21213-27-4

Upstream product

• 13865-07-1 (methoxy(phenylthio)methyl)benzene 
• 24850-33-7 allyltributylstanane 
• 76-63-1 allytriphenyltin 
• 155127-04-1 1-phenyl-1-(phenylthio)-1-(tributylstannyl)methane 
• 138904-87-7 1-[(1-phenylthio)benzyl]-1H-benzotriazole 
• 762-72-1 allyl-trimethyl-silane 
• 7695-69-4 bis(phenylthio)methylbenzene 
• 13865-50-4 methoxymethyl phenyl sulfide 
• 1212-08-4 S-Phenyl benzenethiosulfonate 
• 29817-09-2 1-methylene-2-phenylcyclopropane 
• 4351-54-6 cyclohexyl formate 
• 106-95-6 allyl bromide 
• 100-58-3 phenylmagnesium bromide 
• 108-98-5 thiophenol 

Downstream Products

• 67100-15-6 2-(2-phenyl-2-(phenylsulfonyl)ethyl)oxirane 
• 38425-47-7 3-phenyl-2-cyclobuten-1-one 
• 78710-67-5 2-hydroxymethyl-1-phenyl-1-phenylsulfonylcyclopropane 
• 92243-56-6 cis/trans-3-phenylcyclobutanol 
• 824-90-8 1-phenylbut-1-ene 

Relevant academic research and scientific papers

Sequential one-pot addition of excess aryl-grignard reagents and electrophiles to O-alkyl thioformates

The sequential addition of aromatic Grignard reagents to O-alkyl thioformates proceeded to completion within 30s to give aryl benzylic sulfanes in good yields. This reaction may begin with the nucleophilic attack of the Grignard reagent onto the carbon atom of the O-alkyl thioformates, followed by the elimination of ROMgBr to generate aromatic thioaldehydes, which then react with a second molecule of the Grignard reagent at the sulfur atom to form arylsulfanyl benzylic Grignard reagents. To confirm the generation of aromatic thioaldehydes, the reaction between O-alkyl thioformates and phenyl Grignard reagent was carried out in the presence of cyclopentadiene. As a result, hetero-Diels-Alder adducts of the thioaldehyde and the diene were formed. The treatment of a mixture of the thioformate and phenyl Grignard reagent with iodine gave 1,2-bis(phenylsulfanyl)-1,2-diphenyl ethane as a product, which indicated the formation of arylsulfanyl benzylic Grignard reagents in the reaction mixture. When electrophiles were added to the Grignard reagents that were generated insitu, four-component coupling products, that is, O-alkyl thioformates, two molecules of Grignard reagents, and electrophiles, were obtained in moderate-to-good yields. The use of silyl chloride or allylic bromides gave the adducts within 5min, whereas the reaction with benzylic halides required more than 30min. The addition to carbonyl compounds was complete within 1min and the use of lithium bromide as an additive enhanced the yields of the four-component coupling products. Finally, oxiranes and imines also participated in the coupling reaction. Into the melting pot: The addition of excess aryl Grignard reagents and electrophiles to O-alkyl thioformates gives aryl sulfanes through four-component coupling reactions (see scheme). These reactions may involve the formation of aromatic thioaldehydes and aryl-benzylic Grignard reagents as intermediates. For addition to carbonyl compounds, the use of lithium halides as an additive enhanced the efficiency of the reaction. Copyright

Rh(II)-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides

In this paper, Rh2(OAc)4-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides is reported. A series of tosylhydrazones derived from aldehydes were successfully used for [2,3]-sigmatropic rearrangement by reaction with either allylic phenyl sulfides or propargyl phenyl sulfides. The reaction conditions were optimized and afforded the products in moderate to good yields. In addition, a novel and convenient approach for the synthesis of cyclobutenones and cyclopropanes has been developed through direct oxidation of the rearrangement products.

An efficient radical procedure for the halogenation and chalcogenation of B-alkylcatecholboranes

An efficient formal anti-Markovnikov addition of HX (X = Cl, Br, I, SR and SeR) to olefins under mild reaction conditionsisdes cribed. The procedure isbas ed on the hydroboration of alkeneswith catecholborane. The conversion of the intermediate B-alkylcatecholboranesto the corresponding halides, sulfides and selenides is based on a common process, i.e., generation of a radical from the alkylborane followed by abstraction of a heteroatom from an aromatic sulfonyl reagent. The efficiency of these radical reactionsis remarkable. The mildness of the reaction conditions is well illustrated by the preparation of iodoalkanes. Despite the notorious reactivity of iodoalkanes under radical reaction conditions, no product degradation wasobs erved.

Benzylic intermolecular carbon-carbon bond formation by selective anodic oxidation of dithioacetals.

[reaction: see text]. Novel anodic intermolecular carbon-carbon bond formation has been accomplished by the oxidative carbon-sulfur bond fission of benzylic dithioacetals to give a wide variety of aromatic compounds. The substitution reaction successfully

α-(Benzotriazolyl)methyl phenyl thioethers: Convenient reagents for α-phenylthioalkylation of silylated nucleophiles

Stable, crystalline α-(benzotriazolyl)methyl phenyl thioethers (1), easily prepared from carbonyl compounds, thiophenol and benzotriazole, are convenient reagents for the phenylthiomethylation of trimethylsilyl cyanide, trimethylallylsilane, and trimethyl

Lewis Acid Activated Reactions of Mixed (O,Se) Acetals with Allyltrimethylsilane and Allyltributylstannane

On the basis of preferential complexation of oxygen or selenium atoms by different Lewis acids, it was expected that, depending on the Lewis acid employed, the title reactions would lead to selective formation of homoallyl ethers or homoallyl selenides.This has not been confirmed by experiment: in almost all the reactions tried homoallyl ethers largely predominated, or were the exclusive allylation products, even when strongly oxygenophilic Lewis acids such as TiCl4 were used.In the cases of the latter type of Lewis acids, the results observed with (O,Se) and a couple of (O, S) mixed acetals are interpreted in terms of two major factors operating in opposite directions. 1H NMR data of a mixture of TiCl4 and (O,Se) acetal indicate that preferential (but not exclusive) complexation of the oxygen moiety takes place indeed.However, because of the much stronger C-O bond as compared to the C-Se bond, this latter (also activated by the Lewis acid to some extent) undergoes cleavage by allyl metals to give homoallyl ethers as predominating products.In contrast with BF3*OEt2, boron trichloride and boron tribromide were found to react with (O, Se) acetals to give the corresponding α-halo selenides, which in turn were cleanly transformed into homoallyl selenides on reaction with allyltrimethylsilane in the presence of tin tetrachloride.

Oxidative Generation of Thioalkyl Cations from 2-Tributylstannyl-1,3-dithianes and 1-(Tributylstannyl)alkyl Sulfides and Their Reactions with Olefinic Nucleophiles

2-Tributylstannyl-1,3-dithianes and 1-(tributylstannyl)alkyl sulfides are oxidized with ammonium hexanitratocerate(IV) or ferrocenium hexafluorophosphate to generate their cation radicals, which dissociate into the carbocations and tributylstannyl radical

Stereoselective Additions of Nucleophilic Alkenes to Chiral Thionium Ions

A convenient one-pot process has been developed for conversion of an aldehyde to an arylthionium ion (e.g., Schemes IV and V), which can be trapped by a nucleophilic alkene.The stereochemistry of the reactions of such chiral and prochiral arylthionium ions with achiral and prochiral nucleophilic alkenes has been studied.The major adducts are those predicted by qualitative application of the Cram-Felkin rule.Quantitatively, however, the nature of the thionium aryl group has a marked effect.For example, whereas 12 reacts with the phenylthionium ion derived from 2-phenyl propanol to give keto sulfides 13a and 14a in a ratio of 4:1, the corresponding reaction of the mesitylthionium ion affords the analogous keto sulfides 24a and 25a in a ratio of > 98:2.In reactions between prochiral thionium ions and prochiral enol silanes, good simple (anti) relative stereochemistry is observed, especially with enol silane 35 (Scheme VII, Table IV).Mesitylthionium ions of α-chiral aldehydes react with prochiral enol silanes to give one of the four possible products in predominance (Scheme VIII, Table V).Again, however, enol silane 35 is found to be a superior reagent, giving 41 in 97percent stereoisomeric purity.The α-methyl-β-arylthio ketones produced in these thionium ion reactions can be transformed by a straightforward process, which includes desulfurization, into chain compounds having anti 1,3-dimethyl branches (e.g., Scheme IX).An iterative application of this scheme can be used to prepare deoxypolypropionate structures, as shown in Scheme X.

METHOXY(PHENYLTHIO)METHANE AS AN AMBI-EQUVIVALENT OF A METHOXY- OR PHENYLTHIOMETHYLENE 1,1-DIPOLE

Methoxy(phenylthio)methane undergoes electrophilic alkylation followed by nucleophilic allylation or propargylation which is dramatically changed depending on the Lewis acid employed providing a methoxy- or phenylthiomethylene 1,1-dipole synthon.