2540-53-6Relevant academic research and scientific papers
Direct reductive amination of ketones with ammonium salt catalysed by Cp*Ir(iii) complexes bearing an amidato ligand
Dai, Zengjin,Pan, Ying-Min,Wang, Shou-Guo,Yin, Qin,Zhang, Xumu
, p. 8934 - 8939 (2021/11/04)
A series of half-sandwich Ir(iii) complexes1-6bearing an amidato bidentate ligand were conveniently synthesized and applied to the catalytic Leuckart-Wallach reaction to produce racemic α-chiral primary amines. With 0.1 mol% of complex1, a broad range of ketones, including aryl ketones, dialkyl ketones, cyclic ketones, α-keto acids, α-keto esters and diketones, could be transformed to their corresponding primary amines with moderate to excellent yields (40%-95%). Asymmetric transformation was also attempted with chiral Ir complexes3-6, and 16% ee of the desired primary amine was obtained. Despite the unsatisfactory enantio-control achieved so far, the current exploration might stimulate more efforts towards the discovery of better chiral catalysts for this challenging but important transformation.
Synthesis of Unprotected 2-Arylglycines by Transamination of Arylglyoxylic Acids with 2-(2-Chlorophenyl)glycine
Inada, Haruki,Shibuya, Masatoshi,Yamamoto, Yoshihiko
, p. 11047 - 11059 (2020/10/12)
The transamination of α-keto acids with 2-phenylglycine is an effective methodology for directly synthesizing unprotected α-amino acids. However, the synthesis of 2-arylglycines by transamination is problematic because the corresponding products, 2-arylglycines, transaminate the starting arylglyoxylic acids. Herein, we demonstrate the use of commercially available l-2-(2-chlorophenyl)glycine as the nitrogen source in the transamination of arylglyoxylic acids, producing the corresponding 2-arylglycines without interference from the undesired self-transamination process.
Reductive amination of ketonic compounds catalyzed by Cp*Ir(III) complexes bearing a picolinamidato ligand
Tanaka, Kouichi,Miki, Takashi,Murata, Kunihiko,Yamaguchi, Ayumi,Kayaki, Yoshihito,Kuwata, Shigeki,Ikariya, Takao,Watanabe, Masahito
, p. 10962 - 10977 (2019/09/03)
Cp*Ir complexes bearing a 2-picolinamide moiety serve as effective catalysts for the direct reductive amination of ketonic compounds to give primary amines under transfer hydrogenation conditions using ammonium formate as both the nitrogen and hydrogen source. The clean and operationally simple transformation proceeds with a substrate to catalyst molar ratio (S/C) of up to 20,000 at relatively low temperature and exhibits excellent chemoselectivity toward primary amines.
CATALYST COMPOUNDS
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Paragraph 0314; 0324, (2015/03/28)
The present invention relates to an iridium-based catalyst compound for hydrogenating reducible moieties, especially imines and iminiums, the catalyst compounds being defined by the formulas: where ring B is either itself polycyclic, or ring B together with R is polycyclic. The catalysts of the invention are particularly effective in reductive amination procedures 10 which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
Primary amines by transfer hydrogenative reductive amination of ketones by using cyclometalated IrIII catalysts
Talwar, Dinesh,Salguero, Noemi Poyatos,Robertson, Craig M.,Xiao, Jianliang
supporting information, p. 245 - 252 (2014/01/17)
Cyclometalated iridium complexes are found to be versatile catalysts for the direct reductive amination (DRA) of carbonyls to give primary amines under transfer-hydrogenation conditions with ammonium formate as both the nitrogen and hydrogen source. These complexes are easy to synthesise and their ligands can be easily tuned. The activity and chemoselectivity of the catalyst towards primary amines is excellent, with a substrate to catalyst ratio (S/C) of 1000 being feasible. Both aromatic and aliphatic primary amines were obtained in high yields. Moreover, a first example of homogeneously catalysed transfer-hydrogenative DRA has been realised for β-keto ethers, leading to the corresponding β-amino ethers. In addition, non-natural α-amino acids could also be obtained in excellent yields with this method. Reduce the work! A broad range of ketones have been successfully aminated to afford primary amines under transfer-hydrogenation conditions by using ammonium formate as the amine source and 0.1 mol % of a cyclometalated IrIII catalyst (see scheme). Copyright
CATALYST COMPOUNDS
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Paragraph 00163; 00173, (2013/11/05)
The present invention relates to an iridium-based catalyst compound for hydrogenating reducible moieties, especially imines and iminiums, the catalyst compounds being defined by the formulas: where ring B is either itself polycyclic, or ring B together with R is polycyclic. The catalysts of the invention are particularly effective in reductive amination procedures 10 which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
Efficient access to (1H)-isoindolin-1-one-3-carboxylic acid derivatives by orthopalladation and carbonylation of methyl arylglycinate substrates
Nieto, Sonia,Sayago, Francisco J.,Laborda, Pedro,Soler, Tatiana,Cativiela, Carlos,Urriolabeitia, Esteban P.
experimental part, p. 4185 - 4191 (2011/07/08)
The orthopalladation of methyl arylglycinate derivatives has been studied. The reaction proceeds efficiently for different electron-withdrawing and electron-releasing substituents at the aryl ring. The carbonylation of the orthopalladated complexes affords, in a single step, substituted (1H)-isoindolin-1-one-3-carboxylates. These compounds constitute valuable synthetic intermediates and can be transformed diastereoselectively into octahydroisoindole-1-carboxylic acid derivatives, an important scaffold in the synthesis of many biologically active compounds.
Synthesis of new imidazolidin-2,4-dione and 2-thioxoimidazolidin-4-ones via C-phenylglycine derivatives
De Sousa Luis, Jose Alixandre,Barbosa Filho, Jose Maria,Lira, Bruno Freitas,Medeiros, Isac Almeida,De Morais, Liana Clebia Soares Lima,Dos Santos, Alexsandro Fernandes,De Oliveira, Cledualdo Soares,De Athayde-Filho, Petronio Filgueiras
experimental part, p. 128 - 137 (2010/05/18)
Hydantoins and their derivatives constitute a group of pharmaceutical compounds with anticonvulsant and antiarrhythmic properties, and are also used against diabetes. N-3 and C-5 substituted imidazolidines are examples of such products. As such, we have developed a synthesis of 2,4-dione and 2-thioxo-4-one imidazolidinic derivatives by reaction of amino acids with C-phenylglycine, phenyl isocyanate and phenyl isothiocyanate. Four amino-derivatives IG(1-4) and eight imidazolidinic derivatives, IM(1-8), were obtained in yields of 70-74%. The mass, infrared, 1H and 13C-NMR spectra of representative products are discussed.
Synthesis of arylglycines by reaction of diethyl N-Boc-iminomalonate with organomagnesium reagents
Calí,Begtrup
, p. 63 - 66 (2007/10/03)
Diethyl N-Boc-iminomalonate (3), prepared on multigram scale, served as a stable and highly reactive electrophilic glycine equivalent which reacted with organomagnesium compounds affording substituted aryl N-Boc-aminomalonates. Subsequent hydrolysis produced arylglycines.
A facile synthesis of substituted phenylglycines
Davies, Antony J.,Ashwood, Michael S.,Cottrell, Ian F.
, p. 1095 - 1102 (2007/10/03)
A convenient scaleable process for the preparation of substituted phenylglycines 2 by a modified Strecker reaction is described. Bisulfite- mediated addition of benzylamine and cyanide anion to substituted benzaldehydes 3 gave the aminonitriles 4 which were hydrolysed in two steps to the N-protected amino acid 1. Debenzylation using catalytic transfer hydrogenation gave the title compounds in good yield.
