全文获取类型
收费全文 | 12946篇 |
免费 | 2750篇 |
国内免费 | 1669篇 |
专业分类
化学 | 16696篇 |
晶体学 | 21篇 |
力学 | 129篇 |
综合类 | 41篇 |
数学 | 111篇 |
物理学 | 367篇 |
出版年
2024年 | 6篇 |
2023年 | 254篇 |
2022年 | 299篇 |
2021年 | 512篇 |
2020年 | 1042篇 |
2019年 | 721篇 |
2018年 | 714篇 |
2017年 | 502篇 |
2016年 | 867篇 |
2015年 | 947篇 |
2014年 | 1045篇 |
2013年 | 1266篇 |
2012年 | 923篇 |
2011年 | 978篇 |
2010年 | 770篇 |
2009年 | 808篇 |
2008年 | 857篇 |
2007年 | 697篇 |
2006年 | 701篇 |
2005年 | 641篇 |
2004年 | 642篇 |
2003年 | 504篇 |
2002年 | 206篇 |
2001年 | 177篇 |
2000年 | 139篇 |
1999年 | 109篇 |
1998年 | 101篇 |
1997年 | 173篇 |
1996年 | 131篇 |
1995年 | 143篇 |
1994年 | 101篇 |
1993年 | 76篇 |
1992年 | 73篇 |
1991年 | 30篇 |
1990年 | 27篇 |
1989年 | 37篇 |
1988年 | 34篇 |
1987年 | 21篇 |
1986年 | 20篇 |
1985年 | 19篇 |
1984年 | 11篇 |
1983年 | 14篇 |
1982年 | 11篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1977年 | 4篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 59 毫秒
81.
Dr. Yashapal Singh Prof. Dr. Alexei V. Demchenko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(5):1042-1051
Following the recent discovery that traditional silver(I) oxide-promoted glycosidations of glycosyl bromides (Koenigs–Knorr reaction) can be greatly accelerated in the presence of catalytic TMSOTf, reported herein is a dedicated study of all major aspects of this reaction. A thorough investigation of numerous silver salts and careful refinement of the reaction conditions led to an improved mechanistic understanding. This, in turn, led to a significant reduction in the amount of silver salt required for these glycosylations. The progress of this reaction can be monitored by naked eye, and the completion of the reaction can be judged by the disappearance of characteristic dark color of Ag2O. Further evidence on higher reactivity of benzoylated α-bromides in comparison to that of their benzylated counterparts has been acquired. 相似文献
82.
Michał Dąbrowski Dr. Przemysław Wyrębek Dr. Damian Trzybiński Prof. Krzysztof Woźniak Prof. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3782-3794
Robust, selective, and stable in the presence of ethylene, ruthenium olefin metathesis pre-catalyst, {[3-benzyl-1-(10-phenyl-9-phenanthryl)]-2-imidazolidinylidene}dichloro(o-isopropoxyphenylmethylene)ruthenium(II), Ru-3 , bearing an unsymetrical N-heterocyclic carbene (uNHC) ligand, has been synthesized. The initiation rate of Ru-3 was examined by ring-closing metathesis and cross-metathesis reactions with a broad spectrum of olefins, showing an unprecendented selectivity. It was also tested in industrially relevant ethenolysis reactions of olefinic substrates from renewable feedstock with very good yields and selectivities. 相似文献
83.
Dr. Alasdair I. McKay Dr. James Barwick-Silk Max Savage Prof. Michael C. Willis Prof. Andrew S. Weller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(13):2883-2889
The synthesis of rhodium complexes with weakly binding highly fluorinated benzene ligands is described: 1,2,3-F3C6H3, 1,2,3,4-F4C6H2 and 1,2,3,4,5-F5C6H are shown to bind with cationic [Rh(Cy2P(CH2)xPCy2)]+ fragments (x=1, 2). Their structures and reactivity with alkenes, and use in catalysis for promoting the Tishchenko reaction of a simple aldehyde, are demonstrated. Key to the synthesis of these complexes is the highly concentrated reaction conditions and use of the [Al{OC(CF3)3}4]− anion. 相似文献
84.
Dr. Yong Guan Jonathan W. Attard Prof. Dr. Anita E. Mattson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1742-1747
The stereocontrolled construction of biologically relevant chromanones and tetrahydroxanthones has been achieved through the addition of alkynes to benzopyrylium trilfates under the influence of copper bis(oxazoline) catalysis. Excellent levels of enantiocontrol (63–98 % ee) are achieved in the addition of a variety of alkynes to an array of chromenones with a hydrogen in the 2-position. Promising levels of enantiocontrol (54–67 % ee) are achieved in the alkynylation of chromenones with esters in the 2-position, generating tertiary ether stereocenters resembling those frequently found in naturally occurring metabolites. 相似文献
85.
Yang Yang Ying Jiang Prof. Dr. Wei Du Prof. Dr. Ying-Chun Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1754-1758
Isobenzofulvene species are versatile synthons in organic chemistry, which have been employed in diverse challenging higher-order cycloaddition reactions. Here, the first chemoselective and asymmetric cross [10+2] cycloaddition reaction between activated 2-alkylidene-1-indanones and a variety of electron-deficient alkenes has been developed, relying on the in situ generation of dearomative 1-hydroxyl isobenzofulvene anion intermediates under the catalysis of a newly designed bulky cinchona-derived phase-transfer compound. An array of fused frameworks with multifunctionalities were generally furnished in excellent diastereo- and enantioselectivity, even at 1 mol % catalyst loadings. 相似文献
86.
Pedro D. García-Fernández Cristina Izquierdo Dr. Javier Iglesias-Sigüenza Dr. Elena Díez Prof. Rosario Fernández Prof. José M. Lassaletta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):629-633
The formal insertion of alkenes into aromatic chloro- and bromoalkynes takes place under cationic gold catalysis. This haloalkynylation reaction can be performed with cyclic, gem-disubstituted and monosubstituted alkenes, using BINAP, triazolo[4,3-b]isoquinolin-3-ylidene ligands or SPhos, respectively. The products were isolated in moderate to excellent yields and with complete diastereo- and regioselectivity; the halogen atom bonding the more substituted carbon of the alkene. Preliminary experiments showed that the enantioselective haloalkynylation of cyclopentene can be performed with (S)-BINAP to afford the insertion products with moderate to good enantioselectivities. 相似文献
87.
Isabel Guerrero Dr. Zsolt Kelemen Prof. Dr. Clara Viñas Dr. Isabel Romero Prof. Dr. Francesc Teixidor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):5027-5036
Metallacarboranes with the shape of the Greek letter θ, such as [Co(C2B9H11)2]−, were tested, for the first time, as efficient photoredox catalysts in the oxidation of aromatic and aliphatic alcohols in water. Their efficiency is linked to their high solubility in water, their high oxidizing power (Co4+/3+), and their absence of fluorescence on excitation, among others. In most of the studied examples, using a catalyst load of 0.4 mol % gave high yields of 90–95 % with selectivity greater than 99 %. By reducing the catalyst load to 0.01 mol %, quantitative conversion of reactants to products was achieved, in some cases with greater than 99 % yield, high catalyst efficiency reaching a turnover number of 10 000, and a higher yield with a 45 times lower concentration of catalyst. The metallacarboranes can be recovered easily by precipitation on addition of [NMe4]Cl. A pathway for the photoredox-catalyzed oxidation of alcohols is proposed. 相似文献
88.
Dr. Francesco Della Monica Dr. Veronica Paradiso Prof. Dr. Alfonso Grassi Dr. Stefano Milione Prof. Dr. Luigi Cavallo Prof. Dr. Carmine Capacchione 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5347-5353
A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers. 相似文献
89.
Dr. Karl P. J. Gustafson Arnar Guðmundsson Dr. Éva G. Bajnóczi Dr. Ning Yuan Prof. Xiaodong Zou Prof. Ingmar Persson Prof. Jan-E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3411-3419
The activation process of a known Ru-catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X-ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert-butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1-phenylethanol a fast-dynamic equilibrium was observed. 相似文献
90.
Dr. Taku Kitanosono Prof. Dr. Shū Kobayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9408-9429
Ever-evolving catalyst advances in synthetic protocols using water as a reaction medium have enriched the understanding of sustainable organic chemistry. Because conventional classification and definitions were ambivalent, it is proposed here that catalytic reactions using water be collectively called to be “in water”, with further classification into seven types. When accelerated in water as heterogeneous mixtures, the reactions can be regarded as following an “on-water” mechanism. The original term “on water” coined by Sharpless is incongruous with catalytic reactions, whereas on-water used in this review covers all the interfaces involving water where chemical reactions are accelerated. As a result of the unconcluded dispute on the antiquated catalyst-free “on water” model, the modified model defines three water layers: water molecules that are oriented to extrude protons toward the oil phase in the inner layer, those enwrapped by a secondary layer, and finally the bulk water layer. In light of the latitudinous outlook on the role of water at the interface, selected examples of reactions, in particular those reported over the past decade, that follow an “on-water” mechanism are reviewed herein. 相似文献