199276-69-2

Upstream product

• 53422-48-3 2-chloroethyl azide 
• 1004-22-4 (phenylethynyl)sodium 
• 10229-11-5 4-phenyl-but-3-yn-1-ol 
• 85375-43-5 4-methyl-N-(4-phenylbut-3-yn-1-yl)benzenesulfonamide 

Downstream Products

• 135469-70-4 4-phenyl-3-butyn-1-amine 
• 700-91-4 2-phenyl-1-pyrroline 
• 182324-83-0 4-methyl-N-(4-phenylbut-3-yn-1-yl)benzenesulfonamide 
• 3042-22-6 2-phenyl-1H-pyrrole 
• 97505-87-8 2-phenylpyrroline 

Relevant academic research and scientific papers

Atom-Economical Cross-Coupling of Internal and Terminal Alkynes to Access 1,3-Enynes

Selective carbon-carbon (C-C) bond formation in chemical synthesis generally requires prefunctionalized building blocks. However, the requisite prefunctionalization steps undermine the overall efficiency of synthetic sequences that rely on such reactions, which is particularly problematic in large-scale applications, such as in the commercial production of pharmaceuticals. Herein, we describe a selective and catalytic method for synthesizing 1,3-enynes without prefunctionalized building blocks. In this transformation several classes of unactivated internal acceptor alkynes can be coupled with terminal donor alkynes to deliver 1,3-enynes in a highly regio- and stereoselective manner. The scope of compatible acceptor alkynes includes propargyl alcohols, (homo)propargyl amine derivatives, and (homo)propargyl carboxamides. This method is facilitated by a tailored P,N-ligand that enables regioselective addition and suppresses secondary E/Z-isomerization of the product. The reaction is scalable and can operate effectively with as low as 0.5 mol % catalyst loading. The products are versatile intermediates that can participate in various downstream transformations. We also present preliminary mechanistic experiments that are consistent with a redox-neutral Pd(II) catalytic cycle.

Cu-Catalyzed Tandem Aerobic Oxidative Cyclization for the Synthesis of 3,3′-Bipyrroles from the Homopropargylic Amines

A Cu-catalyzed method for the synthesis of 3,3′-bipyrroles from homopropargylic amines through tandem aerobic oxidative cyclization involving the formation of C-C bond has been developed. The features of this reaction are a small number of Cu catalysis and simple starting substrates. Moreover, this procedure exhibits good functional group tolerance and a series of 3,3′-bipyrroles derivatives are obtained in moderate to good yields.

The acid-mediated intramolecular 1,3-dipolar cycloaddition of derived 2-nitro-1,1-ethenediamines for the synthesis of novel fused bicyclic isoxazoles

The discovery of a novel synthesis of new fused bicyclic isoxazoles, for example, N-methyl-3-phenyl-5,6-dihydro-4H-isoxazolo[3,4-c]azepin-8-amine (2a), N-methyl-3-phenyl-4,5-dihydroisoxazolo[3,4-c]pyridin-7-amine (2b) and N-methyl-3-phenyl-4H-pyrrolo[3,4-

Et2Zn-catalyzed intramolecular hydroamination of alkynyl sulfonamides and the related tandem cyclization/addition reaction

(Chemical Equation Presented) Intramolecular hydroamination of alkynyl amides was effected by a catalytic amount of Et2Zn (20 mol %) to form indole derivatives, and a tandem cyclization/nucleophilic addition procedure involving reaction of the indole zinc salt intermediate with acid chlorides or halides was developed to provide an efficient approach to C3-substituted indole derivatives when an excess of Et2Zn (120 mol %) was used.

Facile synthesis of medium-sized cyclic amines based on Friedel-Crafts reaction via iminium cation by use of acetylene dicobalt complex

An intramolecular Friedel-Crafts reaction of N-methoxymethyl sulfoneamides 3e-j containing an acetylene dicobalt moiety was found to proceed smoothly to afford eight- and nine-membered cyclic amines 4e-j in high yields.

Cyclization reactions of homopropargyl azide derivatives catalyzed by PtCl4 in ethanol solution: Synthesis of functionalized pyrrole derivatives

PtCl4-catalyzed cyclization reactions of homopropargyl azide derivatives to pyrrole rings were investigated. Using ethanol as solvent with 2,6-di-tert-butyl-4-methylpyridine as the base was found to be the best set of conditions for effecting this ring-closing reaction. These reaction conditions can be applied to the preparation of functionalized pyrrole derivatives, with no effect on the functional groups.

A study of vinyl radical cyclization onto the azido group by addition of sulfanyl, stannyl, and silyl radicals to alkynyl azides

Thermal radical reactions of azidoalkynes 2, 8, 14, and 21a-c with thiols 1a-c afford 2-sulfanylvinyl radicals by selective addition of sulfanyl radicals to the triple bond. 1-Phenylvinyl radicals 23 and 30a, as well as vinyl radical 30b, undergo fast 5-cyclization onto the aromatic azide function to give cyclized indoles. In contrast, both 1-phenyl (15, 17) and 1-alkyl (3a,b, 9) vinyl radicals fail to add to their aliphatic azido substituents and exclusively undergo cyclization onto the aromatic sulfanyl ring and H transfer from the thiol precursor. Azidoalkynes 14 and 21a react with Bu3SnH and TMSS under radical conditions to give instead the corresponding amines as a result of preferential attack of Bu3Sn · and (TMS)3Si · radicals on the azido group rather than on the triple bond. Evidence is provided that alkyl radical cyclizations onto azides are not feasible in the presence of thiol, in contrast with the reported utility of these cyclization reactions in the presence of Bu3SnH and TMSS.

Sulfanyl radical addition to alkynyl azides: An insight into vinyl radical cyclization onto the azido function

5-Exo-Cyclization of 2-sulfanylvinyl radicals 16 and 21 is a fast process which prevents intramolecular addition to the sulfanyl aromatic ring and hydrogen abstraction. In contrast, the 2-sulfanylvinyl radicals 3 and 9 are reluctant to add to their alipha

Palladium-Catalyzed Intramolecular Addition of Amines to Acetylenes. Synthesis of Cyclic Imines

Intramolecular aminopalladation of alkynylamines gave intermediary alkenylpalladium compounds that hydrolyzed and isomerized to thermodynamically stable cyclic imines.Treatment of 3-alkynylamines with a catalytic amount of PdCl2(MeCN)2 gave exclusively 1-