全文获取类型
收费全文 | 410篇 |
免费 | 76篇 |
国内免费 | 21篇 |
学科分类
数理化 | 507篇 |
出版年
2023年 | 5篇 |
2022年 | 10篇 |
2021年 | 7篇 |
2020年 | 16篇 |
2019年 | 16篇 |
2018年 | 4篇 |
2017年 | 6篇 |
2016年 | 26篇 |
2015年 | 33篇 |
2014年 | 34篇 |
2013年 | 47篇 |
2012年 | 25篇 |
2011年 | 28篇 |
2010年 | 32篇 |
2009年 | 24篇 |
2008年 | 19篇 |
2007年 | 28篇 |
2006年 | 26篇 |
2005年 | 28篇 |
2004年 | 27篇 |
2003年 | 43篇 |
2002年 | 3篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1996年 | 1篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 2篇 |
排序方式: 共有507条查询结果,搜索用时 6 毫秒
1.
2.
3.
4.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):303-313
The reaction of electron‐deficient alkenes with alkoxyalkynyl Fischer carbene complexes (FCCs) represents a straightforward route to a new type of captodative (donor–acceptor) alkynylcyclopropanes, which have been prepared in moderate to high yields and in a diastereoselective manner. Some studies regarding the employment of additives to facilitate the recovery of the metal moiety after the reaction are also described. Finally, the first example of a cyclopropanation reaction through employing Fischer carbene complexes under microwave irradiation is presented; this method proved to be an advantageous alternative to the thermal reaction. 相似文献
5.
We have demonstrated that the readily available amido-keto compounds 5, with prearranged carbonyl and glycine moieties, under strongly basic conditions easily undergo complete and highly diastereoselective cyclization, affording a generalized and practical access to the conformationally constrained phenylserine derivatives 4. High chemical yields, virtually complete diastereoselectivity combined with the operational convenience of the experimental procedures render this method useful for preparation of these diastereomerically pure derivatives. 相似文献
6.
Fan CA Hu XD Tu YQ Wang BM Song ZL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4301-4310
A novel and highly diastereoselective samarium-catalyzed tandem rearrangement/reduction of secondary alpha-hydroxy epoxides, which involves a C1 to C3 carbon migration rearrangement and a very interesting hetero-Tishchenko reduction of the intermediate aldehyde and the reductant aldehyde, has been reported. This reaction could be developed to provide a facile and stereoselective construction of 2-quarternary 1,3-diol units with an hydroxymethyl moiety attached to the diastereogenic quaternary carbon center. Detailed investigations have been carried out concerning the screening of the aldehydes as a reductant, the optimization of reaction conditions, and the substrate scope of this tandem reaction. A catalytic cycle for this reaction, the electronic and steric effects of the reductant aldehydes, and the mechanism for the acyl migration of 1,3-diol monoesters are proposed. 相似文献
7.
Trost BM Shen HC Horne DB Toste FD Steinmetz BG Koradin C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2577-2590
The Ru-catalyzed intramolecular [5+2] cycloaddition of cyclopropylenynes is investigated with respect to the regio- and diastereoselectivity as well as the functional group compatibility of the reaction. Evidence for the mechanism as occurring through a ruthenacyclopentene intermediate is elucidated from 1) the study of the diastereoselectivity of the cycloaddition; 2) the effect of variation of substituents on the regioselectivity of cyclopropyl bond cleavage in 1,2-trans- and 1,2-cis-disubstituted cyclopropanes and 3) examples that clearly do not involve ruthenacyclohexene as intermediates as products still incorporate the cyclopropyl moiety. The scope and limitations of the Ru-catalyzed cycloaddition are discussed and compared with the Rh-catalyzed reaction. The potential power of this methodology towards natural product total synthesis is demonstrated by the formation of several polycyclic systems with the chosen reaction conditions and readily available cyclopropylenyne substrates. 相似文献
8.
Sandra Hübner Dirk Michalik Dr. Haijun Jiao Dr. Helfried Neumann Dr. Stefan Klaus Dirk Strübing Dr. Anke Spannenberg Dr. Matthias Beller Prof. Dr. 《化学:亚洲杂志》2007,2(6):734-746
Chiral N‐dienyl lactams are crucial building blocks for the synthesis of complex organic compounds. However, their generation is rather challenging. This paper reports the novel one‐pot reaction of (S)‐methyl pyroglutamate as the a mide component with different a ldehydes and d ienophiles (AAD reaction) to give novel chiral 1‐amido‐2‐cyclohexenes. The corresponding N‐dienyl lactams generated in situ undergo subsequent Diels–Alder reactions in good yield and diastereoselectivity. The scope and limitations of the three‐component protocol were investigated. X‐ray and NMR spectroscopic analysis of the products as well as DFT calculations of the intermediates were also performed to explain the observed stereoselectivity and structural features. 相似文献
9.
10.
A. S. Saghiyan A. V. Geolchanyan L. L. Manasyan G. M. Mkrtchyan N. R. Martirosyan S. A. Dadayan T. V. Kochickyan V. S. Harutyunyan A. A. Avetisyan V. I. Tararov V. I. Maleev Yu. N. Belokon' 《Russian Chemical Bulletin》2004,53(4):932-935
An efficient method was developed for the asymmetric synthesis of (R)-S-(1,2,4-triazol-3-yl)cysteines by the addition of 3,4-disubstituted 1,2,4-triazole-5-thiols at the electrophilic C=C bond in a NiII complex of a Schiff base of dehydroalanine with (S)-N-(N-benzylprolyl)aminobenzophenone. The stereoselectivity of the formation of diastereomeric complexes with the (S,R) configuration under conditions of thermodynamic control of the nucleophilic addition exceeds 94%. Acid treatment of the reaction mixtures afforded enantiomerically pure (R)-S-hetarylcysteines (ee >98%). 相似文献