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1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis
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Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
2.
Addition of functionalized zinc-copper reagents to the title complexes proceeds in a highly diastereoselective fashion to afford dienol complexes. The relative configurations of adducts 3d were determined by single X-ray diffraction analysis. 相似文献
3.
4.
The reactions of 2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-trione with dimethyl sulfate, benzyl chloride, and allyl bromide afforded the corresponding 2-alkyl-2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-triones and 3-(alkoxy)-6,11-dihydroanthra[2,1-d]isothiazole-6,11-diones. The reactions of 2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-trione and its S-oxide with a formaldehyde—secondary amine system yielded 2-[(alkylamino)methyl]-2,3,6,11-tetrahydroanthra[2,1-d]isothiazole-3,6,11-triones and 2-[(alkylamino)methyl]-3,6,11-trioxo-2,3,6,11-tetrahydroanthra[2,1-d]isothiazole 1-oxides, respectively. 相似文献
5.
Hyun Joo Rhee 《Tetrahedron letters》2004,45(43):8019-8022
Stereoselective synthesis of (+)-lauthisan has been accomplished starting from d-glyceraldehyde acetonide by combination of diastereoselective alkylation and ring-closing metathesis. High degree of 1,3-asymmetric induction has been realized in ether system. 相似文献
6.
Mingbao Zhang Raymond Reeves Cheng Bi Robert Dally Gaetan Ladouceur William Bullock Jefferson Chin 《Tetrahedron letters》2004,45(27):5229-5231
Three novel, optically active, 6-substituted 2-(aminomethyl)chromans were synthesized from readily available chroman 2-carboxylic acid precursors. These chroman-containing primary amines are useful building blocks for the synthesis of chroman-derived pharmaceutical agents. 相似文献
7.
Dong‐Cheol Shin Yun‐Hi Kim Hong You Jae Gyu Jin Soon‐Ki Kwon 《Journal of polymer science. Part A, Polymer chemistry》2004,42(22):5636-5646
A poly(p‐phenylenevinylene) (PPV) derivative containing a bulky (2,2‐diphenylvinyl)phenyl group in the side chain, EHDVP‐PPV, was synthesized by Gilch route. The reduced tolane‐bisbenzyl (TBB) defects, as well as the structure of the polymer, was confirmed by various spectroscopic methods. The intramolecular energy transfer from the (2,2‐diphenylvinyl)phenyl side group to the PPV backbone was studied by UV‐vis and photoluminescence (PL) of the obtained polymer and model compound. The polymer film showed maximum absorption and emission peaks at 454 and 546 nm, respectively, and high PL efficiency of 57%. A yellow electroluminescence (λmax = 548 nm) was obtained with intensities of 6479 cd/m2 when the light‐emitting diodes of ITO/PEDOT/EHDVP‐PPV/LiF/Al were fabricated. The maximum power efficiency of the devices was 0.729 lm/W with a turn‐on voltage of 3.6 V. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5636–5646, 2004 相似文献
8.
The First Intramolecular Charge Transfer Transition Based on 2-Ureido-4[1H]-pyrimidinone Binding Module 总被引:1,自引:0,他引:1
The first intramolecular charge transfer transition based on 2-ureido-4[1H]-pyrimidinone binding module was reported. 相似文献
9.
It has been shown that the kinetics of intramolecular processes and time-resolved spectra with allowance for the quantum beats of the resonant states of isomers or isolated subsystems of levels of one isomeric form can be described with the use of a molecular model interpreting the effect of beats as a nonradiative transition. We have obtained an expression for the nonradiative transition probability, which is directly proportional to the beat frequency and depends oscillatorily on time, thus modeling the effect of beats. The parameter of the molecular system model is the beat frequency directly related to the parameter characterizing the intramolecular interisomeric interactions (the corresponding nondiagonal element of the energy matrix) rather than the value of the nonradiative transition probability. The character of the change in the level populations and, accordingly, in the band intensities in the spectra in the proposed model is in good agreement with the experiment, including the fine structure of the time dependences — oscillations of the line intensities. In analyzing the temporal experiment with a high resolution, it is necessary to take into account the instrument function leading to quantitative and qualitative changes in the time dependences. The traditional model of nonradiative transitions with a constant probability value has a very limited range of applicability — very high beat frequencies compared to the probability of optical transitions. 相似文献
10.
V. A. Petrosyan 《Russian Chemical Bulletin》1995,44(8):1353-1364
The results of studies on electrosynthesis involving carb- and heteroanions generated by cathodic deprotonation of acids (CDA), carried out in the laboratory headed by the author, are surveyed. These studies resulted in the elaboration of efficient electrochemical versions of the known Michaelis-Becker, Wittig-Horner, and Perkin reactions; electrochemical analogs of homolytic aromatic substitution, alkylation, heterocyclization,etc. were developed. Based on CDA, convenient and promising methods for preparing variousN-, O-, P-, S-, andC-alkylated and arylated substances have been developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1411–1422, August, 1995.The author is grateful to Professor V. A. Dorokhov, Professor V. P. Litvinov, and researchers from the laboratories of N. D. Zelinsky Institute of Organic Chemistry headed by them, who participated in joint studies.The work was carried out with financial support from the International Science Foundation (Grant No. MHYOO). 相似文献