全文获取类型
收费全文 | 255篇 |
免费 | 99篇 |
国内免费 | 15篇 |
专业分类
化学 | 368篇 |
物理学 | 1篇 |
出版年
2023年 | 3篇 |
2022年 | 7篇 |
2021年 | 8篇 |
2020年 | 24篇 |
2019年 | 13篇 |
2018年 | 17篇 |
2017年 | 7篇 |
2016年 | 33篇 |
2015年 | 32篇 |
2014年 | 29篇 |
2013年 | 29篇 |
2012年 | 20篇 |
2011年 | 11篇 |
2010年 | 13篇 |
2009年 | 18篇 |
2008年 | 13篇 |
2007年 | 14篇 |
2006年 | 6篇 |
2005年 | 7篇 |
2004年 | 11篇 |
2003年 | 13篇 |
2002年 | 15篇 |
2001年 | 9篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有369条查询结果,搜索用时 31 毫秒
31.
32.
Ring Expansions of Boroles with Diazo Compounds: Steric Control of C or N Insertion and Aromatic/Nonaromatic Products 下载免费PDF全文
Prof. Dr. Holger Braunschweig Dr. Florian Hupp Dr. Ivo Krummenacher Lisa Mailänder Florian Rauch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17844-17849
Access to novel imine‐substituted 1,2‐azaborinines, as well as highly arylated boracyclohexa‐3,5‐dienes has been developed by ring expansion of boroles with diazoalkanes with varying degrees of steric bulk. The formation of a diazoalkane intermediate is also discussed for the reaction of ortho‐brominated p‐tolyl‐azide with 1,2,3,4,5‐pentaphenylborole. Structural details as well as UV/Vis spectroscopic and cyclic voltammetric data are provided. These boron‐containing heterocycles have the potential to serve as building blocks for boron‐containing materials. 相似文献
33.
34.
Martín C Molina F Alvarez E Belderrain TR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(52):14885-14895
The Pd(0) complexes [(NHC)PdL(n)] (NHC=N-heterocyclic carbene ligand; L=styrene for n=2 or PR(3) for n=1) efficiently catalyse olefin cyclopropanation by using ethyl diazoacetate (EDA) as the carbene source with activities that improve on previously described catalytic systems based on this metal. Mechanistic studies have shown that all of these catalyst precursors deliver the same catalytic species in solution, that is, [(IPr)Pd(sty)], a 14e(-) unsaturated intermediate that further reacts with EDA to afford [(IPr)Pd(=CHCO(2)Et)(sty)], from which the cyclopropane is formed. 相似文献
35.
36.
37.
38.
Dr. Yoko Hasegawa Dr. Thomas Cantin Dr. Jonathan Decaens Dr. Samuel Couve-Bonnaire Prof. Dr. André B. Charette Prof. Dr. Thomas Poisson Prof. Dr. Philippe Jubault 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201438
The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh2((S)-TCPTAD)4 or Rh2((R)-BTPCP)4 catalysts (up to 95 % yield, >95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular C−H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r. 相似文献
39.
《Mendeleev Communications》2022,32(4):482-484
Rhodium(III) complexes catalyze the insertion of carbenoids generated from diazo compounds into E?H bonds (E = B, Si, N, but not C), although less efficiently than classical rhodium(II) carboxylates, despite formally higher oxidation state of the metal. 相似文献
40.
Riley L. Svec Paul J. Hergenrother 《Angewandte Chemie (International ed. in English)》2020,59(5):1857-1862
Diazomethane is one of the most versatile reagents in organic synthesis, but its utility is limited by its hazardous nature. Although alternative methods exist to perform the unique chemistry of diazomethane, these suffer from diminished reactivity and/or correspondingly harsher conditions. Herein, we describe the repurposing of imidazotetrazines (such as temozolomide, TMZ, the standard of care for glioblastoma) for use as synthetic precursors of alkyl diazonium reagents. TMZ was employed to conduct esterifications and metal‐catalyzed cyclopropanations, and results show that methyl ester formation from a wide variety of substrates is especially efficient and operationally simple. TMZ is a commercially available solid that is non‐explosive and non‐toxic, and should find broad utility as a replacement for diazomethane. 相似文献