35162-74-4

Upstream product

• 106-25-2 Nerol 
• 882-33-7 diphenyldisulfane 
• 124-63-0 methanesulfonyl chloride 
• 106-24-1 Geraniol 
• 2973-86-6 lithium thiophenoxide 
• 930-69-8 sodium thiophenolate 
• 108-98-5 thiophenol 
• 4551-15-9 phenylthiotrimethylsilane 
• 85217-72-7 geranyl methyl carbonate 
• 113034-93-8 9-(phenylthio)-9-borabicyclo<3.3.1>nonane 
• 72863-23-1 3,7-dimethyl-3-(p-tolylsulfonyl)-1,6-octadiene 
• 78-70-6 3,7-dimethylocta-1,6-dien-3-ol 
• 19451-54-8 3,7-dimethyl-octa-2,6-dienyl diphenyl phosphate 
• 19451-55-9 Neryl diphenyl phosphate 

Downstream Products

• 125556-26-5 (Z)-6,10-Dimethyl-4-phenylthio-5,9-undecadienal ethylene acetal 
• 83577-63-3 (2,6-dimethyl-2-vinylhept-5-enyl)(phenyl)sulfane 
• 245514-65-2 (Z)-(R)-2-[(2S,5R)-5-((Z)-(S)-1-Hydroxy-1,5,9-trimethyl-3-phenylsulfanyl-deca-4,8-dienyl)-tetrahydro-furan-2-yl]-6,10-dimethyl-4-phenylsulfanyl-undeca-5,9-dien-2-ol 
• 128266-14-8 benzyl ether of 10,14-dimethyl-6-hydroxymethylpentadeca-5E,9Z,13-trien-1-ol 
• 128266-13-7 benzyl ether of 10,14-dimethyl-5-hydroxy-6-formylpentadeca-9Z,13-dien-1-ol 
• 121926-71-4 (5E)-1-benzyloxy-6,10-dimethyl-4-phenylthio-5,9-undecadien-2-ol 
• 38011-83-5 trans-1-(4,8-dimethylnona-3,7-dien-1-yl)-4-methoxybenzene 
• 56691-80-6 geranyl phenyl sulfone 
• 31236-12-1 3,7-dimethyl-octa-2,6-dienyl phenyl sulfoxide 
• 74832-85-2 6,7-oxido-3,7-dimethyl-1-(benzenesulfonyl)-(2E)-octene 
• 471295-24-6 (2,6-dimethyl-1-phenylsulfanyl-2-vinyl-hept-5-enyl)-trimethyl-silane 
• 792966-17-7 [(E)-6,10-dimethylundeca-1,5,9-trien-4-yl](phenyl)sulfane 

Relevant academic research and scientific papers

Reaction of Allyl Diphenyl Phosphates with Soft Bases

The title phosphates were found to react with a variety of soft bases to give nucleophilic substitution products in high yields.The reaction proceeded regiospecifically under mild reaction conditions with preservation of the double bond geometry.

Total Synthesis of (+)-Antroquinonol and (+)-Antroquinonol D

The first total synthesis of (+)-antroquinonol and (+)-antroquinonol D, two structurally unique quinonols with a sesquiterpene side chain, is described. The route features an iridium-catalyzed olefin isomerization-Claisen rearrangement reaction (ICR), lac

DECHALCOGENATIVE METHODS FOR THE PREPARATION OF ALLYLIC SULFIDES

A dechalcogenative method for the preparation of an allylic sulfide comprises contacting an activated chalcogenide of Formula (I) with a thiol of Formula (II) for a period of time sufficient to form an intermediate of Formula (III), and supplying sufficient activation energy to the intermediate of Formula (III), in a suitable solvent, preferably in the absence of a phosphine or other thiophile, to induce a [2,3]-sigmatropic rearrangement therein to form an allylic sulfide of Formula (IV), with concomitant loss of chalcogen Z, as set forth in the following reaction scheme, wherein X is an activating group selected from the group consisting of CN, S-pyridyl, S-heteroaryl, SO2-aryl, and SO3Y; Y is an alkali metal ion; Z is Se or S; R1, R2, R3, R4, and R5 are each independently H or a hydrocarbon moiety; and R is an organic moiety.

Dechalcogenative allylic selenosulfide and disulfide rearrangements: Complementary methods for the formation of allylic sulfides in the absence of electrophiles. Scope, limitations, and application to the functionalization of unprotected peptides in aqueous media

Primary allylic selenosulfates (seleno Bunte salts) and selenocyanates transfer the allylic selenide moiety to thiols giving primary allylic selenosulfides, which undergo rearrangement in the presence of PPh3 with the loss of selenium to give allylically rearranged allyl alkyl sulfides. This rearrangement may be conducted with prenyl-type selenosulfides to give isoprenyl alkyl sulfides. Alkyl secondary and tertiary allylic disulfides, formed by sulfide transfer from allylic heteroaryl disulfides to thiols, undergo desulfurative allylic rearrangement on treatment with PPh3 in methanolic acetonitrile at room temperature. With nerolidyl alkyl disulfides this rearrangement provides an electrophile-free method for the introduction of the farnesyl chain onto thiols. Both rearrangements are compatible with the full range of functionality found in the proteinogenic amino acids, and it is demonstrated that the desulfurative rearrangement functions in aqueous media, enabling the derivatization of unprotected peptides. It is also demonstrated that the allylic disulfide rearrangement can be induced in the absence of phosphine at room temperature by treatment with piperidine, or simply by refluxing in methanol. Under these latter conditions the reaction is also applicable to allyl aryl disulfides, providing allylically rearranged allyl aryl sulfides in good yields.

Synthesis of allylsilanes by reductive lithiation of thioethers

Although much work in reductive lithiation has been done, the utilization of allylthioethers bearing various substituents to prepare allylsilanes has not been explored. The main reason clearly stems from the anticipated lack of regioselectivity. We describe herein the first study on the regioselectivity of the reductive silylation involving dissymmetric allylthioethers. We surveyed a broad spectrum of parameters and showed that this process displays a great dependence of the reaction conditions. We also discovered that an electron transporter, DBB or naphthalene, can cleave THF at room temperature by sonication, to generate a strong base, 4-lithiobutoxide. This feature was successfully exploited to the straightforward synthesis of bis-silanes in one pot. Examples are provided for maximizing both the chemical yield and the regioselectivity of the reductive silylation through the tuning of the reaction conditions. By changing these conditions, several allylsilanes can be selectively synthesized from one thioether.

Oxidation of sulfides to sulfoxides and sulfones with 30% hydrogen peroxide under organic solvent- and halogen-free conditions

Aromatic and aliphatic sulfides are oxidized to sulfoxides or sulfones in high yield with 30% hydrogen peroxide under organic solvent- and halogen-free conditions. Dialkyl and alkyl aryl sulfides are cleanly oxidized to sulfoxides using aqueous hydrogen peroxide without catalysts. The best catalyst for the sulfone synthesis consists of sodium tungstate, phenylphosphonic acid, and methyltrioctylammonium hydrogensulfate. Co-existing primary or secondary alcohol or olefinic moieties are unaffected under such conditions.

Catalytic and asymmetric [2,3]sigmatropic rearrangement: Co(III)-salen catalyzed S-ylide formation from allyl aryl sulfides and their rearrangement

Reaction of allyl aryl sulfides and α-diazoacetic acid esters in the presence of optically active Co(III)-salen complex (8-Br) provided 3- substituted 2-arylthio-4-pentenoic acid esters stereoselectively by way of enantioselective S-ylide formation and subsequent diastereoselective [2,3]sigmatropic rearrangement. For example, the reaction of cinnamyl phenyl sulfide and (-)-menthyl α-diazoacetate provided (-)-menthyl (2R,3S)-2- phenylthio-3-phenyl-4-pentenoate of 74% de preferentially.

Effective combination of two-directional synthesis and rhenium(VII) chemistry: Total synthesis of meso polyether teurilene

The efficient total synthesis of the cytotoxic meso polyether teurilene (1), rarely occurring in nature, has been achieved through the effective combination of the concept of two-directional synthesis and the rapidly progressing rhenium(VII) chemistry. In

The palladium-catalyzed cross-coupling reaction of 9-organothio-9-borabicyclo[3.3.1]nonanes with organic electrophiles: Synthesis of unsymmetrical sulfides

The synthesis of unsymmetrical sulfides was carried out in high yields by the palladium-catalyzed cross-coupling reaction of 9-organothio-9-borabicyclo[3.3.1]nonane (9-RS-9-BBN) with organic electrophiles, such as iodoarenes, 1-iodo-1-alkenes, allyl carbonate and propargyl carbonate. Iodoarenes and 1-iodo-1-atkenes were smoothly converted into the corresponding sulfides at 50 °C in the presence of PdC12(dppf) (3 mol%) and K3PO4 (3 equiv.) in DMF. In contrast, the cross-coupling reaction of 9-RS-9-BBN with allyl or propargyl carbonates occurred in DMF without the assistance of a base. Both reactions catalyzed by Pd(dba)2-dppf regioselectively produced allyl and allenyl sulfides in excellent yields. The scope and limitations of the reactions, as well as the effects of varying the reaction conditions, are discussed.

Direct synthesis of allyl sulfides from allyl alcohols and thiols

In the presence of boron trifluoride-diethyl ether complex, various allyl alcohols [(-)-myrtenol, geraniol, cinnamyl alcohol, linalool, 1-octen-3-ol, 2-hydroxybenzyl alcohol and bicyclic diols] were reacted with thiophenol, 1-butanethiol, trimethyl(phenylthio)silane or hexamethylsilane in dichloromethane at room temperature to give the corresponding allyl sulfides in good to excellent yields. The mild conditions for this transformation allowed chemoselectivity.