全文获取类型
收费全文 | 4996篇 |
免费 | 1019篇 |
国内免费 | 728篇 |
专业分类
化学 | 6070篇 |
晶体学 | 11篇 |
力学 | 86篇 |
综合类 | 10篇 |
数学 | 167篇 |
物理学 | 399篇 |
出版年
2024年 | 5篇 |
2023年 | 56篇 |
2022年 | 103篇 |
2021年 | 135篇 |
2020年 | 276篇 |
2019年 | 127篇 |
2018年 | 196篇 |
2017年 | 131篇 |
2016年 | 279篇 |
2015年 | 366篇 |
2014年 | 355篇 |
2013年 | 467篇 |
2012年 | 404篇 |
2011年 | 391篇 |
2010年 | 358篇 |
2009年 | 370篇 |
2008年 | 428篇 |
2007年 | 354篇 |
2006年 | 336篇 |
2005年 | 302篇 |
2004年 | 273篇 |
2003年 | 358篇 |
2002年 | 88篇 |
2001年 | 89篇 |
2000年 | 80篇 |
1999年 | 55篇 |
1998年 | 40篇 |
1997年 | 73篇 |
1996年 | 71篇 |
1995年 | 61篇 |
1994年 | 24篇 |
1993年 | 18篇 |
1992年 | 24篇 |
1991年 | 9篇 |
1990年 | 11篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
排序方式: 共有6743条查询结果,搜索用时 15 毫秒
101.
Gibson SE Kaufmann KA Loch JA Steed JW White AJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2566-2576
Understanding the interaction of chiral ligands, alkynes, and alkenes with cobaltcarbonyl sources is critical to learning more about the mechanism of the catalytic, asymmetric Pauson-Khand reaction. We have successfully characterized complexes of the type [Co2(alkyne)(binap)(CO)4] (BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine)) and shown that diastereomer interconversion occurs under Pauson-Khand reaction conditions when alkyne=HC[triple bond]CCO2Me. Attempts to isolate [Co2(alkyne)(binap)(CO)x] complexes with coordinated alkenes led to the formation of cobaltacyclopentadiene species. 相似文献
102.
103.
104.
3位含有季碳手性中心的吲哚啉并环化合物是一类非常重要的化合物, 广泛存在于各种天然产物和具有生物活性的分子中. 化学家们发展了多种有效的途径来合成这类化合物. 其中以方便易得的吲哚衍生物为起始原料, 利用不对称去芳构化\环化串联的方法最为简单高效, 但多数工作都是从色胺或色醇衍生物出发, 合成二氢吡咯并吲哚啉或二氢呋喃并吲哚啉化合物. 因此, 发展其他类型的吲哚衍生物的不对称去芳构化\环化反应显得非常有必要. 作者课题组发展了手性磷酸催化的吲哚衍生物与甲基乙烯基酮的不对称Michael加成\环化串联反应. 以5 mol% (R)-SPINOL为骨架的手性磷酸(R)-4c为催化剂, 以中等到良好的收率和优秀的对映选择性构建了一系列手性吲哚[2,3-b]并氢化喹啉化合物, 而且该催化体系对于克级规模反应同样能够获得很好的结果. 相似文献
105.
螯合辅助溶剂挥发共组装法制备的炭-氧化铝复合材料为载体,分别使用水、乙醇或二者混合物为氯铂酸的分散介质,浸渍制备炭-氧化铝复合材料负载Pt催化剂.通过XRD,N2物理吸附以及TEM表征可知,乙醇作为浸渍溶剂时,最有利于Pt的分散,而混合溶剂浸渍制备的催化剂Pt颗粒最大.2-氧-4-苯基丁酸乙酯不对称加氢反应结果表明,氯铂酸水溶液浸渍得到的催化剂Pt纳米粒子的粒径有利于获得高的光学选择性,催化剂经辛可尼丁修饰后,以乙酸为反应溶剂,可获得最高84.8%的光学选择性.此外,该催化剂重复利用性能优异,可以重复利用22次,活性没有下降. 相似文献
106.
《化学:亚洲杂志》2017,12(12):1309-1313
An asymmetric route to (−)‐α‐lycorane and (−)‐zephyranthine, and a formal total synthesis of (+)‐clivonine were achieved. A pivotal intermediate, which serves as a potent precursor for the divergent syntheses of these natural products, was accessed by a diastereoselective Pd‐catalyzed cinnamylation of an N ‐tert ‐butanesulfinyl imine. 相似文献
107.
《化学:亚洲杂志》2017,12(16):2127-2133
In this work, β‐Co(OH)2 nanosheets are explored as efficient pseudocapacitive materials for the fabrication of 1.6 V class high‐energy supercapacitors in asymmetric fashion. The as‐synthesized β‐Co(OH)2 nanosheets displayed an excellent electrochemical performance owing to their unique structure, morphology, and reversible reaction kinetics (fast faradic reaction) in both the three‐electrode and asymmetric configuration (with activated carbon, AC). For example, in the three‐electrode set‐up, β‐Co(OH)2 exhibits a high specific capacitance of ∼675 F g−1 at a scan rate of 1 mV s−1. In the asymmetric supercapacitor, the β‐Co(OH)2∥AC cell delivers a maximum energy density of 37.3 Wh kg−1 at a power density of 800 W kg−1. Even at harsh conditions (8 kW kg−1), an energy density of 15.64 Wh kg−1 is registered for the β‐Co(OH)2∥AC assembly. Such an impressive performance of β‐Co(OH)2 nanosheets in the asymmetric configuration reveals the emergence of pseudocapacitive electrodes towards the fabrication of high‐energy electrochemical charge storage systems. 相似文献
108.
Control of N‐Heterocyclic Carbene Catalyzed Reactions of Enals: Asymmetric Synthesis of Oxindole‐γ‐Amino Acid Derivatives 下载免费PDF全文
Dr. Xiang‐Yu Chen Jia‐Wen Xiong Qiang Liu Sun Li He Sheng Dr. Carolina von Essen Prof. Dr. Kari Rissanen Prof. Dr. Dieter Enders 《Angewandte Chemie (International ed. in English)》2018,57(1):300-304
A strategy to control the switch between a non‐cycloaddition reaction and a cycloaddition reaction of enals, using N‐heterocyclic carbene (NHC) catalyisis, has been developed. The new scalable protocol leads to γ‐amino‐acid esters bearing a tetrasubstituted stereocenter in good yields and high stereoselectivities by homo‐Mannich reactions of enals and isatin‐derived ketimines. By simply changing the N‐ketimine substituent to an ortho‐hydroxy phenyl group, the corresponding spirocyclic oxindolo‐γ‐lactams are obtained. 相似文献
109.
N‐Heterocyclic Carbene Catalysis via Azolium Dienolates: An Efficient Strategy for Remote Enantioselective Functionalizations 下载免费PDF全文
Dr. Xiang‐Yu Chen Qiang Liu Dr. Pankaj Chauhan Prof. Dr. Dieter Enders 《Angewandte Chemie (International ed. in English)》2018,57(15):3862-3873
N‐heterocyclic carbene (NHC) catalysis has emerged as a powerful strategy in organic synthesis. In recent years a number of reviews have been published on NHC‐catalyzed transformations involving Breslow intermediates, acyl azoliums, α,β‐unsaturated acyl azoliums, homoenolate equivalents, and azolium enolates. However, the azolium dienolate intermediates generated by NHCs have been employed in asymmetric synthesis only very recently, especially in cycloadditions dealing with remote functionalization. This Minireview highlights all the developments and the new advances in NHC‐catalyzed asymmetric cycloaddition reactions involving azolium dienolate intermediates. 相似文献
110.
Catalytic Asymmetric Oxidative γ‐Coupling of α,β‐Unsaturated Aldehydes with Air as the Terminal Oxidant 下载免费PDF全文
Line Næsborg Vasco Corti Lars Astrup Leth Dr. Pernille H. Poulsen Prof. Karl Anker Jørgensen 《Angewandte Chemie (International ed. in English)》2018,57(6):1606-1610
A novel concept for catalytic asymmetric coupling reactions is presented. Merging organocatalysis with single‐electron oxidation by using a catalytic amount of a copper(II) salt and air as the terminal oxidant, we have developed a highly stereoselective carbon–carbon oxidative coupling reaction of α,β‐unsaturated aldehydes. The concept relies on the generation of a dienamine intermediate, which is oxidized to an open‐shell activated species that undergoes highly selective γ‐homo‐ and γ‐heterocoupling reactions. In the majority of examples presented, only a single stereoisomer was formed. 相似文献