23426-02-0Relevant articles and documents
Rhodium-catalyzed 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds: Large accelerating effects of bases and ligands
Itooka, Ryoh,Iguchi, Yuki,Miyaura, Norio
, p. 6000 - 6004 (2003)
The effects of ligands and bases in the rhodium(I)-catalyzed 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds were reinvestigated to carry out the reaction under mild conditions. Rhodium(I) complexes possessing a 1,5-cyclooctadiene (cod) and a hydroxo ligand such as [RhOH(cod)]2 exhibited excellent catalyst activities compared to those of the corresponding rhodium-acac or -chloro complexes and their phosphine derivatives. The reaction was further accelerated in the presence of KOH, thus allowing the 1,4-addition even at 0 °C. A cationic rhodium-(I)-(R)-binap complex, [Rh(R-binap)(nbd)]BF4, catalyzed the reaction at 25-50 °C in the presence of Et3N with high enantioselectivities of up to 99% ee for α,β-unsaturated ketones, 92% for aldehydes, 94% for esters, and 92% for amides.
A conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds catalyzed by 2β-CD-[Rh(OH)(cod)]2 or [RhCl(cod)]2 in a single aqueous medium
Itooka, Ryoh,Iguchi, Yuki,Miyaura, Norio
, p. 722 - 723 (2001)
The rhodium-catalyzed conjugate addition of tolylboronic acid to α,β-unsaturated ketones, esters or amides was carried out in water. [RhCl(cod)]2 and 2β-cyclodextrin-[Rh(OH)(cod)]2 complexes were found to catalyze the reaction efficiently in a single aqueous medium.
Rh-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to 3-Arylpropenoates: Enantioselective Synthesis of (R)-Tolterodine
Zullo, Valerio,Iuliano, Anna
supporting information, p. 1377 - 1384 (2019/01/04)
A highly enantioselective conjugate addition of arylboronic acids to 3-arylpropenoates is presented. The rhodium complexes obtained from deoxycholic acid derived binaphthyl phosphites showed good activity as well as very high enantioselectivity (ee up to 99 %) in the conjugate addition to different ethyl-3-arylpropenoates, allowing to obtain useful chiral building blocks for the synthesis of active pharmaceutical ingredients. The method was applied to the enantioselective synthesis of the antimuscarinic drug (R)-tolterodine.
Rh-catalyzed 1,4-addition of triallyl(aryl)silanes to α,β-unsaturated carbonyl compounds
Kamei, Toshiyuki,Uryu, Mizuho,Shimada, Toyoshi
supporting information, p. 1622 - 1624 (2018/03/22)
Rh-catalyzed 1,4-addition of triallyl(aryl)silane to α,β-unsaturated carbonyl compounds was developed. Triallyl(aryl)silanes were used as air- and moisture-stable silicon nucleophiles. Allylsilanes were converted to silanols in situ and underwent transmetalation. This method can accept a wide range of functionalized triallyl(aryl)silane and α,β-unsaturated carbonyl compounds.
Ligand-free nickel-catalysed 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds
Chen, Wen,Sun, Lu,Huang, Xi,Wang, Jiayi,Peng, Yanqing,Song, Gonghua
, p. 1474 - 1482 (2015/05/19)
A simple and efficient ligand-free nickel-based catalytic system has been developed for the 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds. With catalyst loadings of 1-2 mol%, a series of 1,4-adducts from chalcones and cinnamates was obtained in moderate to excellent yields within 5-30 min under a nitrogen atmosphere and microwave irradiation. The 1,4-addition of arylboronic acids to acrylates is less efficient.
Construction of 3-arylpropylamines using Heck arylations. the total synthesis of cinacalcet hydrochloride, alverine, and tolpropamine
Prediger, Patrícia,Da Silva, Allan Ribeiro,Correia, Carlos Roque Duarte
, p. 3333 - 3341 (2014/05/06)
New synthetic routes toward the commercial drugs cinacalcet hydrochloride, alverine, and tolpropamine were developed using a Heck-Matsuda arylation as the key-step. Several reaction conditions were evaluated for the Heck-Matsuda reaction using allylamine derivatives and arenediazonium salts. For cinacalcet hydrochloride, N-formylamide provided the best result, furnishing the synthetic target in a very high overall yield (75% over five steps). For alverine, the best results were obtained using a double Heck-Matsuda strategy, providing alverine in an excellent overall yield (69%) from N-acetyl diallylamine in three steps. Tolpropamine was synthesized in a 46% yield over five steps using an efficient reductive Heck-Matsuda arylation between p-bromo-methylcinnamate with 3-chloro tolyldiazonium salt, generating the ,diaryl propionate that was converted to tolpropamine.
Asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated esters catalyzed by dicationic palladium(II)-chiraphos complex for short-step synthesis of SmithKline Beecham's endothelin receptor antagonist
Nishikata, Takashi,Kiyomura, Shunsuke,Yamamoto, Yasunori,Miyaura, Norio
scheme or table, p. 2487 - 2490 (2009/04/07)
An asymmetric 1,4-addition of arylboronic acids to RCH=CHCO2Ar (Ar = Ph or 4-acetylphenyl) was carried out at 50°C in aqueous acetone in the presence of [Pd(chiraphos)(Ph-CN)2](SbF6)2. The reaction gave optically active β-aryl esters in up to 98% ee. The protocol provided a simple access to an endothelin receptor antagonist reported by SmithKline Beecham. Georg Thieme Verlag Stuttgart.
