182324-83-0

Upstream product

• 135469-70-4 4-phenyl-3-butyn-1-amine 
• 98-59-9 p-toluenesulfonyl chloride 
• 591-50-4 iodobenzene 
• 161040-05-7 N-(but-3-yn-1-yl)-4-methylbenzenesulfonamide 
• 18303-04-3 N-[(tert-butoxy)carbonyl]-4-methylbenzenesulfonamide 
• 70-55-3 toluene-4-sulfonamide 
• 338463-00-6 N-(tert-butoxycarbonyl)-N-but-3-ynyl-4-methylbenzenesulfonamide 
• 1307726-08-4 tert-butyl N-(4-phenylbut-3-yn-1-yl)-N-tosylcarbamate 
• 199276-69-2 (4-azidobut-1-yn-1-yl)benzene 
• 85375-43-5 4-methyl-N-(4-phenylbut-3-yn-1-yl)benzenesulfonamide 
• 10229-11-5 4-phenyl-but-3-yn-1-ol 

Downstream Products

• 247155-37-9 N-ethynyl-4-methyl-N-(4-phenyl-but-3-ynyl)-benzenesulfonamide 
• 247155-36-8 4-methyl-N-(4-phenyl-but-3-ynyl)-N-trimethylsilanylethynyl-benzenesulfonamide 
• 5435-06-3 4-methyl-N-[4-phenyl(4-deutero)butyl]benzene-1-sulfonamide 
• 1285256-77-0 C₁₉H₂₁NO₂S 
• 1286189-75-0 (E)-2-benzylidene-4-(N-tosylamino)butanoic acid 
• 1391858-81-3 N-(2-cyclopropylideneethyl)-4-methyl-N-(4-phenylbut-3-yn-1-yl)benzenesulfonamide 
• 97505-84-5 2-Phenyl-1-p-toluolsulfonyl-Δ²-pyrrolin 

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.

Synthesis of Polysubstituted Fused Pyrroles by Gold-Catalyzed Cycloisomerization/1,2-Sulfonyl Migration of Yndiamides

Yndiamides (bis-N-substituted alkynes) are valuable precursors to azacycles. Here we report a cycloisomerization/1,2-sulfonyl migration of alkynyl-yndiamides to form tetrahydropyrrolopyrroles, unprecedented heterocyclic scaffolds that are relevant to medicinal chemistry. This functional group tolerant transformation can be achieved using Au(I) catalysis that proceeds at ambient temperature, and a thermally promoted process. The utility of the products is demonstrated by a range of reactions to functionalize the fused pyrrole core.

Facile preparation of 2-aryl-3-iodopyrroles with N-tosyl 4-aryl-3-butyn-1-ylamines, I2, andtBuOK

Treatment of N-tosyl 4-aryl-3-butyn-1-ylamines with I2 and K2CO3, followed by the reaction withtBuOK under mild conditions gave 2-aryl-3-iodopyrroles in good yields. The present approach is a one-pot method for the preparation of 2-aryl-3-iodopyrroles from N-tosyl 4-aryl-3-butyn-1-ylamines, which could be easily prepared from aryl iodides, N-(3-butyn-1-yl)phthalimides, and p-toluenesulfonyl chloride.

3-Thiolated pyrroles/pyrrolines: controllable synthesis and usage for the construction of thiolated fluorophores

Thiolation/cyclization of homopropargylic tosylamides allowed the selective synthesis of 3-thiolated pyrroles and pyrrolines controlled by solvents. Moreover, the desired 3-thiolated pyrroles were readily transformed to organic fluorophores benzothienopyrrole and bisthiolated boron dipyrromethene (S-BODIPY).

TMSOTf mediated '5/6-: Endo-dig ' reductive hydroamination for the stereoselective synthesis of pyrrolidine and piperidine derivatives

A TMSOTf mediated 5/6-endo-dig reductive hydroamination cascade on internal alkynylamines gave expedient, stereoselective access to pyrrolidine and piperidine derivatives. We also demonstrate that a protecting group on nitrogen has a profound effect on the reactivity as well as diastereoselectivity of the reductive hydroamination cascade.

Gold(I)-Catalyzed Formal Intramolecular Dehydro-Diels-Alder Reaction of Ynamide-ynes: Synthesis of Functionalized Benzo[ b]carbazoles

A gold-catalyzed cycloisomerization of ynamide-ynes via a formal dehydro-Diels-Alder reaction has been developed, providing an attractive route to diversely substituted benzo[b]carbazoles. The reaction likely proceeds via regioselective attack of the pendant alkyne moiety to a keteniminium ion intermediate followed by benzannulation. The method offers several advantages such as high efficiency, mild reaction conditions, and wide functional group tolerance and serves as a highly useful complement to the thermal DDA reactions of ynamide-ynes.

Hydration and Intramolecular Cyclization of Homopropargyl Sulfonamide Derivatives Catalyzed by Silver Hexafluoroantimonate(V): Synthesis of Structurally Diverse 2,3-Dihydro-1H-Pyrroles

We have developed an efficient, simple protocol for synthesis of structurally diverse functionalized 2,3-dihydro-1H-pyrroles by hydration and intramolecular cyclization of homopropargyl sulfonamide derivatives. Mechanistic experiments revealed that the sulfonamide nitrogen participated in the hydration reaction by chelating the Ag atom of the catalyst to assist in the formation of the hydration intermediate. The protocol accommodated a wide range of substrates and was used for a formal synthesis of (S)-nicotine. (Figure presented.).

Palladium-Catalyzed Internal Nucleophile-Assisted Hydration-Olefin Insertion Cascade: Diastereoselective Synthesis of 2,3-Dihydro-1H-inden-1-ones

A novel palladium-catalyzed hydration-olefin insertion cascade assisted by internal nucleophiles was developed for the synthesis of biologically significant 2,3-dihydro-1H-inden-1-ones under mild conditions. A detailed mechanistic study revealed that the assistance of the internal nucleophiles is crucial to trigger the cascade reaction via nucleopalladation of the alkyne moiety. The overall reaction is equivalent to regioselective hydration of alkynes followed by intramolecular Michael addition. This highly efficient and 100% atom-economical domino sequence afforded cis-2,3-disubstituted 2,3-dihydro-1H-inden-1-ones in excellent yields (up to 99%) with complete diastereoselectivity.

Rhodium(III)-catalyzed oxidative bicyclization of 4-arylbut-3-yn-1-amines with internal alkynes through C-H functionalization

A new Rh(III)-catalyzed oxidative bicyclization through C-H functionalization is presented. This reaction allows the selective assembly of diverse benzo[g]indoles from 4-arylbut-3-yn-1-amines and internal alkynes via a sequence of aromatic C(sp2)-H functionalization, cyclodimerization and nucleophilic cyclization.