97600-67-4

Upstream product

• 935-02-4 3-Phenyl-2-propynonitrile 
• 75-65-0 tert-butyl alcohol 
• 119072-55-8 tert-butylisonitrile 
• 932-87-6 1-Bromo-2-phenylacetylene 
• 536-74-3 phenylacetylene 
• 75-64-9 tert-butylamine 
• 637-44-5 phenylpropyolic acid 
• 201230-82-2 carbon monoxide 
• 932-88-7 1-iodo-2-phenylethyne 
• 1609-86-5 Tert-butyl isocyanate 
• 7299-58-3 phenylpropiolyl chloride 
• 98217-45-9 N-tert-butyl-N-<2-(methoxycarbonyl)ethyl>-3-phenylpropynamide 

Downstream Products

• 883-93-2 2-Phenylbenzothiazole 
• 1392485-66-3 (Z)-3-(chloro(phenyl)methylene)-5-phenyldihydrofuran-2(3H)-one 

Relevant academic research and scientific papers

Palladium-Catalyzed Hydrohalogenation of 1,6-Enynes: Hydrogen Halide Salts and Alkyl Halides as Convenient HX Surrogates

Difficulties associated with handling H2 and CO in metal-catalyzed processes have led to the development of chemical surrogates to these species. Despite many successful examples using this strategy, the application of convenient hydrogen halide (HX) surrogates in catalysis has lagged behind considerably. We now report the use of ammonium halides as HX surrogates to accomplish a Pd-catalyzed hydrohalogenation of enynes. These safe and practical salts avoid many drawbacks associated with traditional HX sources including toxicity and corrosiveness. Experimental and computational studies support a reaction mechanism involving a crucial E-to-Z vinyl-Pd isomerization and a carbon-halogen bond-forming reductive elimination. Furthermore, rare examples of C(sp3)-Br and ?Cl reductive elimination from Pd(II) as well as transfer hydroiodination using 1-iodobutane as an alternate HI surrogate are also presented.

Synthesis of alkynamides through reaction of alkyl- or aryl-substituted alkynylaluminums with isocyanates

An efficient and facile method for the preparation of alkynamides through Et3N-catalyzed alumination of alkyl- or aryl-substituted terminal alkynes with AlMe3and sequential nucleophilic addition ofin situgenerated alkynylaluminums to isocyanates is described. This method has the merits of using readily available isocyanates and monosubstituted alkynes, easy access to organoaluminums, short reaction times, and high efficiency. A gram-scale synthesis of the desired alkynamide and its application to the formation of α-methylene-β-lactams demonstrates the synthetic utility of this method.

Visible light-induced co- or cu-catalyzed selenosulfonylation of alkynes: Synthesis of β-(seleno)vinyl sulfones

A visible light-induced Co- or Cu-catalyzed selenosulfonylation of alkynes for the synthesis of β-(seleno)vinyl sulfones is demonstrated. This method utilizes a low-cost cobalt salt or metal copper as the catalysts. The reaction goes through a photoinduced free radical addition of selenosulfonates to alkynes for the 1,2-selenosulfonylation of alkynes under mild conditions.

Efficient synthesis of alkynyl amides via aminocarbonylation of iodoalkynes

Iodoethynylbenzene as iodoalkyne model compound was aminocarbonylated with tert-butylamine under carbon monoxide atmosphere in the presence of in situ palladium(0) catalysts. The formation of the unsaturated carboxamide (alkynyl amide) is always accompanied by that of the Glaser coupling product, diphenylbutadiyne. The yield of the amide-forming reaction was optimised by the systematic variation of the phosphine ligand, carbon monoxide pressure and temperature. The scope of the reaction was investigated by using various primary and secondary amines including amino acid methyl esters as N-nucleophiles. 17α-(Iodoethynyl)-testosterone was also functionalised by using this methodology providing the corresponding 17α-(carboxamidoethynyl)-testosterone derivatives in up to 96% yields. The reaction was extended to 1-(iodoethynyl)cyclohex-1-ene and 1-iodohex-1-yne. Ethyl iodopropiolate gave the enamine type product by the addition of amine to the alkyne functionality which was formed from the iodoalkyne via deiodination under standard aminocarbonylation conditions. The bromo analogue, bromoethynylbenzene has shown lower reactivity than the corresponding iodo derivative.

Co(II)/Ag(I) Synergistically Catalyzed Monoinsertion Reaction of Isocyanide to Terminal Alkynes with H2O: Synthesis of Alkynamide Derivatives

A Co(II)/Ag(I) synergistically catalyzed three-component reaction of isocyanide with terminal alkyne and water to afford alkynamide derivatives is reported. The insertion of monoisocyanide into the C-H bond of terminal alkynes is an efficient, straightforward, atom-economical route to alkynamides, which are useful synthons in organic synthesis. This synergistic process achieves the cleavage of a C-H bond and the construction of new C-C and Ca?O bonds under mild conditions through the reaction of Co(II)-activated isocyanides and a Ag(I)-complex-activated terminal alkyne. This reaction has broad substrate versatility and functional group tolerance.

Pd-catalyzed and CsF-promoted reaction of bromoalkynes with isocyanides: Regioselective synthesis of substituted 5-iminopyrrolones

The palladium-catalyzed and CsF-promoted annulation reaction of bromoalkynes and isocyanides regioselectively affords a diverse set of 5-iminopyrrolone derivatives. This chemistry presumably proceeds through the bromoacrylamide intermediates, which can be readily prepared from the nucleophilic addition reaction of isocyanides to bromoalkynes in the presence of CsF.

Intramolecular Michael Reactions. Addition to the α-Carbon of Ynamides

A number of substituted cinnamamides were synthesized to determine the feasibility of preparing 4-arylnipecotate derivatives via an intramolecular Michael reaction.With these substrates, β-elimination of the cinnamamide residue was the dominant reaction. 3-Phenylpropynamide substrates, however, underwent an unusual "anti-Michael" addition to the α-carbon of the acetylene to produce pyrrolidinones, whose structures were confirmed by independent synthesis.

Allenes. Part 44. Formation of Oxazolines and Benzoxazoles from Allenic nitriles and amides and from Phenylpropynenitrile.

Michael addition of ethanolamines and 2-aminophenol to allenic nitriles, allenic amides and phenylpropynenitrile gives enaminic nitriles and amides which at 290 deg - 320 deg yield oxazolines and benzoxazoles.