129389-45-3Relevant academic research and scientific papers
Deammoniative condensation of primary allylic amines with nonallylic amines
Wang, Yong,Li, Manbo,Ma, Xiantao,Liu, Congrong,Gu, Yonghong,Tian, Shi-Kai
, p. 741 - 751 (2014)
An unprecedented deammoniative condensation reaction of primary allylic amines with nonallylic amines has been developed through C-N bond cleavage. In the presence of 5 mol% palladium diacetate, 10 mol% 1,4-bis(diphenylphosphino) butane (dppb), and 5 mol% p-toluenesulfonic acid (TsOH), a range of α-unbranched primary allylic amines smoothly underwent deammoniative condensation with nonallylic amines in an α-selective fashion to give structurally diverse secondary and tertiary amines in good to excellent yields and E selectivity. Replacing dppb with racemic 2,2-bis(diphenylphosphino)-1,1- binaphthyl (BINAP) permitted the deammoniative condensation of enantioenriched α-chiral primary allylic amines with nonallylic amines to proceed with complete retention of configuration. Electrospray ionization (ESI) mass spectrometric analysis of the reaction mixture permitted the identification of some π-allylpalladium intermediates, and plausible mechanisms have been proposed to account for the regioselectivity and stereospecificity of the deammoniative condensation reaction. A range of enantioenriched primary allylic amines underwent palladium/acid-catalyzed direct substitution with nonallylic amines in a stereospecific manner. Copyright
PQQ-dependent Dehydrogenase Enables One-pot Bi-enzymatic Enantio-convergent Biocatalytic Amination of Racemic sec-Allylic Alcohols
Gandomkar, Somayyeh,Rocha, Raquel,Sorgenfrei, Frieda A.,Montero, Lía Martínez,Fuchs, Michael,Kroutil, Wolfgang
, p. 1290 - 1293 (2020/12/23)
The asymmetric amination of secondary racemic allylic alcohols bears several challenges like the reactivity of the bi-functional substrate/product as well as of the α,β-unsaturated ketone intermediate in an oxidation-reductive amination sequence. Heading for a biocatalytic amination cascade with a minimal number of enzymes, an oxidation step was implemented relying on a single PQQ-dependent dehydrogenase with low enantioselectivity. This enzyme allowed the oxidation of both enantiomers at the expense of iron(III) as oxidant. The stereoselective amination of the α,β-unsaturated ketone intermediate was achieved with transaminases using 1-phenylethylamine as formal reducing agent as well as nitrogen source. Choosing an appropriate transaminase, either the (R)- or (S)-enantiomer was obtained in optically pure form (>98 % ee). The enantio-convergent amination of the racemic allylic alcohols to one single allylic amine enantiomer was achieved in one pot in a sequential cascade.
Iterative Alanine Scanning Mutagenesis Confers Aromatic Ketone Specificity and Activity of L-Amine Dehydrogenases
Mu, Xiaoqing,Wu, Tao,Mao, Yong,Zhao, Yilei,Xu, Yan,Nie, Yao
, p. 5243 - 5253 (2021/11/16)
Direct reductive amination of prochiral ketones catalyzed by amine dehydrogenases is attractive in the synthesis of active pharmaceutical ingredients. Here, we report the protein engineering of L-Bacillus cereus amine dehydrogenase to allow reactivity on synthetically useful aromatic ketone substrates using an iterative, multiple-site alanine scanning mutagenesis approach. Mutagenesis libraries based on molecular docking, iterative alanine scanning, and double-proximity filter approach significantly expand the scope of active pharmaceutical ingredients relevant building blocks. The eventual quintuple mutant (A115G/T136A/L42A/V296A/V293A) showed reactivity toward aromatic ketones 12 a (5-phenyl-pentan-2-one) and 13 a (6-phenyl-hexan-2-one), which have not been reported to serve as targets of reductive amination by currently available amine dehydrogenases. Docking simulation and tunnel analysis provided valuable insights into the source of the acquired specificity and activity.
Sequential Two-Step Stereoselective Amination of Allylic Alcohols through the Combination of Laccases and Amine Transaminases
Albarrán-Velo, Jesús,Lavandera, Iván,Gotor-Fernández, Vicente
, p. 200 - 211 (2019/12/03)
A sequential two-step chemoenzymatic methodology for the stereoselective synthesis of (3E)-4-(het)arylbut-3-en-2-amines in a highly selective manner and under mild reaction conditions is described. The approach consists of oxidation of the corresponding racemic alcohol precursors by the use of a catalytic system made up of the laccase from Trametes versicolor and the oxy-radical TEMPO, followed by the asymmetric reductive bio-transamination of the corresponding ketone intermediates. Optimisation of the oxidation reaction, exhaustive amine transaminase screening for the bio-transaminations and the compatibility of the two enzymatic reactions were studied in depth in search of a design of a compatible sequential cascade. This synthetic strategy was successful and the combinations of enzymes displayed a broad substrate scope, with 16 chiral amines being obtained in moderate to good isolated yields (29–75 %) and with excellent enantiomeric excess values (94 to >99 %). Interestingly, both amine enantiomers can be achieved, depending on the selectivity of the amine transaminase employed in the system.
VINYLOGOUS PHENETHYLAMINES AS NEUROTRANSMITTER RELEASERS
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, (2017/12/02)
The disclosure provides monoamine neurotransmitter releaser and/or monoamine uptake inhibitor compounds having biogenic amine transporter activity but lacking substantial activity at 5-HT2 receptor subtypes. The phenethylamine or vinylogous phe
The biogenic amine transporter activity of vinylogous amphetamine analogs
Decker, Ann M.,Partilla, John S.,Baumann, Michael H.,Rothman, Richard B.,Blough, Bruce E.
, p. 1657 - 1663 (2016/08/24)
A series of vinylogous amphetamine analogs was synthesized and examined for their activity at biogenic amine transporters and serotonin-2 receptor (5-HT2) subtypes. (1S,3E)-1-Methyl-4-phenyl-but-3-enylamine (S-6) is a potent dual dopamine/serotonin (DA/5-HT) releaser with no activity at 5-HT2 receptors. This unique profile of actions suggests that analog S-6 is a viable lead compound for identifying new structural classes of DA/5-HT releasers with therapeutic benefit and reduced abuse liability.
Palladium-catalyzed aerobic oxidative coupling of enantioenriched primary allylic amines with sulfonyl hydrazides leading to optically active allylic sulfones
Wang, Ting-Ting,Wang, Fu-Xiang,Yang, Fu-Lai,Tian, Shi-Kai
, p. 3802 - 3805 (2014/04/03)
A range of highly enantioenriched primary allylic amines underwent palladium-catalyzed oxidative coupling with sulfonyl hydrazides open to air at room temperature to give structurally diverse allylic sulfones in moderate to excellent yields with excellent retention of ee. This journal is the Partner Organisations 2014.
Non-enzymatic acylative kinetic resolution of primary allylic amines
Kolleth, Amandine,Cattoen, Martin,Arseniyadis, Stellios,Cossy, Janine
, p. 9338 - 9340 (2013/10/01)
A non-enzymatic acetyl transfer-based kinetic resolution of primary allylic amines is reported. The process involves the use of (1S,2S)-1 in conjunction with a supported ammonium salt and affords the corresponding enantio-enriched N-acetylated allylic ami
Enantioselektive Synthese von Allyl-, Propargyl- und 4-En-2-inyl-aminen durch 1,2-Addition von Organocer-Reagenzien an chirale Aldimine
Enders, Dieter,Schankat, Juergen
, p. 970 - 992 (2007/10/02)
(E)- and (Z)-Allyl-, propargyl, and 4-en-2-ynyl-amines 5 and 14, useful bifunctional building blocks and of pharmaceutical interest, are synthesized in high enantiomeric purity (e.e. >/= 97 percent).Key step is the diastereoselective 1,2-addition (d.e. 86
Enantioselective Synthesis of Allyl- and Propargylamines via Nucleophilic 1,2-Addition to Chiral Aldimines
Enders, Dieter,Schankat, Juergen
, p. 402 - 406 (2007/10/02)
The asymmetric synthesis of allylamines and propargylamines 5 in high enantiomeric purity (e.e >/= 97percent) is described.Key step is the 1,2-addition of organocerium reagents to chiral α,β-unsaturated aldimines 3 to produce secondary amines 4.The chiral
