulfides.

Mono- and bisadducts from the addition of thianthrene cation radical salts to cycloalkenes and alkenes

Thianthrene cation radical salts, Th.+ X-(X- = a, ClO4-; b, PF6-; c, SbF6-), add to cycloalkenes (C5-C8) in acetonitrile (MeCN) to form 1,2-bis(5-thianthreniumyl)cycloalkane salts and 1,2-(5,10-thianthreniumdiyl)cycloalkane salts, most of which have now been isolated and characterized. These are called bis- (3, 6, 9, 12) and monoadducts (4, 7, 10, 13). The proportional amount of the monoadduct obtained in the initial stage of the reaction varied with the cycloalkene in the order C6 ? C5 7 ? C8. Thus, the ratio bis:mono for C5 and C7 was, respectively, about 80/20 and 50/50. In contrast, only about 5% of the C6 monoadduct (7a) and none of 7b, c was obtained, while for C8 none of the bisadducts 12a-c was found. Bisadducts 3 and 9 lost thianthrene (Th) slowly in MeCN solution and changed into monoadducts 4 and 10. A comparable change from 6a into 7a was not observed. The monoadducts, themselves, lost a proton slowly in dry MeCN and opened into 1-(5-thianthreniumyl)cycloalkenes (5, 8, 11, 14). With 3 and 9, particularly, it was possible to follow with NMR spectroscopy the succession of changes, for example, 3 to 4 to 5. The opening of a monoadduct was made faster by adding a small amount of water to the solution. The bisadducts of 4-methylcyclohexene (15a) and 1,5- cyclooctadiene (17a) were isolated and characterized. Although a small amount of monodduct (16a) of 4-methylcyclohexene was found with NMR spectroscopy, it could not be isolated. Bis- and monoadducts were obtained also in additions of Th.+ ClO4- to acyclic alkenes, in relative amounts that, again, varied with the alkene. From cis-2-butene the dominant product was the bisadduct (18), while the monoaduct (19) was characterized with NMR spectroscopy but could not be isolated. In contrast, trans-3-hexene gave mainly the monoadduct (21), while the bis adduct (20) could not be isolated. With 4-methyl-cis-2-pentene, both bis- (22) and monoadduct (23) were isolated, the former being dominant. The conversion of 18 into 19 was characterized with NMR spectroscopy. In all cycloalkene bisadducts, the configurational relationship of the two thianthrenium groups was trans, while in the monoadducts, the bonds to the single thianthrene dication were (necessarily) cis. In both bis- and monoadducts of acyclic alkenes, the configuration of the alkene was retained. The mechanisms of addition with retention of configuration, of conversion of a bis- into a monoadduct, and of opening of a monoadduct are discussed. Products were identified with a combination of NMR spectroscopy, X-ray crystallography, elemental analysis, and (for cycloalkene adducts) reaction with thiophenoxide ion.

Highly active, air-stable palladium catalysts for the C-C and C-S bond-forming reactions of vinyl and aryl chlorides: Use of commercially available [(t-Bu)2P(OH)]2PdCl2, [(t-Bu)2P(OH)PdCl2]2, and [[(t-Bu)2PO···H·· ·OP(t-B0. u)2]PdCl]2 as catalysts

Air-stable palladium complexes [(t-Bu)2P(OH)]2PdCl2, [(t-Bu)2P(OH)PdCl2]2, and [[(t-Bu)2PO···H··· OP(t-Bu)2]PdCl]2 serve as efficient catalysts for a variety of cross-coupling reactions of vinyl and aryl chlorides with arylboronic acids, arylzinc reagents, and thiols to yield the corresponding styrene derivatives, biaryls, and thioethers. 31P NMR and mechanistic studies argue that the phosphinous acid ligands in the complexes can be deprotonated in the presence of a base to yield an electron-rich anionic species, which is likely a catalyst intermediate, and dimeric [[(t-Bu)2PO···H·· ·OP(t-Bu)2]PdCl]2 was isolated and cystallographically characterized. These anionic complexes are anticipated not only to accelerate the rate-determining oxidative addition of aryl chlorides but also to stabilize the palladium complexes in the catalytic cycle.

Clay Catalysis: A Simple and Efficient Synthesis of Enolthioethers from Cyclic Ketones

Montmorillonite KSF in refluxing toluene catalyses the synthesis of 1-alkyl- and 1-arylthioalkenes from ketones and thiols (thiophenol or 1-butanethiol).

A New Syntethic Route to Vinyl Sulfides Utilizing the Reaction of (Phenylthio)carbenes with Nitrile Anions

Reactions of nitrile anion (LiCR2R3CN) and (phenylthio)carbenes generated from 1-chloroalkyl phenyl sulfides (R1CH(Cl)SPh) 2a-e by the action of n-BuLi have been shown to be a useful synthetic route to vinyl sulfides (PhSC(R1)=CR2R3) 3a-k (34-91percent).The nucleophilic attack of the nitrile anion on the carbenic species gave the presumed intermediate β-(phenylthio)-β-lithionitrile, which eliminated LiCN to give the expected vinyl sulfides.The application of the present reaction to the synthesis of cyclic vinyl sulfides was successful: the decomposition of the dianion ofω,ω-bis(phenylthio)alkanenitriles (8b, 8c, 11, and 14) affording the corresponding 1-(phenylthio)cycloalkenes (9, 10, 12, and 15) in 12-87percent yields.

ENOL THIOETHERS AS ENOL SUBSTITUTES. AN ALKYLATION SEQUENCE.

Ionic bromination of enol phenyl thiolethers forms predominantly to exclusively 2-(phenylthio)-3-bromo-1-alkenes, an enolonium equivalent. The allylic bromide participates in displacements with stabilized and nonstabilized nucleophiles. The ability to hydrolyze the enol thioethers to their corresponding ketones equates this sequence to an equivalence of an enolonium ion. The versatility of the sulfur in selective introduction of allylic hydroxyl and amino groups as well as the ability to directly replace the sulfur substituent by hydrogen or alkyl imparts special significance to this approach. The sequence is highly regio-and chemoselective. Applications include the synthesis of lanceol and bisabolene and the introduction of steroid side chains.