132960-13-5Relevant articles and documents
CuCl2-catalyzed highly stereoselective and chemoselective reduction of alkynyl amides into α,β-unsaturated amides using silanes as hydrogen donors
Duan, Lingfei,Jiang, Kai,Zhu, Hua,Yin, Biaolin
supporting information, p. 365 - 369 (2021/01/29)
A CuH-catalyzed Z-selective partial reduction of alkynyl amides to afford α,β-unsaturated amides using silane as the hydrogen donor is developed. This reaction is carried out under mild conditions and able to accommodate a broad scope of alkynyl amides in
N-triflyl-propiolamides: Preparation and transamidation reactions
Fiore, Vito A.,Maas, Gerhard
, p. 3586 - 3595 (2019/05/27)
N-Trifluoromethylsulfonyl-propiolamides have been prepared by two methods: a) N-triflation of secondary acetylenic carboxanilides, prepared in two steps from terminal alkynes, with triflic anhydride (Tf2O) and b) from terminal alkynes and an aryl or alkyl isocyanate followed by Tf2O in a consecutive one-pot reaction. The title compounds are bench-stable and insensitive to water and alcohols but amenable to transamidation reactions with a wide range of amine nucleophiles. Conversely, they are excellent reagents for the propynoylation of ammonia, primary and secondary amines, anilines, and hydrazines.
Enantioselective Addition of Alkynyl Ketones to Nitroolefins Assisted by Br?nsted Base/H-Bonding Catalysis
Campano, Teresa E.,Iriarte, Igor,Olaizola, Olatz,Etxabe, Julen,Mielgo, Antonia,Ganboa, I?aki,Odriozola, José M.,García, Jesús M.,Oiarbide, Mikel,Palomo, Claudio
supporting information, p. 4390 - 4397 (2019/03/07)
Various sets of enolizable alkynyl ketones (including methyl ynones with α-aryl, α-alkenyl, and α-alkoxy groups) were able to react smoothly with nitroolefins with the assistance of bifunctional Br?nsted base/H-bond catalysts to provide adducts with two consecutive tertiary stereocenters in a highly diastereo- and enantioselective fashion. Further transformation of the obtained adducts into optically active acyclic and polycyclic molecules, including some with intricate carbon skeletons, was also demonstrated.
Efficient synthesis of alkynyl amides via aminocarbonylation of iodoalkynes
Szuroczki, Péter,Boros, Borbála,Kollár, László
, p. 6129 - 6136 (2018/09/14)
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.
Controlling the α/γ-Reactivity of Vinylogous Ketone Enolates in Organocatalytic Enantioselective Michael Reactions
Iriarte, Igor,Olaizola, Olatz,Vera, Silvia,Gamboa, I?aki,Oiarbide, Mikel,Palomo, Claudio
supporting information, p. 8860 - 8864 (2017/07/17)
The first regio-, diastereo-, and enantioselective direct Michael reaction of β,γ-unsaturated ketones with nitroolefins is enabled by Br?nsted base/hydrogen-bonding bifunctional catalysis. A squaramide-substituted tertiary amine catalyzes the reaction of a broad range of β,γ-unsaturated ketones to proceed at the α-site exclusively, giving rise to adducts with two consecutive tertiary carbon stereocenters in diastereomeric ratios of up to >20:1 and enantioselectivities generally in the 90–98 % ee range.
N-Methoxy-N-methylcyanoformamide, a Highly Reactive Reagent for the Formation of β-Keto Weinreb Amides and Unsymmetrical Ketones
Nugent, Jeremy,Schwartz, Brett D.
supporting information, p. 3834 - 3837 (2016/08/16)
A rapid and straightforward synthesis of the new and highly reactive reagent N-methoxy-N-methylcyanoformamide from trimethylsilyl cyanide and N-methoxy-N-methylcarbamoylimidazole, is reported. This reagent enables the one-pot preparation of β-carbonyl Wei
Scaffold-divergent synthesis of ring-fused indoles, quinolines, and quinolones via iodonium-induced reaction cascades
Halim, Rosliana,Aurelio, Luigi,Scammells, Peter J.,Flynn, Bernard L.
, p. 4708 - 4718 (2013/06/27)
N-(2-Iodophenyl)imines A are readily formed from Schiff's base condensation of 2-iodoanilines with carbonyls and ketals. These imines provide useful substrates in scaffold-divergent synthesis through the attachment of an alkyne (Songashira coupling or acyl substitution of a Weinreb amide) followed by an iodonium-induced reaction cascade to give ring-fused indoles B, quinolines C, or quinolones D depending on the reaction conditions employed.
Rh(I)-catalyzed decarbonylation of diynones via C-C activation: Orthogonal synthesis of conjugated diynes
Dermenci, Alpay,Whittaker, Rachel E.,Dong, Guangbin
supporting information, p. 2242 - 2245 (2013/06/05)
Utilization of C-C bond activation as a unique mode of reactivity for constructing C-C bonds provides new strategies for preparing important organic molecules. Development of a Rh(I)-catalyzed C-C activation of diynones to synthesize symmetrical and unsymmetrical conjugated diynes through decarbonylation is reported. This C-C cleavage strategy takes advantage of the innate reactivity of conjugated ynones without relying on any ring strain or auxiliary directing group. This alkynation method also has orthogonal properties compared to typical cross-coupling reactions.
Palladium-catalyzed coupling reactions of N-methoxy-N-methylcarbamoyl chloride for the synthesis of N-methoxy-N-methylamides
Murakami, Masahiro,Hoshino, Yujiro,Ito, Hajime,Ito, Yoshihiko
, p. 163 - 164 (2007/10/03)
A new synthetic method of N-methoxy-N-methylamides is developed. The palladium-catalyzed coupling reaction of N-methoxy-N-methylcarbamoyl chloride furnished N-methoxy-N-methylamide in moderate to good yield, wherein a carbonyl equivalent was appended to s
