全文获取类型
收费全文 | 399篇 |
免费 | 11篇 |
专业分类
化学 | 386篇 |
数学 | 5篇 |
物理学 | 19篇 |
出版年
2021年 | 2篇 |
2020年 | 8篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2016年 | 2篇 |
2015年 | 9篇 |
2014年 | 3篇 |
2013年 | 7篇 |
2012年 | 26篇 |
2011年 | 26篇 |
2010年 | 7篇 |
2009年 | 3篇 |
2008年 | 14篇 |
2007年 | 23篇 |
2006年 | 22篇 |
2005年 | 26篇 |
2004年 | 20篇 |
2003年 | 28篇 |
2002年 | 42篇 |
2001年 | 25篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1997年 | 8篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1990年 | 2篇 |
1989年 | 8篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 2篇 |
1982年 | 4篇 |
1981年 | 10篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1967年 | 1篇 |
1941年 | 1篇 |
1940年 | 1篇 |
1937年 | 1篇 |
1936年 | 2篇 |
1933年 | 1篇 |
排序方式: 共有410条查询结果,搜索用时 15 毫秒
11.
The first examples of the use of racemic vinylaziridines in a Pd-catalyzed dynamic kinetic asymmetric transformation have been examined. Optimization studies of the Pd-catalyzed addition of vinylaziridines to isocyanates revealed that the chiral ligand between trans-1,2-diaminocyclohexane and 2-diphenylphosphino-1-naphthoic acid is superior to that involving 2-diphenylphosphino benzoic acid. Surprisingly, high ee's required the use of an acid whose pKa was about 4.7 +/- 0.1 as a cocatalyst. Both acetic acid and hydroxybenzotriazole meet this requirement. Less electrophilic isocyanates (e.g., benzyl, p-methoxyphenyl) gave higher ee's than more electrophilic ones (phenyl or benzoyl). Both N-benzyl and N-arylaziridines react well to give good yields and ee's, whereas N-tosylaziridines gave lower ee's. A 1,1-disubstituted aziridine led to the formation of a tertiary C-N bond with ee's comparable to the formation of the secondary C-N bond. The products were easily reduced almost quantitatively to the sensitive imidazolidines which can be readily hydrolyzed to the vicinal diamines. The reactivity pattern is consistent with a Curtin-Hammett situation wherein the enantiodiscriminating event is the cyclization of a rapidly equilibrating dynamic pi-allyl palladium intermediate. 相似文献
12.
A palladium-catalyzed asymmetric allylic alkylation effects a dynamic kinetic asymmetric transformation of racemic isoprene monoepoxide and a surrogate for Nazarov's reagent in which a quaternary center is created with exellent ee. The resultant adduct allows easy access to a substrate for ring-closing metathesis to form a cyclopentenone and sets the stage for an 11-step synthesis of the cyclopentyl core of the antibiotic antitumor agent viridenomycin. [reaction: see text] 相似文献
13.
14.
15.
The palladium-catalyzed asymmetric allylic alkylation of a 1:1 mixture of dl- and meso-1,2-divinylethylene carbonate is reported. For the first time, both the ionization and nucleophilic addition steps of the catalytic cycle act as enantiodiscriminating steps to give a single product in high enantiomeric excess. The reactions proceed in >98% ee to efficiently generate useful chiral building blocks from acrolein. The absolute and relative configurations of iso-cladospolide B and 11-epi-iso-cladospolide B were verified by total synthesis, solving an apparent discrepancy in the literature. 相似文献
16.
Prof. Dr. Barry M. Trost Dr. Maksim Osipov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16318-16343
The communesin alkaloids are a diverse family of Penicillium‐derived alkaloids. Their caged‐polycyclic structure and intriguing biological profiles have made these natural products attractive targets for total synthesis. Similarly, the ascidian‐derived alkaloid, perophoramidine, is structurally related to the communesins and has also become a popular target for total synthesis. This review serves to summarize the many elegant approaches that have been developed to access the communesin alkaloids and perophoramidine. Likewise, strategies to access the communesin ring system are reviewed. 相似文献
17.
Trost BM 《Organic process research & development》2012,16(2):185-194
The ability to control the alkylation of organic substrates becomes ever more powerful by using metal catalysts. Among the major benefits of metal catalysis is the possibility to perform such processes asymmetrically using only catalytic amounts of the chiral inducing agent which is a ligand to the metal of the catalyst. A unique aspect of asymmetric metal catalyzed processes is the fact that many mechanisms exist for stereoinduction. Furthermore, using the same catalyst system, many types of bonds including but not limited to C-C, C-N, C-O, C-S, C-P, and C-H can be formed asymmetrically. An overview of this process using palladium and molybdenum based metals being developed in my laboratories and how they influence strategy in synthesizing bioactive molecular targets is presented. 相似文献
18.
Astrid Trost W. Kleib?hmer Karl Cammann 《Fresenius' Journal of Analytical Chemistry》1997,359(3):249-253
A rapid and uncomplicated method for the fractionation of PCBs leading to an isolation of the highly toxic non-ortho substituted
PCBs is described. The liquid chromatographic separation was achieved on a stationary phase consisting of activated carbon
and Celite 545. Using eluents with different polarity, isolation of the non-ortho substituted PCBs in a single fraction was
achieved. The fractions were analysed by GC/MS. The method was tested by the determination of non-ortho substituted PCBs in
technical mixtures (Aroclor 1254 and Aroclor 1242). The results were compared with those obtained by using an HPLC fractionation
on a porous graphitic carbon column. Finally, the micro-column fractionation was used for the determination of non-ortho substituted
PCBs in native soil samples.
Received: 5 March 1997 / Revised: 4 June 1997 / Accepted: 6 June 1997 相似文献
19.
20.
Trost BM 《Chemical & pharmaceutical bulletin》2002,50(1):1-14
Palladium catalyzed asymmetric allylic alkylations represent a challenging problem because the mechanism of the reaction places the chiral environment distal to the bond breaking or making events responsible for the asymmetric induction. Furthermore, unlike virtually every other asymmetric process, many strategies can be employed for introduction of asymmetry and many different types of bonds can be formed. While over 100 different ligands have been designed, a family of ligands derived from 2-diphenylphosphinobenzoic or 1-naphthoic acid and chiral scalemic diamines have been successful in inducing excellent enantioselectivity by five different enantiodiscriminating events. These methods have already provided practical strategies towards numerous biological targets--some of which are adenosine and its enantiomer, aflatoxin B, aristeromycin, calanolide A and B, carbovir, cyclophellitol, ethambutol, galanthamine, mannostatin, neplanocin, phyllanthocin, sphingofungins E and F, tetraponaines, vigabatrin, and valienamine. 相似文献