113899-55-1Relevant articles and documents
Isopropylamine as Amine Donor in Transaminase-Catalyzed Reactions: Better Acceptance through Reaction and Enzyme Engineering
Dawood, Ayad W. H.,Wei?, Martin S.,Schulz, Christian,Pavlidis, Ioannis V.,Iding, Hans,de Souza, Rodrigo O. M. A.,Bornscheuer, Uwe T.
, p. 3943 - 3949 (2018)
Amine transaminases (ATA) have now become frequently used biocatalysts in chemo-enzymatic syntheses including industrial applications. They catalyze the transfer of an amine group from a donor to an acceptor leading to an amine product with high enantiopurity. Hence, they represent an environmentally benign alternative for waste intensive chemical amine synthesis. Isopropylamine (IPA) is probably one of the most favored amine donors since it is cheap and achiral, but nevertheless there is no consistency in literature concerning reaction conditions when IPA is best to be used. At the same time there is still a poor understanding which structural properties in ATA are responsible for IPA acceptance. Herein, we demonstrate, on the basis of the 3FCR enzyme scaffold, a substantial improvement in catalytic activity towards IPA as the amine donor. The asymmetric synthesis of industrial relevant amines was used as model reaction. A systematic investigation of the pH-value as well as concentration effects using common benchmark substrates and several ATA indicates the necessity of a substrate- and ATA-dependent reaction engineering.
A highly efficient resolution protocol for 2′-halo-α-methylbenzylamines
Klingensmith, Liane M.,Nadeau, Kelly A.,Moniz, George A.
, p. 4589 - 4593 (2007)
A highly efficient resolution protocol for 2′-halo-α-methylbenzylamines is reported. Commercially available and inexpensive mandelic acid can be used for the resolution of the Br, Cl, and F derivatives to >99% de in a single crystallization. In addition, the reduction of acetophenone oximes using borane-dimethylsulfide is presented as a method for the preparation of racemic amine precursors.
One-Pot C-H Arylation/Lactamization Cascade Reaction of Free Benzylamines
Chand-Thakuri, Pratibha,Landge, Vinod G.,Kapoor, Mohit,Young, Michael C.
, p. 6626 - 6644 (2020/07/14)
An efficient method has been developed for the synthesis of seven-membered biaryl lactams involving Pd-catalyzed, native amine-directed, ortho-arylation of benzylamines followed by in situ lactamization. This cascade sequence is enabled by the use of 2-iodobenzoates, which facilitates C-H arylation from the free amine under conditions that typically require an improved directing group approach. This reaction is characterized by a broad substrate scope with good functional group tolerance. The need for an ester versus carboxylic acid-functionalized coupling partner is also explored, as is the potential for synthesizing eight-membered biaryl lactams. Various applications are also investigated, including access to the aza-brassinolide core.
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.
Substituent effects on chiral resolutions of derivatized 1-phenylalkylamines by heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin GC stationary phase
Issaraseriruk, Natthapol,Sritana-anant, Yongsak,Shitangkoon, Aroonsiri
supporting information, p. 900 - 906 (2018/05/08)
Chiral resolutions of trifluoroacetyl-derivatized 1-phenylalkylamines with different type and position of substituent were investigated by capillary gas chromatography by using heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin diluted in OV-1701 as a chiral stationary phase. The influence of column temperature on retention and enantioselectivity was examined. All enantiomers of meta-substituted analytes as well as fluoro-substituted analytes could be resolved. Temperature had a favorable influence on enantioselectivity for small amines with substituents at the ortho-position. The type of substituent at the stereogenic center of amines also had a crucial effect as the ethyl group led to poor enantioseparation. Among all analytes studied, trifluoroacetyl-derivatized 1-(2′-fluorophenyl)ethylamine exhibited baseline resolution with the shortest analysis time.
Biocatalytic Routes to Enantiomerically Enriched Dibenz[c,e]azepines
France, Scott P.,Aleku, Godwin A.,Sharma, Mahima,Mangas-Sanchez, Juan,Howard, Roger M.,Steflik, Jeremy,Kumar, Rajesh,Adams, Ralph W.,Slabu, Iustina,Crook, Robert,Grogan, Gideon,Wallace, Timothy W.,Turner, Nicholas J.
supporting information, p. 15589 - 15593 (2017/12/02)
Biocatalytic retrosynthetic analysis of dibenz[c,e]azepines has highlighted the use of imine reductase (IRED) and ω-transaminase (ω-TA) biocatalysts to establish the key stereocentres of these molecules. Several enantiocomplementary IREDs were identified
Stereoselective amination of racemic sec-alcohols through sequential application of laccases and transaminases
Martínez-Montero, Lía,Gotor, Vicente,Gotor-Fernández, Vicente,Lavandera, Iván
supporting information, p. 474 - 480 (2017/06/23)
A one-pot/two-step bienzymatic asymmetric amination of secondary alcohols is disclosed. The approach is based on a sequential strategy involving the use of a laccase/TEMPO catalytic system for the oxidation of alcohols into ketone intermediates, and their following transformation into optically enriched amines by using transaminases. Individual optimizations of the oxidation and biotransamination reactions have been carried out, studying later their applicability in a concurrent process. Therefore, 17 racemic (hetero) aromatic sec-alcohols with different substitutions in the aromatic ring have been converted into enantioenriched amines with good to excellent selectivities (90-99% ee) and conversion values (67-99%). The scalability of the process was also demonstrated when two different amine donors were used in the transamination step, such as isopropylamine and cis-2-buten-1,4-diamine. Satisfyingly, both sacrificial amine donors can shift the equilibrium toward the amine formation, leading to the corresponding isolated enantioenriched amines with good to excellent results.
Transaminases applied to the synthesis of high added-value enantiopure amines
Paul, Caroline E.,Rodriguez-Mata, Maria,Busto, Eduardo,Lavandera, Ivan,Gotor-Fernandez, Vicente,Gotor, Vicente,Garcia-Cerrada, Susana,Mendiola, Javier,De Frutos, Oscar,Collado, Ivan
supporting information, p. 788 - 792 (2014/07/08)
Critical parameters affecting the stereoselective amination of (hetero)aromatic ketones using transaminases have been studied, such as temperature, pH, substrate concentration, cosolvent, and source and percentage of amino donor, to further optimize the production of enantiopure amines using both (S)- and (R)-selective biocatalysts from commercial suppliers. Interesting enantiopure amino building blocks have been obtained, overcoming some limitations of traditional chemical synthetic methods. Representative processes were scaled up, affording halogenated and heteroaromatic amines in enantiomerically pure form and good isolated yields.
Liquid chromatographic resolution of fendiline and its analogues on a chiral stationary phase based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid
Lee, Ga Ram,Hyun, Myung Ho
, p. 21386 - 21397 (2015/02/19)
Fendiline, an effective anti-anginal drug for the treatment of coronary heart diseases, and its sixteen analogues were resolved on a CSP based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. Fendiline was resolved quite well with the separation factor (α) of 1.25 and resolution (RS ) of 1.55 when a mobile phase consisting of methanol-acetonitrile-trifluoroacetic acid-triethylamine at a ratio of 80/20/0.1/0.5 (v/v/v/v) was used. The comparison of the chromatographic behaviors for the resolution of fendiline and its analogues indicated that the 3,3-diphenylpropyl group bonded to the secondary amino group of fendiline is important in the chiral recognition and the difference in the steric bulkiness between the phenyl group and the methyl group at the chiral center of fendiline is also important in the chiral recognition.
TRIAZOLYL AMINOPYRIMIDINE COMPOUNDS
-
Page/Page column 11, (2009/01/20)
The present invention provides triazolyl aminopyrimidine compounds useful in the treatment of cancer.
