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1.
Roberto Fernández de la Pradilla 《Tetrahedron》2006,62(11):2684-2692
(E,E) and (Z,E) γ-alkoxy dienyl sulfones undergo nucleophilic epoxidation with remarkable regio- and stereoselectivity to render syn oxiranes in a process mainly controlled by the alkoxy stereocenter. Upon epoxidation γ-hydroxy dienyl sulfoxides provide sulfinyl and sulfonyl oxiranes along with bis-epoxides formed through a Payne rearrangement that can be prevented by silylation of the OH group. Interestingly, the presence of a γ-silyloxy group can invert the stereochemical trend of the molecule affording mainly an anti epoxidation process. 相似文献
2.
Alexandre D.C. Dixon Robert J. Wilson Daniel D. Nguyen Daniel A. Clark 《Tetrahedron letters》2017,58(43):4054-4056
The development of methods for the stereoselective synthesis of polysubstituted 1,3-dienes is a challenge to synthetic chemistry. Herein is reported a selective approach for the synthesis of polysubstituted 1,3-dienes using the ruthenium hydride catalyzed intramolecular silylvinylation of alkynes under 80 psi of ethylene gas. This strategy affords a single diene isomer, is applicable to substrates with aryl and alkyl substitution at the propargyl and homopropargyl positions, and has been utilized in the synthesis of 5- and 6-membered oxasilacycles. 相似文献
3.
Asymmetric hetero‐Diels‐Alder (AHDA) reactions provide a multitude of opportunities for the highly efficient, regio‐ and stereoselective construction of various heterocycles in enantiomerically pure form. The asymmetric aza‐Diels‐Alder (A‐aza‐DA) reaction using diversely hetero‐dienophiles and hetero‐dienes have been increasingly developed as a valuable method for the synthesis of functionalized nitrogen ring systems. The purpose of this review is to give a detailed discussion of the A‐aza‐DA reaction particularly, the stereoselective reactions of imines as dienophiles with Dainshefsky dienes to obtain optically pure aza‐Diels‐Alder products. The development of stereoselective variants of the reaction make use of imines as the dienophile and Dainshefsky dienes is at the forefront of these studies. This review updates the A‐aza‐DA reactions covering the literature from 1972 till date 相似文献
4.
The reaction of biradical [P(μ-NTer)]2 ( 1 , Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl) towards different alkenes (R = 2,3-dimethyl–butadiene, 2,5-dimethyl-2,4-hexadiene, 1,7-octadiene, 1,4-cyclohexadiene) and alkynes (R = 1,4-diphenyl-1,3-butadiyne) was studied experimentally. Although these olefins can react in different ways, only [2+2] cycloaddition products ( 1R ) were observed. The reaction with 2,3-dimethylbutadiene also led to the [2+2] product ( 1dmb ). Thermal treatment of 1dmb above 140 °C resulted in the recovery of biradical 1 upon homolytic bond cleavage of the two P–C bonds and the release of 2,3-dimethylbutadiene. In contrast to this reaction, all other [2+2] additions products ( 1R , R = 1,7-octadiene, 1,4-cyclohexadiene, 1,4-diphenyl-1,3-butadiyne) began to decompose at temperatures between 200 °C and 300 °C. Only unidentified products were obtained but no temperature-controlled equilibrium reactions were observed. Computations were carried out to shed light into the formal [2+2] as well as the possible [4+2] addition reaction. 相似文献
5.
María Durán-Galván 《Tetrahedron》2010,66(39):7707-7908
The synthesis of chiral, nonracemic butadienylcarbinols by employing intermediate (trimethylsilyl)methylallenic alcohols is described. Allenic alcohols are obtained by treatment of aldehydes with (4-bromobut-2-ynyl)trimethylsilane in the presence of a catalytic amount of CrCl3 or CrCl2. Several new tridentate bis(oxazolinyl)carbazole ligands were synthesized and evaluated as the source of chirality. The synthesis of chiral allenic alcohols can be achieved in good yields (58-88%) and enantioselectivities (55-78% ee). Allenic alcohols may be treated with TBAF or 2 M HCl to provide the desired dienes in 43-86% yields. Alternatively, the (trimethylsilyl)methyl allenic alcohols afford iodobutadienyl carbinols when treated with N-iodosuccinimide. 相似文献
6.
The palladium-catalyzed coupling of C-5 iodopyrimidine nucleosides; 1,2-, 1,3-, or 1,ω-dienes; and amines provides a novel and efficient method for the preparation of a wide variety of C-5 aminoalkyl-substituted nucleosides. Adding certain Lewis acids, particularly zinc salts, improves the yields significantly. Secondary amines are the most effective amines for this process. Acyclic and cyclic dienes have been successfully employed. Protection of the 3′- and 5′-hydroxyl groups of iodouridine is required in order to obtain good yields when the coupling process is carried out on 1,3-dienes or long chain or branched non-conjugated dienes. 相似文献
7.
Nucleophilic Addition Reactions of Tricarbonyl [η5−1-(Phenylsulfonyl)cyclohexadienyl]iron(I) Complex
Hydride abstraction of tricarbonyl[η4-1-(phenylsulfonyl)-1,3-cyclohexadiene]iron(0) complex 2 with Ph3C+PF6? regiospecifically provided the title compound 3 in excellent yield. Cationic complex 3 could react with a variety of nucleophiles in good yields. Soft nucleophiles prefer to attack at the C-5 position, whereas hard nucleophiles such as methyllithium and the enolate of ethyl acetate gave the C-5 as well as the C-2 addition products. Some synthetic applications of the addition products were also studied. 相似文献
8.
W. James Feast Miquel Gimeno Alan M. Kenwright 《Journal of fluorine chemistry》2006,127(12):1533-1539
The syntheses and characterisations of 1,1-difluoro-2-heptyl-2-vinylcyclopropane and some of its isomers are described together with attempts to effect free radical ring opening polymerisation. We have recently shown that the parent monomer, 1,1-difluoro-2-vinylcyclopropane, undergoes predominantly 1,4-addition ring opening in contrast to the more usual 1,5-ring opening of other substituted vinylcyclopropanes and we find that the same anomalous behaviour occurs in this work confirming the influence of fluorine on the course of cyclopropane ring opening proposed by Dolbier. The presence of an alkyl chain modifies the ratios of 1,4- to 1,5-ring opening compared to that found in the unsubstituted parent monomer. In addition an the unexpected behaviour of different alkyl substituted buta-1,3-dienes towards difluorocarbene addition is described. 相似文献
9.
Sulfur-substituted azido dienes 1 and 11 , conveniently prepared from the corresponding 3-sulfolenes 5 and 10 , were thermolyzed to give pyrrolizidine and indolizidine products, 6 , 7 and 14 . 相似文献
10.
Cemil İbiş F. Serpil Göksel Gökşin Aydınlı 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):777-783
Reaction of 2-nitropentachlorobutadiene with thiols and amines gave new N,S- and S,S-substituted nitrodiene compounds is discussed. 相似文献