- Development and Scale-Up of Stereoretentive α-Deuteration of Amines
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A stereoretentive deuteration of amino acids and amines has been developed using ruthenium on carbon catalyst, hydrogen gas at atmospheric pressure, and deuterium oxide as a source of deuterium. The process was successfully scaled-up, avoiding the use of expensive and sensitive catalyst and avoiding the use of deuterium gas under pressure. High deuterium incorporation and high yield of labeled compounds were obtained by a simple filtration process.
- Michelotti, Alessia,Rodrigues, Fabien,Roche, Maxime
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supporting information
p. 1741 - 1744
(2017/11/24)
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- Asymmetric synthesis of α-deuterated α-amino acids
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α-Deuterated-α-amino acids represent a very special class of stable isotopically labeled compounds, used in advanced biomedical research. Herein, we disclose a generalized approach for the preparation of α-2H-α-amino acids in enantiomerically pure form and with up to 99% deuteration. The reaction chemistry involved in this process is based on the dynamic kinetic resolution of racemates or (S)-(R) interconversion via the formation of intermediate Ni(ii) complexes derived from unprotected amino acids and recyclable tridentate ligands. Operationally convenient conditions, excellent chemical yields, diastereoselectivity and the degree of the deuteration bode well for the wide application of this methodology for the preparation of tailor-made α-2H-α-amino acids.
- Takeda, Ryosuke,Abe, Hidenori,Shibata, Norio,Moriwaki, Hiroki,Izawa, Kunisuke,Soloshonok, Vadim A.
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supporting information
p. 6978 - 6983
(2017/09/01)
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- Enantiospecific C-H Activation Using Ruthenium Nanocatalysts
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The activation of C-H bonds has revolutionized modern synthetic chemistry. However, no general strategy for enantiospecific C-H activation has been developed to date. We herein report an enantiospecific C-H activation reaction followed by deuterium incorporation at stereogenic centers. Mechanistic studies suggest that the selectivity for the α-position of the directing heteroatom results from a four-membered dimetallacycle as the key intermediate. This work paves the way to novel molecular chemistry on nanoparticles.
- Taglang, Céline,Martínez-Prieto, Luis Miguel,Del Rosal, Iker,Maron, Laurent,Poteau, Romuald,Philippot, Karine,Chaudret, Bruno,Perato, Serge,Sam Lone, Ana?s,Puente, Céline,Dugave, Christophe,Rousseau, Bernard,Pieters, Grégory
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supporting information
p. 10474 - 10477
(2015/09/02)
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- Enantioselective synthesis of α-deuterium labelled chiral α-amino acids via dynamic kinetic resolution of racemic azlactones
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Catalytic dynamic kinetic resolution (DKR) of racemic azlactones with EtOD using squaramide-based dimeric cinchona alkaloid organocatalysts is shown to be a highly effective strategy for the preparation of enantiomerically pure α-deuterated chiral α-amino
- Oh, Joong-Suk,Kim, Kyung Il,Song, Choong Eui
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supporting information; experimental part
p. 7983 - 7985
(2012/01/04)
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- PREPARATION OF α-DEUTERATED L-AMINO ACIDS USING E. coli B/It7-A CELLS CONTAINING TRYPTOPHANASE
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A convenient method of preparation of α-deuterated L-amino acids via stereospecific isotope exchange in D2O catalyzed by lyophilized E. coli B/It7-A cells abundant in tryptophanase is reported
- Faleev, N. G.,Ruvinov, S. B.,Saporovskaya, M. B.,Belikov, V. M.,Zakomyrdina, L. N.,et al.
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p. 7051 - 7054
(2007/10/02)
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- PREPARATION OF α-DEUTERATED L-AMINO ACIDS USING E. coli CELLS CONTAINING TRYPTOPHANASE
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A preparative method has been developed to obtain a series of α-deuterated L-amino acids with high chemical yields and quantitative optical yields by stereospecific isotope exchange in D2O by the action of E. coli cells with high tryptophanase action.
- Faleev, N. G.,Ruvinov, S. B.,Saporovskaya, M. B.,Belikov, V. M.,Zakomyrdina, L. N.,et al.
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p. 2154 - 2156
(2007/10/02)
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- Asymmetric Synthesis of α-Deuterated α-Amino Acids through Nonenzymatic Transamination Reaction and the Determination of Their Enantiomeric Excesses
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Optically active α-deuterated α-amino acids were prepared in methanol-d through Zn2+-catalyzed transamination reaction between the chiral pyridoxamine analogs, (R)- or (S)-15-aminomethyl-14-hydroxy-5,5-dimethyl-2,8-dithia(2,5)pyridinophane and various α-keto acids with enantiomeric excesses ranging from 40 to 94percent.Aliphatic α-keto acids gave α-deuterated α-amino acids, whereas aromatic ones possessing a methylene group between the carbonyl group (ketone) and the aromatic ring underwent concomitant deuterium substitution at the active methylene group to give the amino acids deuterated at both α- and β-positions of the carbonyl group.The use of the (S)-pyridoxamine analog gave the (R)-deuterated α-amino acids in excess and vice versa.The enantiomeric excesses of the amino acids were determined through the analyses of 1H NMR spectra of the Schiff bases produced by the condensation of the amino acids with the chiral pyridoxal analog, (R)- or (S)-15-formyl-14-hydroxy-2,8-dithia(2,5)pyridinophane.The azomethine protons of the diastereomeric Schiff bases were clearly resolved in the spectrum and their intensities well reflected the amount of the diastereomers.
- Tachibana, Yoji,Ando, Makoto,Kuzuhara, Hiroyoshi
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p. 3652 - 3656
(2007/10/02)
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