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1.
Synthesis and Conformational Analysis of Hybrid α/β‐Dipeptides Incorporating S‐Glycosyl‐β2,2‐Amino Acids 下载免费PDF全文
Iván García‐González Dr. Lara Mata Dr. Francisco Corzana Dr. Gonzalo Jiménez‐Osés Prof. Alberto Avenoza Dr. Jesús H. Busto Prof. Jesús M. Peregrina 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(3):1156-1168
We synthesized and carried out the conformational analysis of several hybrid dipeptides consisting of an α‐amino acid attached to a quaternary glyco‐β‐amino acid. In particular, we combined a S‐glycosylated β2,2‐amino acid and two different types of α‐amino acid, namely, aliphatic (alanine) and aromatic (phenylalanine and tryptophan) in the sequence of hybrid α/β‐dipeptides. The key step in the synthesis involved the ring‐opening reaction of a chiral cyclic sulfamidate, inserted in the peptidic sequence, with a sulfur‐containing nucleophile by using 1‐thio‐β‐D ‐glucopyranose derivatives. This reaction of glycosylation occurred with inversion of configuration at the quaternary center. The conformational behavior in aqueous solution of the peptide backbone and the glycosidic linkage for all synthesized hybrid glycopeptides was analyzed by using a protocol that combined NMR experiments and molecular dynamics with time‐averaged restraints (MD‐tar). Interestingly, the presence of the sulfur heteroatom at the quaternary center of the β‐amino acid induced θ torsional angles close to 180° (anti). Notably, this value changed to 60° (gauche) when the peptidic sequence displayed aromatic α‐amino acids due to the presence of CH–π interactions between the phenyl or indole ring and the methyl groups of the β‐amino acid unit. 相似文献
2.
Kazuaki Ishihara Kazuki Nishimura Katsuya Yamakawa 《Angewandte Chemie (International ed. in English)》2020,59(40):17641-17647
Catalytic enantioselective α‐fluorination reactions of carbonyl compounds are among the most powerful and efficient synthetic methods for constructing optically active α‐fluorinated carbonyl compounds. Nevertheless, α‐fluorination of α‐nonbranched carboxylic acid derivatives is still a big challenge because of relatively high pKa values of their α‐hydrogen atoms and difficulty of subsequent synthetic transformation without epimerization. Herein we show that chiral copper(II) complexes of 3‐(2‐naphthyl)‐l ‐alanine‐derived amides are highly effective catalysts for the enantio‐ and site‐selective α‐fluorination of N‐(α‐arylacetyl) and N‐(α‐alkylacetyl) 3,5‐dimethylpyrazoles. The substrate scope of the transformation is very broad (25 examples including a quaternary α‐fluorinated α‐amino acid derivative). α‐Fluorinated products were converted into the corresponding esters, secondary amides, tertiary amides, ketones, and alcohols with almost no epimerization in high yield. 相似文献
3.
Ming‐Sheng Xie Ye‐Fei Zhang Meng Shan Xiao‐Xia Wu Gui‐Rong Qu Hai‐Ming Guo 《Angewandte Chemie (International ed. in English)》2019,58(9):2839-2843
A DMAP‐N‐oxide, featuring an α‐amino acid as the chiral source, was developed, synthesized and applied in asymmetric Steglich rearrangement. A series of O‐acylated azlactones afforded C‐acylated azlactones possessing a quaternary stereocenter in high yields (up to 97 % yield) and excellent enantioselectivities (up to 97 % ee). Compared to the widespread use of pyridine nitrogen, which serves as the nucleophilic site in the asymmetric acyl transfer reaction, we discovered that chiral DMAP‐N‐oxides, in which the oxygen now acts as the nucleophilic site, are efficient acyl transfer catalysts. Our finding might open a new door for the development of chiral DMAP‐N‐oxides for asymmetric acyl transfer reactions. 相似文献
4.
Ming‐Sheng Xie Ye‐Fei Zhang Meng Shan Xiao‐Xia Wu Gui‐Rong Qu Hai‐Ming Guo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(9):2865-2869
A DMAP‐N‐oxide, featuring an α‐amino acid as the chiral source, was developed, synthesized and applied in asymmetric Steglich rearrangement. A series of O‐acylated azlactones afforded C‐acylated azlactones possessing a quaternary stereocenter in high yields (up to 97 % yield) and excellent enantioselectivities (up to 97 % ee). Compared to the widespread use of pyridine nitrogen, which serves as the nucleophilic site in the asymmetric acyl transfer reaction, we discovered that chiral DMAP‐N‐oxides, in which the oxygen now acts as the nucleophilic site, are efficient acyl transfer catalysts. Our finding might open a new door for the development of chiral DMAP‐N‐oxides for asymmetric acyl transfer reactions. 相似文献
5.
Chiral N‐Heterocyclic Carbene Ligands Bearing a Pyridine Moiety for the Copper‐Catalyzed Alkylation of N‐Sulfonylimines with Dialkylzinc Reagents 下载免费PDF全文
Dr. Takahiro Soeta Tomohiro Ishizaka Yuta Tabatake Prof. Dr. Yutaka Ukaji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16773-16778
Amino acid‐derived chiral imidazolium salts, each bearing a pyridine ring, were developed as N‐heterocyclic carbene ligands. The copper‐catalyzed asymmetric alkylation of various N‐sulfonylimines with dialkylzinc reagents in the presence of these chiral imidazolium salts afforded the corresponding alkylated products with high enantioselectivity (up to 99 % ee). The addition of HMPA to the reaction mixture as a co‐solvent is critical in terms of chemical yield and enantioselectivity. A wide range of N‐sulfonylimines and dialkylzinc reagents were found to be applicable to this reaction. 相似文献
6.
Lei Li Qiao Yang Dr. Yuan Wang Prof. Yanxing Jia 《Angewandte Chemie (International ed. in English)》2015,54(21):6255-6259
The catalytic asymmetric total syntheses of (?)‐galanthamine ( 1 ) and (?)‐lycoramine ( 2 ) have been achieved by using a conceptually new strategy featuring two metal‐catalyzed reactions as the key steps. A new method for the construction of 3,4‐fused benzofurans has been developed through a palladium‐catalyzed intramolecular Larock annulation reaction, which was successfully applied to the construction of the ABD tricyclic skeleton of 1 and 2 . To achieve the asymmetric synthesis of 1 and 2 , a ScIII/N,N′‐dioxide complex was used to catalyze the enantioselective conjugate addition of 3‐alkyl‐substituted benzofuranone to methyl vinyl ketone for the construction of a chiral quaternary carbon center. 相似文献
7.
Oleg N. Chupakhin Gennady L. Rusinov Dmitry G. Beresnev Valery N. Charushin Hans Neunhoeffer 《Journal of heterocyclic chemistry》2001,38(4):901-907
A new synthetic approach to condensed 1,2,4‐triazines based on using the tandem AN‐SNipso and SNH‐SNipso reactions has been developed. 5‐Methoxy‐3‐penyl‐1,2,4‐triazine and its N1‐methyl quaternary salt were found to react with C,N‐, C,O‐ and N,N'‐bifunctional nucleophiles (m‐phenylenediamine, resor‐cinol, semicarbazide and ureas) into triazacarbazoles, benzofuro[2,3‐e][1,2,4]‐triazines, and 6‐azapurine derivatives. In all cases nucleophiles attack first the unsubstituted C‐6 carbon of the triazine ring, while the final stage is replacement of the methoxy group affording cyclization products. 相似文献
8.
Hossay Abas Josep Mas‐Rosell Mostafa Mahmoud Amer Derek J. Durand Robin R. Groleau Natalie Fey Jonathan Clayden 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(8):2440-2444
Both E‐ and Z‐N′‐alkenyl urea derivatives of imidazolidinones may be formed selectively from enantiopure α‐amino acids. Generation of their enolate derivatives in the presence of K+ and [18]crown‐6 induces intramolecular migration of the alkenyl group from N′ to Cα with retention of double bond geometry. DFT calculations indicate a partially concerted substitution mechanism. Hydrolysis of the enantiopure products under acid conditions reveals quaternary α‐alkenyl amino acids with stereodivergent control of both absolute configuration and double bond geometry. 相似文献
9.
Chune Dong Junlong Zhang Liangfu Zhang Zuolong Yu 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(1):e21-e21
The crystal structure of the new chiral complex (1R,2R)‐1,2‐diphenyl‐1,2‐bis(8‐quinolinesulfonylamino)‐ ethylenediamine–acetone (1/1), C32H26N4O4S2.C3H6O, is reported. The conformation of the C32H26N4O4S2 (BQSDA) molecule is determined by a bifurcated N—H?N hydrogen‐bond system. The acetone of solvation is linked to the BQSDA molecule by an N—H?O hydrogen bond. 相似文献
10.
The treatment of a β3‐amino acid methyl ester with 2.2 equiv. of lithium diisopropylamide (LDA), followed by reaction with 5 equiv. of N‐fluorobenzenesulfonimide (NFSI) at ?78° for 2.5 h and then 2 h at 0°, gives syn‐fluorination with high diastereoisomeric excess (de). The de and yield in these reactions are somewhat influenced by both the size of the amino acid side chain and the nature of the amine protecting group. In particular, fluorination of N‐Boc‐protected β3‐homophenylalanine, β3‐homoleucine, β3‐homovaline, and β3‐homoalanine methyl esters, 5 and 9 – 11 , respectively, all proceeded with high de (>86% of the syn‐isomer). However, fluorination of N‐Boc‐protected β3‐homophenylglycine methyl ester ( 16 ) occurred with a significantly reduced de. The use of a Cbz or Bz amine‐protecting group (see 3 and 15 ) did not improve the de of fluorination. However, an N‐Ac protecting group (see 17 ) gave a reduced de of 26%. Thus, a large N‐protecting group should be employed in order to maximize selectivity for the syn‐isomer in these fluorination reactions. 相似文献
11.
Jain John T. Balasubramanian 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(8):o436-o440
Maleic acid and fumaric acid, the Z and E isomers of butenedioic acid, form 1:1 adducts with 2‐amino‐1,3‐thiazole, namely 2‐amino‐1,3‐thiazolium hydrogen maleate (2ATHM), C3H5N2S+·C4H3O4−, and 2‐amino‐1,3‐thiazolium hydrogen fumarate (2ATHF), C3H5N2S+·C4H3O4−, respectively. In both compounds, protonation of the ring N atom of the 2‐amino‐1,3‐thiazole and deprotonation of one of the carboxyl groups are observed. The asymmetric unit of 2ATHF contains three independent ion pairs. The hydrogen maleate ion of 2ATHM shows a short intramolecular O—H...O hydrogen bond with an O...O distance of 2.4663 (19) Å. An extensive hydrogen‐bonded network is observed in both compounds, involving N—H...O and O—H...O hydrogen bonds. 2ATHM forms two‐dimensional sheets parallel to the ab plane, extending as independent parallel sheets along the c axis, whereas 2ATHF forms two‐dimensional zigzag layers parallel to the bc plane, extending as independent parallel layers along the a axis. 相似文献
12.
Igor V. Ukrainets Svitlana V. Shishkina Vyacheslav N. Baumer Olga V. Gorokhova Lidiya A. Petrushova Galina Sim 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(5):411-415
The fact that molecular crystals exist as different polymorphic modifications and the identification of as many polymorphs as possible are important considerations for the pharmaceutic industry. The molecule of N‐benzyl‐4‐hydroxy‐1‐methyl‐2,2‐dioxo‐1H‐2λ6,1‐benzothiazine‐3‐carboxamide, C17H16N2O4S, does not contain a stereogenic atom, but intramolecular hydrogen‐bonding interactions engender enantiomeric chiral conformations as a labile racemic mixture. The title compound crystallized in a solvent‐dependent single chiral conformation within one of two conformationally polymorphic P212121 orthorhombic chiral crystals (denoted forms A and B). Each of these pseudo‐enantiomorphic crystals contains one of two pseudo‐enantiomeric diastereomers. Form A was obtained from methylene chloride and form B can be crystallized from N,N‐dimethylformamide, ethanol, ethyl acetate or xylene. Pharmacological studies with solid–particulate suspensions have shown that crystalline form A exhibits an almost fourfold higher antinociceptive activity compared to form B. 相似文献
13.
Wei Xiong Yan Su Zilu Chen Fupei Liang 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(2):m56-m58
In the chiral polymeric title compound, poly[aqua(4,4′‐bipyridine)[μ3‐S‐carboxylatomethyl‐N‐(p‐tosyl)‐l ‐cysteinato]manganese(II)], [Mn(C12H13NO6S2)(C10H8N2)(H2O)]n, the MnII ion is coordinated in a distorted octahedral geometry by one water molecule, three carboxylate O atoms from three S‐carboxyatomethyl‐N‐(p‐tosyl)‐l ‐cysteinate (Ts‐cmc) ligands and two N atoms from two 4,4′‐bipyridine molecules. Each Ts‐cmc ligand behaves as a chiral μ3‐linker connecting three MnII ions. The two‐dimensional frameworks thus formed are further connected by 4,4′‐bipyridine ligands into a three‐dimensional homochiral metal–organic framework. This is a rare case of a homochiral metal–organic framework with a flexible chiral ligand as linker, and this result demonstrates the important role of noncovalent interactions in stabilizing such assemblies. 相似文献
14.
Fernando Formaggio Cristina Peggion Marco Crisma Claudio Toniolo Luba Tchertanov Jean Guilhem Jean‐Paul Mazaleyrat Yolaine Goubard Anne Gaucher Michel Wakselman 《Helvetica chimica acta》2001,84(2):481-501
A variety of model peptides, including four complete homologous series, to the pentamer level, characterized by the recently proposed binaphthyl‐based, axially chiral, Cα‐tetrasubstituted, cyclic α‐amino acid Bin, in combination with Ala, Gly, or Aib residues, was synthesized by solution methods and fully characterized. The solution conformational propensity of these peptides was determined by FT‐IR absorption and 1H‐NMR techniques. Moreover, the molecular structures of the free amino acid (S)‐enantiomer and an Nα‐acylated dipeptide alkylamide with the heterochiral sequence ‐(R)‐Bin‐Phe‐ were assessed in the crystal state by X‐ray diffraction. Taken together, the results point to the conclusion that β‐bends and 310 helices are preferentially adopted by Bin‐containing peptides, although the fully extended conformation would also be adopted in solution by the short oligomers to some extent. We also confirmed the tendency of (R)‐Bin to fold a peptide chain into right‐handed bend and helical structures. The absolute configuration of the Bin residue(s) was correlated with the typically intense exciton‐split Cotton effect of the 1Bb binaphthyl transition near 225 nm. 相似文献
15.
Reijo Sillanp Mikko M. Hnninen 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(5):509-512
The title cocrystal contains two chiral conformational diastereomers, viz. (1S,2R,RN)‐ and (1S,2R,SN)‐, of [2,4‐di‐tert‐butyl‐6‐{[(1‐oxido‐1‐phenylpropan‐2‐yl)(methyl)amino]methyl}phenolato](methanol)‐cis‐dioxidomolybdenum(VI), [Mo(C25H35NO2)O2(CH3OH)], representing the first example of a structurally characterized molybdenum complex with enantiomerically pure ephedrine derivative ligands. The MoVI cations exhibit differently distorted octahedral coordination environments, with two oxide ligands positioned cis to each other. The remainder of the coordination comprises phenoxide, alkoxide and methanol O atoms, with an amine N atom completing the octahedron. The distinct complexes are linked by strong intermolecular O—H...O hydrogen bonds, resulting in one‐dimensional molecular chains. Furthermore, the phenyl rings are involved in weak T‐shaped/edge‐to‐face π–π interactions with each other. 相似文献
16.
Nikolaos C. Papandreou Stella Makedonopoulou Ekaterini A. Antoniadou‐Vyza Irene M. Mavridis Stavros J. Hamodrakas 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(12):o730-o732
The title salt, C18H22N5+·Cl?, is a member of a new series of lipophilic 4,6‐diamino spiro‐s‐triazines which are potent inhibitors of dihydrofolate reductase. The protonated triazine ring deviates from planarity, whereas the cyclohexane ring adopts a chair conformation. A rather unusual hydrogen‐bonding scheme exists in the crystal. There is a centrosymmetric arrangement involving two amino groups and two triazine ring N atoms, with graph‐set R(8) and an N?N distance of 3.098 (3) Å, flanked by two additional R(8) systems, involving two amino groups, a triazine ring N atom and a Cl? anion, with N?Cl distances in the range 3.179 (2)–3.278 (2) Å. Furthermore, the Cl? anion, the protonated triazine ring N atom and an amino group form a hydrogen‐bonding system with graph‐set R(6). 相似文献
17.
Ewa Matczak‐Jon Katarzyna
lepokura Pawe Kafarski Izabela Skrzyska Marek Jon 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(6):o261-o266
The crystal structures of two salts, products of the reactions between [(5‐methyl‐2‐pyridyl)aminomethylene]bis(phosphonic acid) and 4‐aminopyridine or ammonia, namely bis(4‐aminopyridinium) hydrogen [(5‐methyl‐2‐pyridinio)aminomethylene]diphosphonate 2.4‐hydrate, 2C5H7N2+·C7H10N2O6P22−·2.4H2O, (I), and triammonium hydrogen [(5‐methyl‐2‐pyridyl)aminomethylene]diphosphonate monohydrate, 3NH4+·C7H9N2O6P23−·H2O, (II), have been determined. In (I), the Z configuration of the ring N—C and amino N—H bonds of the bisphosphonate dianion with respect to the Cring—Namino bond is consistent with that of the parent zwitterion. Removing the H atom from the pyridyl N atom results in the opposite E configuration of the bisphosphonate trianion in (II). Compound (I) exhibits a three‐dimensional hydrogen‐bonded network, in which 4‐aminopyridinium cations and water molecules are joined to ribbons composed of anionic dimers linked by O—H...O and N—H...O hydrogen bonds. The supramolecular motif resulting from a combination of these three interactions is a common phenomenon in crystals of all of the Z‐isomeric zwitterions of 4‐ and 5‐substituted (2‐pyridylaminomethylene)bis(phosphonic acid)s studied to date. In (II), ammonium cations and water molecules are linked to chains of trianions, resulting in the formation of double layers. 相似文献
18.
Diastereocontrolled Monoprotodeboronation of β‐Sulfinimido gem‐Bis(boronates): A General and Stereoselective Route to α,β‐Disubstituted β‐Aminoalkylboronates 下载免费PDF全文
Xiangyu Li Prof. Dr. Dennis G. Hall 《Angewandte Chemie (International ed. in English)》2018,57(32):10304-10308
β‐Aminoalkylboronic acids are bioisosteres of the pharmaceutically important class of β‐amino acids but few stereoselective methods exist for their preparation. The 1,2‐addition of lithiated 1,1‐diborylalkanes onto chiral N‐tert‐butanesulfinyl aldimines produces β‐sulfinimido gem‐bis(boronates) in good to excellent yields with high diastereoselectivity. The optimized conditions involve the use of rubidium fluoride and water, and are compatible with functionalized alkyl, aryl, alkenyl, and alkynyl substituents. Under these conditions, the geminal quaternary alkyl bis(pinacolatoboryl) intermediates undergo a highly diastereoselective monoprotodeboronation to afford a wide range of syn‐α,β‐disubstituted β‐aminoalkylboronates. This novel application of protodeboronation chemistry was shown to result from a kinetically controlled, diastereotopic‐group‐selective B?C bond protolysis dictated by the configuration of the adjacent stereogenic C?N center. Facile acidic cleavage of the sulfinimide auxiliary produces the free aminoboronates with high enantiomeric purity. 相似文献
19.
Makoto Eishima Shigeru Ohba Masumi Suzuki Chiaki Nagasawa Takeshi Sugai 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(11):1391-1393
In the racemic crystals of (1S,2R)‐ or (1R,2S)‐1‐[N‐(chloroacetyl)carbamoylamino]‐2,3‐dihydro‐1H‐inden‐2‐yl chloroacetate, C14H14Cl2N2O4, (I), the enantiomeric molecules form a dimeric structure via the N—H?O cyclic hydrogen bond of the carbamoyl moieties. In the chiral crystals of (—)‐(1S,2R)‐1‐[N‐(chloroacetyl)carbamoylamino]‐2,3‐dihydro‐1H‐inden‐2‐yl chloroacetate, C14H14Cl2N2O4, (II), the N—H?O intermolecular hydrogen bond forms a zigzag chain around the twofold screw axis. The melting points and calculated densities of (I) and (II) are 446 and 396 K, and 1.481 and 1.445 Mg m?3, respectively. 相似文献
20.
The title compound, [Cu2(C9H10NO3)2(NO3)2(C10H8N2)(H2O)2]n, contains CuII atoms and l ‐tyrosinate (l ‐tyr) and 4,4′‐bipyridine (4,4′‐bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two l ‐tyr ligands, one N atom from a 4,4′‐bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4′‐bipy ligands, forming an undulated chiral two‐dimensional sheet. O—H...O and N—H...O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4′‐bipy ligands by considering the ratios of the metal ion and organic components. 相似文献