312329-77-4

Upstream product

• 1576-37-0 N-benzyl-p-toluenesulfonamide 
• 72773-04-7 N-formylbenzotriazole 
• 98-59-9 p-toluenesulfonyl chloride 
• 100-46-9 benzylamine 
• 64-18-6 formic acid 

Downstream Products

• 312329-82-1 N-(2,2-dichlorovinyl)-N-benzyl-4-methyl-benzenesulfonamide 
• 853688-20-7 N-benzyl-N-(2,2-dibromovinyl)-4-methylbenzenesulfonamide 

Relevant academic research and scientific papers

Au(I)-Catalyzed Oxidative Functionalization of Yndiamides

Yndiamides, underexplored cousins of ynamides, offer rich synthetic potential as doubly nitrogenated two carbon building blocks. Here we report a gold-catalyzed oxidative functionalization of yndiamides to access unnatural amino acid derivatives, using a wide range of nucleophiles as a source of the amino acid side chain. The transformation proceeds under mild conditions, is highly functional group tolerant, and displays excellent regioselectivity through subtle steric differentiation of the yndiamide nitrogen atom substituents.

Regio- And Stereoselective Addition of Bronsted Acids to Yndiamides: Synthesis of N, O, N - And N, S, N -Trisubstituted Ketene Acetals

Yndiamides, N,N-disubstituted alkynes, are versatile building blocks for the synthesis of nitrogen-containing organic molecules. Unlike ynamides, relatives that are inherently polarized by a single nitrogen substituent, their pseudo-symmetric nature renders regioselective reactions challenging. Here we report investigations into the regioselective addition of Br nsted acids to non-symmetric yndiamides, a reaction that delivers N,O,N- and N,S,N-trisubstituted ketene acetals with excellent regio- and stereoselectivity.

Cs2CO3-Mediated Vicinal Thiosulfonylation of 1,1-Dibromo-1-Alkenes with Thiosulfonates: An Expedient Synthesis of (E)-1,2-Thiosulfonylethenes

A new and highly efficient vicinal thiosulfonylation of 1,1-dibromo-1-alkenes with thiosulfonates in the presence of cesium carbonate has been developed. The metal-free diheterofunctionalization is an operationally simple to access a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields with high levels of stereoselectivities. Further, scalable reactions have been demonstrated for this transformation, thus illustrating its efficiency and practicality. (Figure presented.).

Highly Selective Syn Addition of 1,3-Diones to Internal Ynamides Catalyzed by Zinc Iodide

1,3-Diones are already established as nucleophiles to perform additions to ynamides; the highly selective hydroalkoxylation of internal ynamides is now described. Several catalytic systems have been compared to perform this transformation, including transition-metal-based catalysts and Lewis acids. ZnI2 was found to be both very active and highly selective providing only E adducts through a syn addition. Investigation of the scope and limitations showed that this catalyst was compatible with various functional groups. In addition to seventeen examples of ynamide hydroalkoxylation, one example of ynamide hydroarylation is reported.

Copper-Catalyzed Synthesis and Applications of Yndiamides

The first synthetic route to yndiamides, a novel class of double aza-substituted alkyne, has been established by the copper(I)-catalyzed cross-coupling of 1,1-dibromoenamides with nitrogen nucleophiles. The utility of these compounds is demonstrated in a

Efficient and Flexible Synthesis of Highly Functionalised 4-Aminooxazoles by a Gold-Catalysed Intermolecular Formal [3+2] Dipolar Cycloaddition

Oxazoles are important motifs within bioactive and functional materials. Complex, fully substituted and functionalised 4-aminooxazoles are accessed by an efficient intermolecular reaction between an ynamide and an N-acylpyridinium N-aminide in the presence of a gold catalyst. The formal [3+2] dipolar cycloaddition employs a nucleophilic nitrenoid approach to access the 1,3-N,O-dipole character in a controllable fashion. The selectivity for a cycloaddition pathway provides a stark contrast against the indiscriminate reactivity of electrophilic acyl nitrenes. Protocols for the formation of acyl-functionalised aminides are reported from accessible precursors including carboxylic esters and acids. The function of these aminides in the oxazole-forming reaction has been explored and it is shown that substantial elaboration is accommodated despite proximity to the reactive centre. As a result functional oxazole-based motifs, such as chiral oxazoles with biologically pertinent substitution patterns, are readily accessible. The use of ynamide types that are unexplored or little used in gold catalysis has been evaluated. Unusual all-heteroatom substitution patterns around the oxazole are shown to be accessible using thio-ynamides. The study shows that a close stoichiometry of reactants is suitable alongside relatively low loadings of the bench-stable precatalysts in practically straightforward multi-mmol scale reactions. The efficiency and flexibility of this regioselective intermolecular preparation is demonstrated in the ready synthesis of oxazoles with substantial structural and functional group variation.

Palladium-mediated [2+1] cycloaddition of norbornene derivatives with ynamides

An efficient palladium-catalyzed [2+1] cycloaddition between ynamides and norbornenes or norbornadienes is reported. Both phosphapalladacycles and palladium/secondary phosphine oxide catalytic systems were found to be competent for the transformation allowing the preparation of aminomethylenecyclopropanes. The reaction showed general applicability to various functionalized bicyclo[2.2.1]hept-2-enes and ynamides. A chiral phosphapalladacycle was tested to carry out this transformation in an enantioselective fashion.

Synthesis of ynamides from formamides

N-Formyl-tosylamides can be efficiently converted to N-ethynyl-tosylamides in two steps via the corresponding dichlorovinylamides.

Palladium-catalyzed Suzuki-Miyaura coupling reactions involving β,β-dihaloenamides: Application to the synthesis of disubstituted ynamides

β,β-Dihaloenamides can be successfully involved in palladium-catalyzed Suzuki-Miyaura coupling reactions. Whereas the resulting tri substituted (Z)-β-bromoenamides could participate in a second cross-coupling leading to β,β-disubstituted enamides, the (Z)-β-chloroenamides have been converted to disubstituted ynamides by an E2 elimination.

Synthesis of ynamides and ynol ethers via formamides and formates

The efficient conversion of N-formyl-tosylamides to N-ethynyl-tosylamides via the corresponding dichlorovinylamides is described. Furthermore syntheses of N-formyl-tosylamides are reported.