33491-05-3

Upstream product

• 60512-56-3 1-(2,2-dibromovinyl)-4-methylbenzene 
• 75-25-2 Bromoform 
• 104-81-4 4-Methylbenzyl bromide 
• 506-68-3 bromocyane 
• 90-02-8 salicylaldehyde 
• 558-13-4 carbon tetrabromide 
• 104-87-0 4-methyl-benzaldehyde 
• 1777-53-3 1-(p-tolyl)-2-(triphenylphosphoranylidene)ethanone 
• 2227-58-9 3-(4-methylphenyl)prop-2-ynoic acid 
• 3201-61-4 -triphenyl-phosphoran 
• 72591-22-1 p-(2,2,2-Tribromaethyl)-toluol 
• 766-97-2 4-n-methylphenylacetylene 

Downstream Products

• 39654-02-9 p-tolyl(p-tolylethynyl)sulfane 
• 35205-60-8 diethyl 2-(1-(p-tolyl)ethylidene)malonate 
• 90504-41-9 Triphenyl-(3-p-tolyl-prop-2-ynylidene)-λ⁵-phosphane 
• 33675-56-8 1-(iodoethynyl)-4-methylbenzene 
• 22666-07-5 di-p-tolylbutadiyne 
• 619-41-0 4-(bromoacetyl)toluene 
• 3038-62-8 4-Methyltolazoline 
• 108030-81-5 2-(4-methoxyphenyl)pyrazine 
• 1231255-94-9 1-((Z)-4-bromo-3-propylhept-3-en-1-ynyl)-4-methylbenzene 
• 1258403-20-1 1-((Z)-2-bromo-1-iodovinyl)-4-methylbenzene 
• 65143-37-5 2-oxo-2-(4-tolyl)ethyl acetate 
• 1198612-93-9 5-bromo-4-p-tolyl-1H-1,2,3-triazole 
• 5301-96-2 4-(p-tolyl)-1H-[1,2,3]triazole 
• 57196-75-5 2,5-bis(p-tolyl)furan 

Relevant academic research and scientific papers

Nickel-Catalyzed Difunctionalization of Alkynyl Bromides with Thiosulfonates and N -Arylthio Succinimides: A Convenient Synthesis of 1,2-Thiosulfonylethenes and 1,1-Dithioethenes

An efficient nickel-catalyzed vicinal thiosulfonylation of 1-bromoalkynes with thiosulfonates in the presence of cesium carbonate is described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provides a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields. The extensive substrate scope of both alkynyl bromides and thiosulfonates is explored with a broad range of functional groups. Indole-derived 1,1-bromoalkenes were also successfully explored in this 1,2-thiosulfonylation process. Moreover, the nickel-catalyzed geminal -dithiolation of alkynyl bromides with N -arylthio succinimides provides 1,1-dithioalkenes in high yields. The present protocol is reliable on gram scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene is achieved in a scale-up synthesis. Following control experiments, a plausible mechanism is proposed to rationalize the experimental outcome and the vicinal thio-sulfonylation.

Regio- and Stereoselective N-addition to an Open Bromo Vinyl Cation

A protocol for the synthesis of thus far inaccessible bromo vinyl triflimides is presented. Our previously reported concept of assisted vinyl cation formation was engaged to achieve both a protonation of relatively electron poor bromo alkynes and a reaction with high regio- and stereoselectivity. To the best of our knowledge, this is the first stereoselective addition of an N-nucleophile to an open β-halovinyl cation.

Visible-Light-Promoted Formation of C—C and C—P Bonds Derived from Evolution of Bromoalkynes under Additive-Free Conditions: Synthesis of 1,1-Dibromo-1-en-3-ynes and Alkynylphosphine Oxides

The controllable achievement of C—C and C—P bond formations is developed via visible-light-promoted bromoalkyne dimerization or its further transformation with secondary phosphine oxides. The 1,1-dibromo-1-en-3-ynes are formed when bromoalkyne is exposed to visible-light. While alkynylphosphine oxides are generated when bromoalkynes are mixed with secondary phosphine oxides.

Fully Substituted Conjugate Benzofuran Core: Multiyne Cascade Coupling and Oxidation of Cyclopropenone

An unprecedented C═C double bond cleavage of cyclopropenone and dioxygen activation by multiyne cascade coupling has been developed. This chemistry provides a novel, simple, and efficient approach to synthesize fully substituted conjugate benzofuran derivatives from simple substrates under mild conditions. The density functional theory (DFT) calculations reveal that the unique homolytic cleavages of cyclopropenone and molecular oxygen are crucial to the success of this reaction.

Palladium-Catalyzed Carbonylation in the Synthesis of N-Ynonylsulfoximines

Palladium-catalyzed carbonylation reactions with Cr(CO)6 as carbonyl source are key for the preparation of N-ynonylsulfoximines from NH-sulfoximines and bromoalkynes. The couplings proceed at room temperature with a wide range of substrate combinations affording the corresponding products in good yields. (Figure presented.).

Catalytic Synthesis of Dibenzazepines and Dibenzazocines by 7-Exo- and 8-Endo-Dig-Selective Cycloisomerization

The 7-exo- and 8-endo-dig-selective gold-catalyzed cycloisomerizations of 2-propargylamino biphenyl derivatives were developed. The reaction of terminal alkynes gave dibenzo[b,d]azepines by 7-exo-dig cycloisomerization. In contrast, when internal alkynes were subjected to the reaction, 8-endo-dig cycloisomerization proceeded to provide dibenzo[b,d]azocines. The nucleophilicity at the reaction site and the electron-withdrawing effect of a tosyl group were important for the present selective transformation. This protocol could be used for ynamide substrates and a silver-catalyzed reaction gave 7-exo-dig products selectively.

A Radical-Initiated Fragmentary Rearrangement Cascade of Ene-Ynamides to [1,2]-Annulated Indoles via Site-Selective Cyclization

Straightforward access to [1,2]-annulated indoles, key substructures in natural products, is highly desirable yet challenging. Herein, a radical triggered fragmentary cyclization cascade reaction of ene-ynamides is presented, providing a rapid access into [1,2]-annulated indoles by an intermolecular radical addition, intramolecular cyclization, desulfonylative aryl migration, and site-selective C(sp2)-N cyclization sequence. DFT calculations support oxidation of N-centered radical species to cations prior to the C-N bond formation, followed by an unusual aza-Nazarov cyclization.

Epoxyanthracene Derivatives and Dicarbonylation on Benzene Ring via Hexadehydro-Diels-Alder (HDDA) Derived Benzynes with Oxazoles

A capture reaction of hexadehydro-Diels-Alder (HDDA) derived benzyne with various substituted oxazoles is reported. With methyl, hydrogen, or phenyl as the substituent at 2-position of oxazole, tetraynes afforded epoxyanthracene derivatives or underwent dicarbonylation on benzene ring. The reaction does not require any catalyst or additive. The mechanism behind the reaction was investigated. The obtained polycyclic product structure has potential application value in optoelectronic materials. The availability of dicarbonylated arene implies the uniqueness of HDDA benzyne reaction compared with traditional benzyne.

Direct oxidation ofN-ynylsulfonamides intoN-sulfonyloxoacetamides with DMSO as a nucleophilic oxidant

N-Arylethynylsulfonamides are oxidized intoN-sulfonyl-2-aryloxoacetamides directly and efficiently with dimethyl sulfoxide (DMSO) as both an oxidant and solvent with microwave assistance. DFT calculations indicate that DMSO nucleophilically attacks the ethylic triple bond and transfers its oxygen atom to the triple bond to form zwitterionic anionicN-sulfonyliminiums to trigger the reaction. Then it nucleophilically attacks the generated iminium intermediates to accomplish the oxidationviathe second oxygen atom transfer. The current method provides a straightforward and efficient strategy to transform variousN-arylethynylsulfonamides intoN-sulfonyl-2-aryloxoacetamides, sulfonyl oxoacetimides, without any other electrophilic activators or oxidants.

Access to Benzoxazepines and Fully Substituted Indoles via HDDA Coupling

The HDDA-derived benzyne intermediate was captured by oxazolines based on the addition reaction of benzyne to the Ca?N double bond. Benzoxazepine derivatives, fused benzoxazepine derivatives, and fully substituted indoles are synthesized in one step. The reaction does not require any catalyst or additives. Possible reaction mechanisms are presented.