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1.
Introducing Deep Eutectic Solvents to Polar Organometallic Chemistry: Chemoselective Addition of Organolithium and Grignard Reagents to Ketones in Air 下载免费PDF全文
Cristian Vidal Dr. Joaquín García‐Álvarez Dr. Alberto Hernán‐Gómez Dr. Alan R. Kennedy Prof. Eva Hevia 《Angewandte Chemie (International ed. in English)》2014,53(23):5969-5973
Despite their enormous synthetic relevance, the use of polar organolithium and Grignard reagents is greatly limited by their requirements of low temperatures in order to control their reactivity as well as the need of dry organic solvents and inert atmosphere protocols to avoid their fast decomposition. Breaking new ground on the applications of these commodity organometallics in synthesis under more environmentally friendly conditions, this work introduces deep eutetic solvents (DESs) as a green alternative media to carry out chemoselective additions of ketones in air at room temperature. Comparing their reactivities in DES with those observed in pure water suggest that a kinetic activation of the alkylating reagents is taking place, favoring nucleophilic addition over the competitive hydrolysis, which can be rationalized through formation of halide‐rich magnesiate or lithiate species. 相似文献
2.
V. D. Dyachenko 《Chemistry of Heterocyclic Compounds》2005,41(8):1005-1008
3-Ethoxycarbonyl-4,6-diphenyl-3,4-dihydropyridine-2(1H)-thione was synthesized by the interaction of benzylideneacetophenone
with cyanoacetic ester and hydrogen sulfide. Its structure was investigated by X-ray structural analysis.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1180–1183, August, 2005. 相似文献
3.
AbstractWe developed a facile one-pot procedure for the synthesis of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-thione under ultrasonic irradiation. The method is based on a three components reaction of aldehydes, ketones, and thiourea under basic conditions affording isolated yields of up to 95% within a reaction time of 30–90?min. 相似文献
4.
Abdullatif Azab Dorit Moradov Abed Al-Aziz Al-Quntar Morris Srebnik 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):937-943
Abstract Direct addition of organolithium to 1-alkynylphosphonates (1) afforded vinylphosphonates and enamine phosphonates (2) in good to excellent yields. The reaction was carried out in dry THF at low temperature and proved to be completely stereoselective (syn addition). Alkyl, aryl, and haloalkyl groups were attached to the alkynyl entity, so the resulting vinylphosphonates contained various functional groups. The stereochemistry of the products as well as mechanism of the reaction were determined based on 1H and 13C NMR. The synthesis of enamine phosphonates in the absence of complicated, highly expensive organometallic catalysis has not been previously reported. 相似文献
5.
IntroductionInrecentyears ,dihydropyrimidinethionederivativeshaveattractedconsiderableinterestduetotheirpromisingactivitiesasanticarcinogenicagents ,1cardiovasculara gents2 andcalciumchannelblockers .3Inaddition ,somederivativesofdihydropyrimidinethionewer… 相似文献
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3,4-Dihydro-5(1H)-pyrromethenones are easier attacked at themeso-position by electrophiles than 5(1H)-pyrromethenones. This is demonstrated both by aMannich-type-substitution or deuterium-exchange-experiments and by the addition of O-, S-, and N-Nucleophiles to the exocyclic double bond of the model-dihydropyrromethenone (Z)-1 under very mild reaction conditions. Applying these results to the chemistry of 2,3-dihydro-bilatrienes-abc, their chemical characteristics—especially their tautomeric behavior and their dominant C-5-selectivity towards electrophiles—become better understandable. 相似文献
8.
Jayashree Nath 《合成通讯》2013,43(20):2976-2982
Borax in the presence of a very small amount of 5 M sulfuric acid efficiently catalyses the three-component condensation of an aldehyde, β-ketoester, and urea or thiourea to afford the corresponding 3,4-dihydropyrimidin-2(1H)-ones or 3,4-dihydropyrimidin-2(1H)-thiones in good to excellent yields under solvent-free conditions at 80 °C. Compared with the classical Biginelli reaction conditions, this new method has the advantage of excellent yield, short reaction time (1–2 h), easy workup, and no use of volatile organic solvent. 相似文献
9.
Hamid Reza Shaterian Asghar Hosseinian Majid Ghashang 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):126-134
An efficient, facile, simple, and green synthetic protocol for the Biginelli reaction has been developed for the preparation of 3,4-dihydropyrimidin-2(1H)-thione derivatives under thermal and microwave irradiation, solvent-free conditions, in the presence of aluminum hydrogen phosphate, Al(H2PO4)3, as an environmentally friendly heterogeneous recyclable catalyst, in high to excellent yields and short reaction time. In addition, the catalyst could be easily recovered from the reaction mixture by simple filtration and reused several times without any loss of activity. 相似文献
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《合成通讯》2013,43(22):3953-3960
Abstract The resin-bound bismethylthiomethylene cyclic malonic acid ester 3 was built up efficiently. Resin 3 can react with arylamines and subsequent thermal cyclizations give 2-alkylthio-4-(1H)-quinolones. Furthermore, conjugate addition of Grignard reagents to the resin 3 forms the resin 6 which was reacted with aryl amines and subsequent thermal-cyclization-cleavages afford the 2-alkyl-4-(1H)-quinolones. 相似文献
12.
Xianwei Sun Prof. Dr. Zhenlei Song Hongze Li Changzheng Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(51):17589-17594
A [1,4]‐S‐ to O‐silyl migration has been exploited to chemoselectively transform esters into ketones by using organolithium reagents, allowing multicomponent synthesis of α‐thioketones. Mechanistic studies reveal that this migration proceeds in an intramolecular manner and is more favorable than the corresponding [1,5]‐S‐ to O‐ and [1,3]‐C‐ to O‐silyl migrations. The resulting α‐thioketones are valuable building blocks for the synthesis of cyclic or multifunctionalized organosulfur compounds. 相似文献
13.
P. M. Kushakova Yu. V. Basan A. I. Yulisova V. V. Lifontova S. M. Ramsh A. V. Garabadgiu L. N. Belobrzeckaja Costa 《Chemistry of Heterocyclic Compounds》2006,42(8):1078-1085
Alkylation of 1-methyltetrahydropyrimidine-2(1H)-thione (N-methylpropylenethiourea) with chloro-and bromoacetic acids and
their esters have given the 8-methyl-3-oxo-2,3,6,7-tetrahydro-5H-[1,3]thiazolo[3,2-a]pyrimidin-8-ium chloride or bromide.
The former is readily hydrolyzed in 95% ethanol to 3-[(3-methylamino)propyl]-1,3-thiazolidine-2,4-dione hydrochloride while
the second is more stable towards hydrolysis such that the corresponding hydrobromide is not separated. A paradoxical trend
in the extent of the hydrolysis decreasing with the content of the water in the alcoholic solution comes to a complete stop
in water. A possible explanation of this phenomenon is given.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1242–1251, August, 2006. 相似文献
14.
Ren-Lin Zheng Xiu-Xiu Zeng Hai-Yun He Jun He Sheng-Yong Yang Luo-Ting Yu 《合成通讯》2013,43(10):1521-1531
An improved synthesis of 6-aryl-3-cyanopyridine-2-(1H)-thiones utilizing enaminones as starting materials catalyzed by 1,4-diazabicyclo[2.2.2]octane (DABCO) was described. Moreover, a convenient one-pot conversion of aryl ketones to 6-aryl-3-cyanopyridine-2-(1H)-thiones was also developed in moderate to good yields (up to 80%). 相似文献
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Formation of Contiguous Quaternary and Tertiary Stereocenters by Sequential Asymmetric Conjugate Addition of Grignard Reagents to 2‐Substituted Enones and Mg–Enolate Trapping 下载免费PDF全文
Dr. Nicolas Germain Prof. Dr. Alexandre Alexakis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(23):8597-8606
Herein a comprehensive study is provided on the asymmetric conjugate addition (ACA) of Grignard reagents to α‐substituted cyclic enones. After the elucidation of the optimal experimental conditions, the scope of Grignard reagents and Michael acceptors was examined. Whereas secondary Grignards gave better enantioselectivities with 2‐cyclopentenones, both linear and branched Grignard reagents were tolerated for the ACA to 2‐methylcyclohexenone. The sequential ACA–enolate trapping, which leads to quaternary stereocenters, was then studied. Thus, many electrophiles have been tested, thereby giving rise to highly functionalized cyclic ketones with contiguous α‐quaternary and β‐tertiary centers. The present technique is believed to bring a new approach to versatile terpenoid‐like skeletons of bioactive natural products. Straightforward derivatizations of enantioenriched saturated cyclic ketones further support the potential of the present methodology in synthesis. 相似文献
17.
Zhao Yang WANG Jia Ling CUI Bao Shan DU* Qing Hua CHEN Department of Chemistry Beijing Normal University Beijing Present address: Dept. of Chem. South China Nor. Univ Guangzhou Present address: School of Pharm. Beijing Univ 《中国化学快报》2001,(4)
Recently, much effort has been made in the development of generally applicable organic synthesis of 5-alkyloxy-2(5H)-furanones due to their essential structure entities in the synthesis of some biologically active natural products and their application as useful intermediates in organic synthesis1. Their reactions such as Michael addition, Diels-Alder reaction and photocatalyzed conjugate addition have been studied extensively2-4.However, Michael addition reaction of Grignard reagents to 5-m… 相似文献
18.
P. M. Kushakova A. I. Yulisova S. M. Ramsh A. V. Garabadgiu 《Chemistry of Heterocyclic Compounds》2006,42(4):520-529
In the absence of bases all the attempted variations for the alkylation of tetrahydropyrimidine-2(1H)-thione with á-halocarboxylic
acids gave only the bicyclic product-2-R-6,7-dihydro-5H-[1,3]thiazolo[3,2-a]pyrimidin-3(2H)-one hydrohalide. However the hydrohalide
of the “ open” S-ethoxycarbonyl derivative of propyleneisothiourea can be obtained by treatment of tetrahydropyrimidine-2(1H)-thione
with ethyl chloro-or bromoacetate in anhydrous acetone at room temperature. Alkylation of 5,5-dimethyltetrahydro-2(1H)-pyrimidinethione
with chloro-or bromoacetic acid in anhydrous acetone at room temperature gave the hydrohalide of the “open” S-carboxymethyl
derivative of dimethylpropyleneisothiourea. All remaining variations for the alkylation of this substrate with á-halocarboxylic
acids or their esters gave only the corresponding bicyclic compounds-the hydrohalide of 2-R-6,6-dimethyl-6,7-dihydro-5H-[1,3]thiazolo[3,2-a]pyrimidin-3(2H)-one-independently
of the reaction conditions.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 593–604, April, 2006. 相似文献
19.
利用三溴化铟催化的Biginelli反应原位合成3,4-二氢嘧啶-2-酮 总被引:18,自引:0,他引:18
一些二氢嘧啶酮衍生物具有重要的药物活性 ,可用作钙拮抗剂、降压剂和α1- 1 - a-拮抗剂 [1] .目前 ,从海洋生物中分离得到的一些具有生物活性的生物碱也具有二氢嘧啶酮的核 [2 ] .因此 ,近年来 ,这类化合物的合成已引起人们的极大兴趣 .文献 [3 ]采用乙酰乙酸乙酯、苯甲醛和脲在强酸性条件下进行原位缩合 ,得到二氢嘧啶酮的衍生物 ,但是该反应的产率不高 .三溴化铟作为一个温和的路易斯酸 [4 ,5] ,可以高效地催化此类反应 .在这一催化体系中 ,不仅 β-酮酸酯可以发生缩合反应 ,而且相对困难的 β-二酮也可以发生此类反应 ,使一些在传统 Bi… 相似文献
20.
Jacek G. So?nicki 《Tetrahedron》2007,63(48):11862-11877
Organolithium and lithium allyldibutylmagnesate reagents add to readily available NH, NMe, NBn, and NPh substituted pyridine-2-thiones yielding 4- and/or 6-substituted 3,4- or 3,6-dihydropyridine-2-thiones, respectively. The regioselectivity of the addition is dependent on the solvent, temperature, substituent at the nitrogen, and the type or organometallic reactant used, and allows tailoring of both systems. A simple conversion of 6-substituted β,γ-unsaturated δ-thiolactams into their α,β-unsaturated isomers makes the above processes a highly versatile synthetic methodology to access 6-substituted 5,6-dihydropyridine-2-thiones—valuable Michael acceptors. 相似文献