ChemInform Abstract: NOVEL ANIONIC REAGENTS FOR THE STEREOSELECTIVE SYNTHESIS OF Γ-HYDROXY-α-AMINO-ACIDS. AN X-RAY CRYSTALLOGRAPHIC STUDY OF 2R(S)-BENZOYLAMINO-N-TERT-BUTYL-4R(S)-HYDROXY-4-(4-METHOXYPHENYL)-3R(S)-METHYLBUTANAMIDE

1983 ◽  
Vol 14 (50) ◽  
Author(s):  
B. J. BANKS ◽  
A. G. M. BARRETT ◽  
M. A. RUSSELL ◽  
D. J. WILLIAMS
Keyword(s):  
Amino Acids ◽  
Stereoselective Synthesis ◽  
X Ray ◽  
Tert Butyl ◽  
Crystallographic Study

Conformational study of the 3,6-dihydro-2H-1,4-oxazin-2-one fragment in 8-tert-butyl-7-methoxy-8-methyl-9-oxa-6-azaspiro[4.5]decane-2,10-dione stereoisomers

2017 ◽  
Vol 73 (7) ◽  
pp. 556-562
Author(s):  
Ewa Żesławska ◽  
Anna Jakubowska ◽  
Wojciech Nitek
Keyword(s):  
Amino Acids ◽  
Crystal Structures ◽  
Stereoselective Synthesis ◽  
Biologically Active ◽  
Asymmetric Unit ◽  
Conformational Study ◽  
X Ray Diffraction ◽  
X Ray ◽  
Natural Amino Acids ◽  
Heterocyclic Moiety

Unnatural cyclic α-amino acids play an important role in the search for biologically active compounds and macromolecules. Enantiomers of natural amino acids with a D configuration are not naturally encoded, but can be chemically synthesized. The crystal structures of two enantiomers obtained by a method of stereoselective synthesis, namely (5R,8S)-8-tert-butyl-7-methoxy-8-methyl-9-oxa-6-azaspiro[4.5]decane-2,10-dione, (1), and (5S,8R)-8-tert-butyl-7-methoxy-8-methyl-9-oxa-6-azaspiro[4.5]decane-2,10-dione, (2), both C14H21NO4, were determined by X-ray diffraction. Both enantiomers crystallize isostructurally in the space group P21, with one molecule in the asymmetric unit and with the same packing motif. The crystal structures are stabilized by C—H...O hydrogen bonds, resulting in the formation of chains along the [100] and [010] directions. The conformation of the 3,6-dihydro-2H-1,4-oxazin-2-one fragment was compared with other crystal structures possessing this heterocyclic moiety. The comparison showed that the title compounds are not exceptional among structures containing the 3,6-dihydro-2H-1,4-oxazin-2-one fragment. The planar moiety was more frequently observed in derivatives in which this fragment was not condensed with other rings.

Oxidation-Induced Acyl Group Transfer from Hydroquinone Esters to Nucleophiles

1998 ◽  
Vol 53 (7) ◽  
pp. 765-773 ◽  
Author(s):  
Gerald Reischl ◽  
Medhat El-Mobayed ◽  
Rudolf Beißwenger ◽  
Klaus Regier ◽  
Cäcilia Maichle-Mössmer ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Amino Acids ◽  
Chemical Oxidation ◽  
Acyl Transfer ◽  
X Ray ◽  
Group Transfer ◽  
Tert Butyl ◽  
X Ray Crystallography ◽  
Toluenesulfonic Acid ◽  
Mediated Oxidation

Bivalent oxidation of 3,5-di-tert-butyl-hydroquinone monoesters leads to phenoxenium ions, which can transfer an acyl group to nucleophiles. Based on this principle, dipeptides, glyco-amino acids and N-sulfonyl-amino acids were synthesized from hydroquinone esters of amino acids and p-toluenesulfonic acid. For this reaction, direct anodic and indirect mediated oxidation, as well as chemical oxidation with NBS or trisarylammoniumyl salts, was used. The mechanism of the acyl transfer is discussed in terms of a direct and/or a mediated process. A spirocyclic key intermediate was isolated and its molecular structure determined by X-ray crystallography.

scholarly journals A study on the synthesis of β-amino acids: the first synthesis of a bicyclic hemiaminal (3,3-dimethyl-1-(2,4,5-trifluorophenyl) tetrahydro-3H,5H-oxazolo[3,4-c] [1,3] oxazin-5-one)

2020 ◽  
Author(s):  
Ozlem Gundogdu ◽  
Ertan Sahin ◽  
Yunus Kara
Keyword(s):  
Amino Acids ◽  
Hydrogenation Reaction ◽  
Oxazole Ring ◽  
X Ray ◽  
Tert Butyl ◽  
Rearrangement Reaction

We synthesized (4S)-4-(2-((tert-butyldimethylsilyl)oxy)ethyl)-5-(2,4,5-trifluorophenyl) oxazolidin-2-one and examined its Pd/C-catalyzed hydrogenation reaction. The condensation and rearrangement reaction of acetone with (4S)-4-(2-((tert-butyl dimethylsilyl)oxy)ethyl)-5-(2,4,5-trifluorophenyl)oxazolidin-2-one resulted in the formation of a hemiaminal structure containing a fused oxazine-oxazole ring, whose exact configuration was determined by X-ray crystal analysis. A mechanism was proposed to explain the formation of the fused oxazine-oxazole ring, which has a hemiaminal structure.

X-ray Crystallographic Study of Alkylammonium Anthracene-9-carboxylates as a Model for Fibrous Structure of Binary Anthracene Salt Gels

2004 ◽  
Vol 69 (6) ◽  
pp. 1292-1300 ◽  
Author(s):  
Tahahiro Tani ◽  
Kazuki Sada ◽  
Masatsugu Ayabe ◽  
Yuya Iwashita ◽  
Takanori Kishida ◽  
...  
Keyword(s):  
Alkyl Chain ◽  
Columnar Structure ◽  
Hydrogen Bond Network ◽  
One Dimensional ◽  
X Ray ◽  
Crystallographic Study ◽  
Alkylammonium Salts ◽  
Bond Network ◽  
Fibrous Assemblies ◽  
Long Alkyl Chain

Crystal structure of hexylammonium anthracene-9-carboxylate was investigated. The salt was arranged by a one-dimensional hydrogen bond network to form a columnar structure in the crystalline state. This columnar structure should be the model of fibrous assemblies in the organogels of anthracene-9-carboxylate alkylammonium salts having a long alkyl chain.

scholarly journals X-ray Crystallographic Study of the Erabutoxins and of a Diiodo Derivative

1971 ◽  
Vol 246 (13) ◽  
pp. 4366-4368 ◽  
Author(s):  
Barbara W. Low ◽  
Reginald Potter ◽  
Richard B. Jackson ◽  
Nobuo Tamiya ◽  
Showbu Sato
Keyword(s):  
X Ray ◽  
Crystallographic Study

scholarly journals Peculiarities of promiscuous l-threonine transaldolases for enantioselective synthesis of β-hydroxy-α-amino acids

2021 ◽  
Author(s):  
Shan Wang ◽  
Hai Deng
Keyword(s):  
Amino Acids ◽  
Organic Molecules ◽  
Stereoselective Synthesis ◽  
Enantioselective Synthesis ◽  
General Mechanism ◽  
Future Developments ◽  
Key Points ◽  
Biomaterial Science ◽  
One Step ◽  
Harsh Conditions

Abstract The introduction of β-hydroxy-α-amino acids (βHAAs) into organic molecules has received considerable attention as these molecules have often found widespread applications in bioorganic chemistry, medicinal chemistry and biomaterial science. Despite innovation of asymmetric synthesis of βHAAs, stereoselective synthesis to control the two chiral centres at Cα and Cβ positions is still challenging, with poor atomic economy and multi protection and deprotection steps. These syntheses are often operated under harsh conditions. Therefore, a biotransformation approach using biocatalysts is needed to selectively introduce these two chiral centres into structurally diverse molecules. Yet, there are few ways that enable one-step synthesis of βHAAs. One is to extend the substrate scope of the existing enzyme inventory. Threonine aldolases have been explored to produce βHAAs. However, the enzymes have poor controlled installation at Cβ position, often resulting in a mixture of diastereoisomers which are difficult to be separated. In this respect, l-threonine transaldolases (LTTAs) offer an excellent potential as the enzymes often provide controlled stereochemistry at Cα and Cβ positions. Another is to mine LTTA homologues and engineer the enzymes using directed evolution with the aim of finding engineered biocatalysts to accept broad substrates with enhanced conversion and stereoselectivity. Here, we review the development of LTTAs that incorporate various aldehyde acceptors to generate structurally diverse βHAAs and highlight areas for future developments. Key points • The general mechanism of the transaldolation reaction catalysed by LTTAs • Recent advances in LTTAs from different biosynthetic pathways • Applications of LTTAs as biocatalysts for production of βHAAs

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