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1.
Breznik M Grdadolnik SG Giester G Leban I Kikelj D 《The Journal of organic chemistry》2001,66(21):7044-7050
We report that the cis/trans ratio of the proline peptide bond can be strongly influenced by the chirality of the acyl residue preceding proline. Acyl moieties derived from (2S)-2,6-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid (8) and (2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoic acid (5) in acyl-Pro molecules influence isomerization of the proline peptide bond constraining the omega dihedral angle to the trans orientation. Structures of benzyl (2S)-1-([(2S)-2,6-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl]carbonyl)-2-pyrrolidinecarboxylate (3) derived from 2D (1)H NMR conformational analysis and crystallographic data exhibit only the trans conformation of proline peptide bond. On the other hand the diastereomer 4, which contains an (R) acyl moiety, exhibits two sets of signals in (1)H NMR spectra. The signals were assigned to trans (72%) and cis (28%) conformers. Crystallographic analysis of 4 showed that only the cis conformation is present in the crystalline state. The (1)H NMR chemical shift pattern of three sets of signals observed in 2 was observed also in benzyl (2S)-1-[(2R/S)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoyl]-2-pyrrolidinecarboxylate. (R)-Carboxylic acid 5, after coupling with (S)-ProOBn, yielded benzyl (2S)-1-[(2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoyl]-2-pyrrolidinecarboxylate (6), which in DMSO-d(6) exhibited only the trans conformation of the proline peptide bond. These results suggest that in these particular cases acyl-Pro peptide bond isomerization is strongly influenced by the stereochemistry of the acyl residue preceding proline. (2S)-2,6-Dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid (8) and (2R)-3-methoxy-2-methyl-2-(4-methyl-2-nitrophenoxy)-3-oxopropanoic acid (5) are promising chiral peptidomimetic building blocks that can be used as acyl moieties to force the proline peptide bond into the trans conformation in a variety of acyl-Pro molecules. 相似文献
2.
The syntheses of methyl 4‐(4‐nitrophenyl)‐3‐oxomorpholine‐2‐carboxylate ( 3a ) and ethyl 4‐(4‐nitrophenyl)‐2‐oxomorpholine‐3‐carboxylate ( 5b ), important building blocks for the synthesis of factor Xa inhibitor rivaroxaban analogs with potential dual antithrombotic activity, via Rh2(OAc)4‐catalyzed O? H and N? H carbene insertion reactions are described. 相似文献
3.
Vincent Kikelj 《Tetrahedron letters》2008,49(20):3273-3275
A new synthesis of nucleoside analogues has been developed. The cyclocondensation of a glycosylated diazadiene or thiazadiene, with acyl chlorides or α-halogenoketones, respectively, resulted in good yields and excellent regioselectivities. We report an efficient method for the production of glucosyl pyrimidinones and glucosylamino thiazoles. 相似文献
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Todorović Danijel Tomić Mladen Bojanić Ranko Bajatović Dušan Anđelković Aleksandar S. 《Journal of Thermal Analysis and Calorimetry》2020,141(1):559-572
Journal of Thermal Analysis and Calorimetry - System for domestic hot water (DHW) preparation generally represents a considerable portion of the energy and water consumption in hotels worldwide. As... 相似文献
6.
Danijel Krizmanić 《Extremes》2016,19(1):7-23
For a strictly stationary sequence of nonnegative regularly varying random variables (X n ) we study functional weak convergence of partial maxima processes \(M_{n}(t) = \bigvee _{i=1}^{\lfloor nt \rfloor }X_{i},\,t \in [0,1]\) in the space D[0, 1] with the Skorohod J 1 topology. Under the strong mixing condition, we give sufficient conditions for such convergence when clustering of large values do not occur. We apply this result to stochastic volatility processes. Further we give conditions under which the regular variation property is a necessary condition for J 1 and M 1 functional convergences in the case of weak dependence. We also prove that strong mixing implies the so-called Condition \(\mathcal {A}(a_{n})\) with the time component. 相似文献
7.
A general synthesis of new alkyl 4-alkyl-2-hydroxy-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylate peptidomimetic building blocks from the corresponding alkyl 3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylates through carbanion oxidation is described. 相似文献
8.
Stefanic P Simoncic Z Breznik M Plavec J Anderluh M Addicks E Giannis A Kikelj D 《Organic & biomolecular chemistry》2004,2(10):1511-1517
The proline peptide bond was shown by 2D proton NMR studies to exist exclusively in the trans conformation in benzyl (2S)-1-[[(2S)-2-methyl-6-nitro-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl]carbonyl]-2-pyrrolidinecarboxylate [(S,S)-11], benzyl (2S)-1-[[(2S)-2-methyl-7-nitro-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl]carbonyl]-2-pyrrolidinecarboxylate [(S,S)-9], and in the corresponding 6-amino and 7-amino carboxylic acids (S,S)-3 and (S,S)-4. On the other hand, the diastereomers (R,S)-11 and (R,S)-9 containing an (R)[2-methyl-6/7-nitro-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl]carbonyl moiety, and the diastereoisomers (R,S)-3 and (R,S)-4 incorporating an (R)[6/7-amino-2-methyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl]carbonyl moiety were found to exist as equilibria of trans(63-83%) and cis(17-37%) isomers. These conformationally defined templates were applied in the construction of RGD mimetics possessing antagonistic activity at the platelet fibrinogen receptor. 相似文献
9.
Danijel Krizmanić 《Lithuanian Mathematical Journal》2018,58(4):457-479
For linear processes with independent identically distributed innovations that are regularly varying with tail index α ∈ (0, 2), we study the functional convergence of the joint partial-sum and partial-maxima processes. We derive a functional limit theorem under certain assumptions on the coefficients of the linear processes, which enable the functional convergence in the space of ?2-valued càdlàg functions on [0, 1] with the Skorokhod weak M2 topology.We also obtain a joint convergence in the M2 topology on the first coordinate and in theM1 topology on the second coordinate. 相似文献
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