全文获取类型
收费全文 | 1305篇 |
免费 | 58篇 |
国内免费 | 4篇 |
专业分类
化学 | 1074篇 |
晶体学 | 1篇 |
力学 | 17篇 |
数学 | 136篇 |
物理学 | 139篇 |
出版年
2023年 | 10篇 |
2022年 | 9篇 |
2021年 | 17篇 |
2020年 | 34篇 |
2019年 | 27篇 |
2018年 | 10篇 |
2017年 | 9篇 |
2016年 | 64篇 |
2015年 | 45篇 |
2014年 | 58篇 |
2013年 | 70篇 |
2012年 | 112篇 |
2011年 | 99篇 |
2010年 | 64篇 |
2009年 | 50篇 |
2008年 | 95篇 |
2007年 | 74篇 |
2006年 | 89篇 |
2005年 | 67篇 |
2004年 | 84篇 |
2003年 | 61篇 |
2002年 | 48篇 |
2001年 | 30篇 |
2000年 | 15篇 |
1999年 | 15篇 |
1998年 | 13篇 |
1997年 | 13篇 |
1996年 | 20篇 |
1995年 | 15篇 |
1994年 | 19篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1965年 | 1篇 |
1963年 | 1篇 |
1960年 | 1篇 |
排序方式: 共有1367条查询结果,搜索用时 0 毫秒
61.
The potent antibiotic thiazolylpeptide GE2270 A was synthesized starting from N-tert-butyloxycarbonyl protected valine in a longest linear sequence of 20 steps and with an overall yield of 4.8 %. Key strategy was the assembly of the 2,3,6-trisubstituted pyridine core by consecutive cross-coupling reactions starting from 2,6-dibromo-3-iodopyridine. The complete Southern fragment was installed by Negishi cross-coupling of 3-zincated 2,6-dibromopyridine at the terminal 2-iodothiazole of a trithiazole (87 %). The substituent at C-6 representing the Northern part of the molecule was introduced in form of the truncated tert-butyl 2-bromothiazole-4-carboxylate after metalation to a zinc reagent by another Negishi cross-coupling (48 %). Decisive step of the whole sequence was the macrocyclization to a 29-membered macrolactam, which was conducted as an intramolecular Stille cross-coupling occurring at C-2 of the pyridine core and providing the desired product in 75 % yield. The required stannane was obtained by amide bond formation (87 %) between a complex dithiazole fragment representing the Eastern part of GE2270 A and a 3,6-disubstituted 2-bromopyridine. Final steps included attachment of a serine-proline amide dipeptide to the Northern part of the molecule (65 %), formation of the oxazoline ring and silyl ether deprotection (55 % overall). 相似文献
62.
63.
64.
65.
Polydentate ligands with benzene-o-dithiolato donor groups are useful building blocks in supramolecular coordination chemistry. The coordination chemistry of bis- and tris(benzene-o-dithiolato) ligands and mixed benzene-o-dithiolato/catecholato ligands is reviewed. These ligands exhibit a versatile coordination chemistry both in solution and in the solid state. 相似文献
66.
Schulze Isfort C Kreickmann T Pape T Fröhlich R Hahn FE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(8):2344-2357
The benzene-o-dithiol/catechol ligands H4-2 and H4-3 react with [TiO(acac)2] to give the dinuclear, double-stranded anionic complexes [Ti2(L)2(mu-OCH3)2](2-) ([22](2-), L=2(4-); [23](2-), L=3(4-)). NMR spectroscopic investigations reveal that the complex anion [Ti2(2)2(mu-OCH3)(2)](2-) is formed as a mixture of three of four possible isomers/pairs of enantiomers, whereas only one isomer of the complex anion [Ti2(3)2(mu-OCH3)(2)](2-) is obtained. The crystal structure analysis of (PNP)2[Ti2(3)2(mu-OCH3)2] shows a parallel orientation of the ligand strands, whereas the structure determination for (AsPh4)2[Ti2(2)2(mu-OCH3)2] does not yield conclusive results about the orientation of the ligand strands due the presence of different isomers in solution, the possible co-crystallisation of different isomers and severe disorder in the crystal. NMR spectroscopy shows that ligand H4-3 reacts at elevated temperature with [TiO(acac)2] to give the triple-stranded helicate (PNP)4[Ti2(3)3] ((PNP)4[24]) as a mixture of two isomers, one with a parallel orientation of the ligand strands and one with an antiparallel orientation. Exclusively the triple-stranded helicates [Ti2(L)(3)](4-) ([25](4-), L=1(4-); [26](2-), L=4(4-)) are formed in the reaction of ligands H4-1 and H4-4 with [TiO(acac)2]. The molecular structures of Na(PNP)3[Ti2(1)3]CH(3)OHH(2)OEt(2)O (Na(PNP)3[25]CH(3)OHH(2)OEt(2)O) and Na(1.5)(PNP)(6.5)[Ti2(4)3]2.3 DMF (Na(1.5)(PNP)(6.5)[26]2.3 DMF) reveal a parallel orientation of the ligand strands in both complexes, which is retained in solution. The sodium cations present in the crystal structures lead to two different kinds of aggregation in the solid state. Na-[25]-Na-[25]-Na polymeric chains are formed from compound Na(PNP)3[25], with the sodium cations coordinated by the carbonyl groups of two ligand strands from two different [Ti2(1)3](4-) ions in addition to solvent molecules. In contrast to this, two [Ti2(4)3](4-) ions are connected by a sodium cation that is coordinated by the three meta oxygen atoms of the catecholato groups of each complex tetraanion to form a central {NaO6} octahedron in the anionic pentanuclear complex {[26]-Na-[26]}(7-). 相似文献
67.
Nucleophilic substitutions on pentachloropyridine with 4-(dimethylamino)pyridine, 4-aminopyridine, and 4-(pyrrolidin-1-yl)pyridine give mono-, tri- and pentacationic pyridine-hetarenium salts. The mono-, tri- and pentacationic 4-aminopyridine derivatives can be deprotonated to neutral compounds in solution, or protonated to di-, hexa- and decacationic pyridine derivatives, respectively. Successive substitutions with different heteroaromatic nucleophiles give pyridines with two distinct types of heteroarenium substituents. 相似文献
68.
Berg T 《Angewandte Chemie (International ed. in English)》2004,43(29):3750-3751
69.
Gansäuer A Lauterbach T Geich-Gimbel D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):4983-4990
A catalyzed synthesis of cyclopropanes and cyclobutanes via radical chemistry is described. The method that generally proceeds in high yields uses epoxides as radical precursors and titanocene(III) complexes as the electron transfer catalysts (see scheme). The key to the success of the transformation is constituted by the chemoselectivity of radical reduction. Electrophilic enol radicals generated through cyclization are reduced rapidly whereas their precursors, nucleophilic alkyl radicals, remain unaffected. 相似文献
70.
Zöller T Iovkova-Berends L Berends T Dietz C Bradtmöller G Jurkschat K 《Inorganic chemistry》2011,50(17):8645-8653
The syntheses and molecular structures of the intramolecularly coordinated tin(II) compounds {CH(2)N(Me)CH(Me)CH(Ph)O}(2)SnL (2, L = lone pair; 4, L = W(CO)(5); 5, L = Cr(CO)(5)) and of the related hydroxido-substituted tin(IV) compound [{CH(2)N(Me)CH(Me)CH(Ph)O}(2)Sn(OH)](2)O, 6a, are reported. Also reported are the molecular structures of the enantiopure N,N'-ethylenebis-(1R,2S)-ephedrine, {CH(2)N(Me)CH(Me)CH(Ph)OH}(2) (1), and its hydrobromide {CH(2)N(Me)CH(Me)CH(Ph)OH}(2)·HBr (1a). 相似文献