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991.
Sabrina I. Kallne Thomas Braun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(35):9465-9469
An unprecedented reaction pathway for the borylation of SCF3‐containing arenes using [Rh(Bpin)(PEt3)3] (pin=pinacolato) is reported. Catalytic processes were developed and the functionalizations proceed under mild reaction conditions. The C H activations occur with a unique regioselectivity for the position ortho to the SCF3 group, which apparently serves as directing group. Borylated SCF3 compounds can serve as versatile building blocks. 相似文献
992.
Manganese‐Catalyzed Dehydrogenative [4+2] Annulation of N?H Imines and Alkynes by C?H/N?H Activation
Ruoyu He Zhi‐Tang Huang Qi‐Yu Zheng Congyang Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(19):5050-5053
Described herein is a manganese‐catalyzed dehydrogenative [4+2] annulation of N H imines and alkynes, a reaction providing highly atom‐economical access to diverse isoquinolines. This transformation represents the first example of manganese‐catalyzed C H activation of imines; the stoichiometric variant of the cyclomanganation was reported in 1971. The redox neutral reaction produces H2 as the major byproduct and eliminates the need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by transition‐metal‐catalyzed C H activation. Mechanistic studies revealed the five‐membered manganacycle and manganese hydride species as key reaction intermediates in the catalytic cycle. 相似文献
993.
Yang Yang Stephen L. Buchwald 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(33):8821-8825
A copper‐based catalytic technique for the regioselective ortho C H cyanation of vinylarenes has been developed. This method provides an effective means for the selective functionalization of vinylarene derivatives. A copper‐catalyzed cyanative dearomatization mechanism is proposed to account for the regiochemical course of this reaction. 相似文献
994.
Miao Wan Zhilin Meng Hongxiang Lou Lei Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(50):14065-14069
A trityl ion mediated C H functionalization of ethers with a wide range of nucleophiles at ambient temperature has been developed. The reaction displays high chemoselectivity and good functional group tolerance. The protocol also exhibits excellent regio‐ and diastereoselectivities for the unsymmetric ethers, thus stereoselectively generating highly functionalized disubstituted 2,5‐trans tetrahydrofurans (THF), 2,6‐trans tetrahydropyrans (THP), 2,6‐trans dihydropyrans (DHP), and 1,3‐trans isochromans, and highlighting the capacity of the protocol in complex molecule synthesis. 相似文献
995.
Jia‐Xuan Yan Hu Li Xiang‐Wei Liu Jiang‐Ling Shi Xin Wang Zhang‐Jie Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(19):5045-5049
3,4‐Dihydroquinolinones were synthesized by the palladium‐catalyzed, oxidative‐addition‐initiated activation and arylation of inert C(sp3) H bonds. Pd(OAc)2 and P(o‐tol)3 were used as the catalyst and ligand, respectively, to improve the efficiency of the reaction. A further advantage of this reaction is that it could be performed in air. A relatively rare seven‐membered palladacycle was proposed as a key intermediate of the catalytic cycle. 相似文献
996.
Ryan Gianatassio Shuhei Kawamura Cecil L Eprile Klement Foo Jason Ge Aaron C. Burns Michael R. Collins Phil S. Baran 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(37):10009-10013
A simple method to convert readily available carboxylic acids into sulfinate salts by employing an interrupted Barton decarboxylation reaction is reported. A medicinally oriented panel of ten new sulfinate reagents was created using this method, including a key trifluoromethylcyclopropanation reagent, TFCS‐Na. The reactivity of six of these salts towards C H functionalization was field‐tested using several different classes of heterocycles. 相似文献
997.
Nusrah Hussain Gustavo Frensch Jiadi Zhang Patrick J. Walsh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(14):3767-3771
The combination of aryl bromides, allylbenzene, base and a palladium catalyst usually results in a Heck reaction. Herein we combine these same reagents, but override the Heck pathway by employing a strong base. In the presence of LiN(SiMe3)2, allylbenzene derivatives undergo reversible deprotonation. Transmetalation of the resulting allyllithium intermediate to LPdAr(Br) and reductive elimination provide the 1,1‐diarylprop‐2‐enes, which are not accessible by the Heck reaction. The regioselectivity in this deprotonative cross‐coupling process is catalyst‐controlled and very high. 相似文献
998.
999.
Ying Dong Bangyu Liu Peng Chen Qun Liu Mang Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(13):3510-3514
The insertion of an aryne into a C S bond can suppress the addition of an S nucleophile to the aryne in the presence of palladium. Catalyzed by Pd(OAc)2, a wide range of α‐carbamoyl ketene dithioacetals readily react with arynes to selectively afford functionalized 2‐quinolinones in high yields under neutral reaction conditions by a C S activation/aryne insertion/intramolecular coupling sequence. The attractive feature of the new strategy also lies in the versatile transformations of the alkythio‐substituted quinolinone products. 相似文献
1000.
Shao‐Jie Lou Dan‐Qian Xu Zhen‐Yuan Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(39):10498-10503
A novel and facile C H bond fluorination proceeds under remarkably mild conditions (close to room temperature in most cases). Both aromatic and olefinic C(sp2) H bonds with a wide range of electronic properties are selectively fluorinated in the presence of a catalytic amount of simple, cheap, and nontoxic nitrate as the promoter. A PdII/PdIV catalytic cycle that is initiated by an in situ generated cationic [Pd(NO3)]+ species was proposed based on preliminary mechanistic studies. 相似文献