全文获取类型
收费全文 | 840篇 |
免费 | 71篇 |
国内免费 | 48篇 |
专业分类
化学 | 932篇 |
力学 | 1篇 |
综合类 | 1篇 |
物理学 | 25篇 |
出版年
2023年 | 5篇 |
2022年 | 13篇 |
2021年 | 14篇 |
2020年 | 28篇 |
2019年 | 18篇 |
2018年 | 26篇 |
2017年 | 18篇 |
2016年 | 33篇 |
2015年 | 34篇 |
2014年 | 41篇 |
2013年 | 84篇 |
2012年 | 30篇 |
2011年 | 51篇 |
2010年 | 43篇 |
2009年 | 40篇 |
2008年 | 51篇 |
2007年 | 37篇 |
2006年 | 52篇 |
2005年 | 62篇 |
2004年 | 70篇 |
2003年 | 43篇 |
2002年 | 21篇 |
2001年 | 12篇 |
2000年 | 14篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 15篇 |
1996年 | 12篇 |
1995年 | 12篇 |
1994年 | 4篇 |
1993年 | 5篇 |
1992年 | 12篇 |
1991年 | 4篇 |
1990年 | 8篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 5篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有959条查询结果,搜索用时 15 毫秒
31.
32.
The Ni-catalyzed cross-coupling of 2-bromo-3,3,3-trifluoropropene and aryl Grignard reagents was investigated. When NiCl2(PPh3)2 was used as a catalyst, the highest yield of α-trifluoromethylstyrene (89%) from 2-bromo-3,3,3-trifluoropropene and PhMgBr was obtained in 1,3-dimethyl-2-imidazolidinone at 50 °C for 30 min. Various α-trifluoromethylstyrene derivatives could be produced in satisfactory yields by NiCl2(PPh3)2-catalyzed coupling using aryl Grignard reagents. 相似文献
33.
The γ-selective allylation of catalytic and stoichiometric alkylzinc-cuprates have been kinetically studied. The reactivity profiles generated by allylation reactions of n-butylzinc chloride catalyzed by CuX compounds (X = I, Br, Cl, CN, SCN) and also catalyzed by n-butylzinc-copper reagents and di n-butylzinc-copper reagents were evaluated. Reactivity profiles for allylation of stoichiometric n-butylzinc-copper reagents and di n-butylzinc-copper reagents were also prepared. All CuX compounds have been screened for the preparation of Grignard reagent derived n-butylzinc-copper reagents and di n-butylzinc-copper reagents.The evaluation of the profiles indicates that the active catalyst might be RCu(X)ZnCl and also to some degree, R2CuZnCl · ZnClX, which both could favor formation of γ-product. All data supports the reductive elimination of σ-allyl Cu (III) complex formed at vinylic terminal to give γ-allylated product with a quite slow isomerization to σ-allyl Cu (III) complex formed at allylic terminal to give α-allylated product. In the allylation mechanism of zinc cuprates, the role of counter ion, ZnCl+ has been discussed. 相似文献
34.
Bayó-Puxan N Fernández A Tulla-Puche J Riego E Cuevas C Alvarez M Albericio F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(35):9001-9009
Thiocoraline is a potent antitumor agent isolated from the marine organism Micromonospora sp. This symmetric bicyclic depsipeptide binds the minor groove of DNA. Here we report two solid-phase strategies for the syntheses of azathiocoraline and its analogues. The thioester linkage was replaced by an amide bond to improve the compound's pharmacokinetic properties. The first strategy is based on a convergent (4+4) approach, whilst the second is a stepwise synthesis, cyclizations in both approaches occurring on the solid support. These two strategies were designed to overcome problems caused by the presence of consecutive noncommercial N-methyl amino acids, to avoid epimerization during cyclization and/or fragment condensation, and to form the disulfide bridge under solid-phase conditions. The heterocyclic moiety was added in the last step of the synthesis to assist the preparation of libraries of new compounds with potential therapeutic applications. 相似文献
35.
The ortho-diphenylphosphanylbenzoyl (o-DPPB) group was explored as a directing leaving group in copper-mediated and copper-catalyzed allylic substitution with Grignard reagents. Complete control of chemo-, regio- and stereoselectivity with complete syn-1,3-chirality transfer was observed as a result of the directed nature of the reaction. No excess of organometallic reagent is required and the directing group can be recovered quantitatively. Coordination studies in the solid state and in solution have shown that two substrates are bound via the phosphine function of the directing group at copper. Dynamic NMR experiments in solution are in agreement with a ligand-exchange process at copper, a prerequisite for the development of a substoichiometric process. 相似文献
36.
37.
Thressa C. Stadtman 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):199-216
Abstract Some enzymes known to contain selenium are enumerated. In four of them which catalyze coupled oxidation-reduction reactions the selenium occurs exclusively in the form of selenocysteine residues. Their structure and function are described in detail. Two other bacterial enzymes which contain selenium in the form of a labile, readily dissociable component are also described. Results on the isolation, identification and structure determination of selenium-containing amino acid transfer ribonucleic acids are presented. These seleno-t RNA's are shown to contain either 5-methyl-aminomethyl-2-selenouridine or other 2-selenouridine derivatives. The role of selenium in a glutamate iso-accepter species is discussed. 相似文献
38.
Mathilde Pantin Florent Bodinier Jordan Saillour Yassine M. Youssouf Fabien Boeda Morwenna S.M. Pearson-Long Philippe Bertus 《Tetrahedron》2019,75(33):4657-4662
A convenient access to 2-hydroxycyclopentenones was designed from acylcyanohydrins, by using titanacyclopropane complexes as nucleophilic partners and an intramolecular aldol condensation in basic conditions. The development of a one-pot procedure allows a step- and atom-economic process, and the use of Grignard reagents other than ethylmagnesium bromide provided valuable 3,4-disubstituted 2-hydroxycyclopentenones. The utility of the hydroxy group was illustrated by further functionalization of the α-position using palladium-mediated cross-coupling reactions. 相似文献
39.
A general and efficient synthetic method of 1,3-bis(phenylseleno)-2-propanol by reducing diphenyl diselenides with sodium borohydride in basic environment and then reacting with epichlorohydrin are described. 相似文献
40.
Reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with LiR reagents containing functional groups readily yields meso substituted derivatives suitable for further transformations with residues such as -p-C6H5Br, -p-C6H5-CCH, -p-C6H5-NH2 or -(CH2)3-CHCH2. Similar reactions of tetrabenzoporphyrin with alkyllithium reagents afforded the first entry into meso mono- and dialkylsubstituted tetrabenzoporphyrins while reaction of bicyclo[2.2.2]oct-type masked isoindole precursors with LiR followed by in situ retro-Diels-Alder reaction also afforded the 5-phenyl and 5,10-diphenyltetrabenzoporphyrins in high purity. 相似文献