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Andrea Ricci 《Tetrahedron》2004,60(1):115-120
The photochemistry of five 11-hydroxy-1,5-cyclopregn-3-en-2-ones (‘lumi’ products from the corresponding pregna-1,4-dien-3-ones) has been investigated. In all cases the photoproducts were 1,11-oxy derivatives, resulting from intramolecular attack of the hydroxyl group to the incipient positive charge at C-1. When a fluorine atom was present at C-6, HF elimination took place concurrently with the nucleophilic addition and led to linearly conjugated dienones, rather than the enones obtained in the other cases. Quantum yields were in the range 0.06-0.2, the lower values applying when a fluorine atom was present in position 6 (not in position 9). The results add new evidence on the role of zwitterionic intermediates in the photochemistry of cross-conjugated dienones and the corresponding lumi photoproducts. 相似文献
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Ayhan S. Demir Ömer Reis Ilker Esiringü Barbaros Reis Sehriban Baris 《Tetrahedron》2007,63(1):160-165
Acylphosphonates, which are easily available from carboxylic acids, are potent acyl anion precursors and undergo cyanide ion promoted phosphonate-phosphate rearrangement to provide the corresponding acyl anion equivalents as reactive intermediates. The protonation of these acyl anion equivalents furnished cyanohydrin O-phosphates in good yields. For the high yield formation of cyanohydrin O-phosphates from arylphosphonates THF should be used and from alkylphosphonates DME was used. 相似文献
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Thermal electrocyclization reactions of benzooctatetraenes and benzodecapentaenes substituted with R=H, Cl, and methyl were studied experimentally and computationally. Methyl and unsubstituted benzooctatetraenes and benzodecapentaenes give the [4.2.0]bicyclooctadiene products by 8π,6π-electrocyclization. Chlorine substitution led to thermal rearrangement of the initially formed 8π,6π-electrocyclization intermediates to give unprecedented products. 相似文献
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Behrouz Emamizadeh Mariam Al Hanai 《Numerical Functional Analysis & Optimization》2013,34(5-6):478-485
In this note we consider an investment problem in real estate. We show that it can be formulated in terms of a constrained optimization problem, and this leads to a linear rearrangement optimization problem. We address existence, uniqueness, and symmetry of the optimal solution. 相似文献
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Tzon Tzer LuSui Sun Cheng 《Applied Mathematics Letters》1995,8(6):95-98
A necessary condition is derived for a quadratic form ptGp to be minimal among all permutations of the nonnegative nontrivial vector p. The quadratic form arises from the stability problem of a fixed-fixed taut string loaded with masses at equidistant points. 相似文献
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《Comptes Rendus Chimie》2017,20(6):648-664
Ynamides have recently evolved as remarkably reactive and versatile building blocks for chemical synthesis. The development of efficient and robust methods for their preparation combined with their recent commercialization have facilitated both the design of an ever-growing number of original methods based on their unique reactivity and their use in other areas such as medicinal chemistry. One crucial aspect of the reactivity of these building blocks is based on their anionic chemistry, which has been extensively studied during the last decade and enabled not only the design and development of remarkably efficient and original reactions but also brought general answers to long-standing problems in organic chemistry and contributed to the emergence of new synthetic paradigms. In this short review, the anionic chemistry of ynamides is overviewed. 相似文献
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Jin Cao Yu-Xuan Su Xin-Yu Zhang Shou-Fei Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202212976
Herein we report the first method for highly enantioselective Brønsted acid catalyzed Heyns rearrangements. These reactions, catalyzed by a chiral spiro phosphoric acid, afforded synthetically valuable chiral α-aryl-α-aminoketones which cannot be obtained by means of previously reported Heyns rearrangement methods. This method features low catalyst loadings, high yields and high enantioselectivities, making these reactions highly practical. We used the method to efficiently synthesize various chiral amines, including some biologically active molecules. We experimentally proved that these acid-catalyzed Heyns rearrangements proceeded via a proton-transfer process involving an enol intermediate and the stereocontrol was realized during the proton-transfer step. 相似文献
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1-Bromo-1-fluoro-[1a,2,7,7a]-tetrahydro-1H-cyclopropa[b]naphthalene (19) has been prepared by the addition of bromofluorocarbene to 1,4-dihydronaphthalene (18). Treatment of a solution of 19 in dry ether with MeLi afforded the tricyclic hydrocarbon 17, resulting from the intramolecular C-H insertion of carbene 16, and two dimerization products, the head-to-head 20 and head-to-tail 21 allene dimers, confirming the formation of title cycloallene 15 as a reactive intermediate. B3LYP/6-31G(d) calculation predicts the activation barriers for insertion product 17 and allene product 15 as 3.70 and 9.52 kcal/mol, respectively. This prediction was in good agreement with our experimental results. 相似文献
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The acid catalyzed rearrangement of two cyclohexanols of spiroannelated four-membered rings has been studied. In accordance with molecular mechanics calculations, far-reaching reorganizations with formation of unsaturated hexacyclic systems, including a fully cycloalkylated cyclohexene with a bispropellane partial structure, were observed. Attempts to convert this bispropellane to a trispropellane failed. 相似文献