188802-38-2Relevant articles and documents
The 'Hirao reduction' revisited: A procedure for the synthesis of terminal vinyl bromides by the reduction of 1,1-dibromoalkenes
Abbas, Sahar,Hayes, Christopher J.,Worden, Stephen
, p. 3215 - 3219 (2000)
A convenient procedure for the synthesis of vinyl bromides is described, which involves the selective reduction of the corresponding 1,1- dibromoalkenes with dimethylphosphite and triethylamine. The 1,1- dibromoalkenes are obtained in excellent yields fro
Synthesis of Polycyclic Nitrogen Heterocycles via Cascade Pd-Catalyzed Alkene Carboamination/Diels-Alder Reactions
White, Derick R.,Wolfe, John P.
, p. 2378 - 2381 (2015)
Cascade Pd-catalyzed alkene carboamination/Diels-Alder reactions between bromodienes and amines bearing two pendant alkenes are described. These transformations generate 4 bonds, 3 rings, and 3-5 stereocenters to afford polycyclic nitrogen heterocycles wi
Electrochemical Nozaki-Hiyama-Kishi Coupling: Scope, Applications, and Mechanism
Baran, Phil S.,Blackmond, Donna G.,Gao, Yang,Hadt, Ryan G.,Hao, Wei,Hill, David E.,McNicholas, Brendon J.,Reisman, Sarah E.,Vantourout, Julien C.
supporting information, p. 9478 - 9488 (2021/07/19)
One of the most oft-employed methods for C-C bond formation involving the coupling of vinyl-halides with aldehydes catalyzed by Ni and Cr (Nozaki-Hiyama-Kishi, NHK) has been rendered more practical using an electroreductive manifold. Although early studies pointed to the feasibility of such a process, those precedents were never applied by others due to cumbersome setups and limited scope. Here we show that a carefully optimized electroreductive procedure can enable a more sustainable approach to NHK, even in an asymmetric fashion on highly complex medicinally relevant systems. The e-NHK can even enable non-canonical substrate classes, such as redox-active esters, to participate with low loadings of Cr when conventional chemical techniques fail. A combination of detailed kinetics, cyclic voltammetry, and in situ UV-vis spectroelectrochemistry of these processes illuminates the subtle features of this mechanistically intricate process.
Nickel-Catalyzed Reductive Cross-Coupling of Vinyl Bromides with Unactivated Alkyl Halides
Gu, Jun,Qiu, Canbin,Lu, Wenbin,Qian, Qun,Lin, Kunhua,Gong, Hegui
supporting information, p. 1867 - 1873 (2017/04/06)
The use of pyridine as the sole ligand for the reductive vinylation of unactivated secondary alkyl halides under Ni-catalyzed conditions has been developed. Both alkyl- and aryl-substituted vinyl bromides are suitable, in which alkyl-decorated α-alkenyl bromides resulted in the α-products in good results.
Iodine-Catalyzed Synthesis of Chalcogenophenes by the Reaction of 1,3-Dienyl Bromides and Potassium Selenocyanate/Potassium Sulfide (KSeCN/K2S)
Maity, Pintu,Ranu, Brindaban C.
, p. 4369 - 4378 (2017/12/26)
The methods available for the synthesis of chalcogenophenes, in general, are associated with drawbacks of harsh conditions, use of costly metals, broad applicability, tedious purification process and low yield. To avoid these drawbacks a transition metal-free iodine-catalyzed reaction of aryl-susbstituted 1,3-dienyl bromides with potassium selenocyanate/potassium sulfide (KSeCN/K2S) leading to the corresponding selenophenes and thiophenes has been developed. Iodine is relatively benign, less expensive and readily available. Several diversely substituted selenophenes and thiophenes have been obtained by this procedure in high yields. Using this procedure 2-(4-chlorophenyl)thiophene, a key intermediate for the synthesis of a melanin concentrating hormone receptor ligand involved in the treatment of eating disorders, weight gain, obesity, depression and anxiety has been synthesized. Although the reaction is one-pot essentially it proceeds in two steps involving a selenocyanate/thiolate intermediate leading to the selenophene/thiophene. The simple operation, use of inexpensive reagents and a metal-free process make this procedure more attractive for an easy access to substituted selenophenes and thiophenes. (Figure presented.).
Ni-catalyzed reductive coupling of α-halocarbonyl derivatives with vinyl bromides
Qiu, Canbin,Yao, Ken,Zhang, Xinghua,Gong, Hegui
supporting information, p. 11332 - 11335 (2016/12/18)
This work describes the vinylation of α-halo carbonyl compounds with vinyl bromides under Ni-catalyzed reductive coupling conditions. While aryl-conjugated vinyl bromides entail pyridine as the sole labile ligand, the alkyl-substituted vinyl bromides require both bipyridine and pyridine as the co-ligands.
Preparation of Vinyl Arenes by Nickel-Catalyzed Reductive Coupling of Aryl Halides with Vinyl Bromides
Liu, Jiandong,Ren, Qinghua,Zhang, Xinghua,Gong, Hegui
supporting information, p. 15544 - 15548 (2016/12/09)
This work emphasizes the synthesis of substituted vinyl arenes by reductive coupling of aryl halides with vinyl bromides under mild and easy-to-operate nickel-catalyzed reaction conditions. A broad range of aryl halides, including heteroaromatics, and vinyl bromides were employed to yielding products in moderate to excellent yields with high functional-group tolerance. The nickel-catalytic system displays good chemoselectivity between the two C(sp2)-halide coupling partners, thus demonstrating a mechanistic pathway distinct from other stepwise protocols.
Ruthenium-Catalyzed Silylation of 1,3-Butadienes with Vinylsilanes
Szudkowska-Fra?tczak, Justyna,Marciniec, Bogdan,Hreczycho, Grzegorz,Kubicki, Maciej,Pawlu?, Piotr
supporting information, p. 2366 - 2369 (2015/06/02)
A novel method for the synthesis of 1-silyl-substituted 1,3-butadienes, based on [RuHCl(CO)(PCy3)2]-catalyzed silylative coupling of terminal (E)-1,3-dienes with vinylsilanes, is reported. The reaction provides a facile and straightf
A direct synthesis of selenophenes by Cu-catalyzed one-pot addition of a selenium moiety to (E,E)-1,3-dienyl bromides and subsequent nucleophilic cyclization
Maity, Pintu,Kundu, Debasish,Roy, Rajdip,Ranu, Brindaban C.
supporting information, p. 4122 - 4125 (2014/09/30)
An efficient protocol for the synthesis of selenophenes and selanyl selenophenes has been achieved by a simple one-pot reaction of 1,3-dienyl bromides and 1,3-dienyl-gem-dibromides respectively with KSeCN catalyzed by CuO nanoparticles. Several aryl, alke
Nickel-catalyzed asymmetric reductive cross-coupling between vinyl and benzyl electrophiles
Cherney, Alan H.,Reisman, Sarah E.
supporting information, p. 14365 - 14368 (2014/12/11)
A Ni-catalyzed asymmetric reductive cross-coupling between vinyl bromides and benzyl chlorides has been developed. This method provides direct access to enantioenriched products bearing aryl-substituted tertiary allylic stereogenic centers from simple, stable starting materials. A broad substrate scope is achieved under mild reaction conditions that preclude the pregeneration of organometallic reagents and the regioselectivity issues commonly associated with asymmetric allylic arylation.
