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1.
《Tetrahedron letters》2019,60(24):1582-1586
Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred. 相似文献
2.
A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated. 相似文献
3.
Atsuo Nakazaki 《Tetrahedron》2006,62(26):6264-6271
The stereoselective total syntheses of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone were accomplished based on a Claisen rearrangement in an alkenyl bicyclic dihydropyran system. The most striking feature of this approach is that the Claisen rearrangement of bicyclic dihydropyran proceeds stereoselectively to provide a multi-functionalized spiro[4.5]decane, which is an efficient precursor for the synthesis of the vetivane sesquiterpenes. 相似文献
4.
The first enantiospecific synthesis of allopupukeanones has been accomplished starting from 6-methylcarvone. A biogenetically patterned rearrangement of a pupukeanane to allopupukeanane was employed as the key step. 相似文献
5.
P. R. Latthe P. S. Shinge Bharati V. Badami P. B. Patil S. N. Holihosur 《Journal of Chemical Sciences》2006,118(3):249-256
3-[4-(Azidocarbonyl)]phenylsydnone (2) obtained from 3-(4-hydrazinocarbonyl) phenylsydnone (1) on Curtius rearrangement with alcohols, water and amines afforded the corresponding carbamates (3a-h), 4,4′-(sydnone-3-yl) diphenyl urea (4) and 4-(heterocyclyl)phenyl ureas (5a-l). Compounds (5a-l) on one-pot ring conversion yielded the 1,3,4-oxadiazolin-2-one derivatives (6a-l), which on reaction with N2H4 gave the 4-amino-1,2,4-triazolin-3-ones (7a-l). All these compounds exhibited moderate antimicrobial activity against the few microbes tested. The carbamates have been
found to be more toxic against fourth instar larvae ofAedes aegypti, in particular, then-butyl derivative (3e). 相似文献
6.
The total synthesis of an alkylcitrate secondary metabolite from the fungi Trichoderma viride is described. An ester dienolate [2,3]-Wittig rearrangement and a S. Julia-Kocienski olefination served as key C/C-connecting transformations. The highly convergent synthesis consists of a longest linear sequence of 17 steps. 相似文献
7.
分子生物学中基因无方向的反向基因组重排问题在数学上已被证明是一个NP困难问题.基于断点图的概念,给出一个时间复杂性为O(max{b^(π),nb(π)}),空间复杂性为0(n)的求其近似最优解的算法.其中n为基因组中基因个数,π=(π1,π2,…,πn)表示n个基因的一种排列,b(π)表示排列π中的断点数.数据实验的结果表明,该近似算法可以求得较好的结果. 相似文献
8.
[3,3]-Sigmatropic rearrangements of allyl tetronates and allyl tetramates to give 3-allyltetronic or -tetramic acids, respectively, proceed within 20-60 min under microwave irradiation (300 W, 130-190 °C). Consecutive (homo)sigmatropic [1,5] H-shifts such as oxa-ene reactions are promoted less effectively, which allows the isolation of Claisen intermediates of sigmatropic domino sequences, in contrast to conventional heating. 相似文献
9.
Jérôme Le NôtreAna Acosta Martinez Pierre H DixneufChristian Bruneau 《Tetrahedron》2003,59(47):9425-9432
Enyne rearrangement of silylated modified terpenoids has been used as the key step for the synthesis of new terpenes and terpenoids. The catalytic system generated in situ from [RuCl2(p-cymene]2, 1,3-bis(mesityl)imidazolinium chloride and cesium carbonate is able to perform the transformation of silylated 1,7-enynes into cyclic siloxanes. Selective cleavage of the silicon-carbon and silicon-oxygen bonds by simple reactions has been performed to afford new terpenes and terpenoids by formal addition of a C5 unit. 相似文献
10.