全文获取类型
收费全文 | 293篇 |
免费 | 24篇 |
国内免费 | 2篇 |
专业分类
化学 | 264篇 |
晶体学 | 5篇 |
数学 | 19篇 |
物理学 | 31篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 4篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 5篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 13篇 |
2013年 | 13篇 |
2012年 | 21篇 |
2011年 | 33篇 |
2010年 | 10篇 |
2009年 | 6篇 |
2008年 | 20篇 |
2007年 | 14篇 |
2006年 | 18篇 |
2005年 | 22篇 |
2004年 | 14篇 |
2003年 | 12篇 |
2002年 | 14篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1997年 | 5篇 |
1996年 | 2篇 |
1994年 | 4篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1982年 | 5篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1970年 | 3篇 |
1969年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有319条查询结果,搜索用时 0 毫秒
311.
A Theoretical and Experimental Study of the Effects of Silyl Substituents in Enantioselective Reactions Catalyzed by Diphenylprolinol Silyl Ether 下载免费PDF全文
Prof. Dr. Yujiro Hayashi Daichi Okamura Tatsuya Yamazaki Yasuto Ameda Hiroaki Gotoh Dr. Seiji Tsuzuki Dr. Tadafumi Uchimaru Prof. Dr. Dieter Seebach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17077-17088
The effect of silyl substituents in diphenylprolinol silyl ether catalysts was investigated. Mechanistically, reactions catalyzed by diphenylprolinol silyl ether can be categorized into three types: two that involve an iminium ion intermediate, such as for the Michael‐type reaction (type A) and the cycloaddition reaction (type B), and one that proceeds via an enamine intermediate (type C). In the Michael‐type reaction via iminium ions (type A), excellent enantioselectivity is realized when the catalyst with a bulky silyl moiety is employed, in which efficient shielding of a diastereotopic face of the iminium ion is directed by the bulky silyl moiety. In the cycloaddition reaction of iminium ions (type B) and reactions via enamines (type C), excellent enantioselectivity is obtained even when the silyl group is less bulky and, in this case, too much bulk reduces the reaction rate. In other cases, the yield increases when diphenylprolinol silyl ethers with bulky substituents are employed, presumably by suppressing side reactions between the nucleophilic catalyst and the reagent. The conformational behaviors of the iminium and enamine species have been determined by theoretical calculations. These data explain the effect of the bulkiness of the silyl substituent on the enantioselectivity and reactivity of the catalysts. 相似文献
312.
Diphenylprolinol Silyl Ether Catalyzed Asymmetric Michael Reaction of Nitroalkanes and β,β‐Disubstituted α,β‐Unsaturated Aldehydes for the Construction of All‐Carbon Quaternary Stereogenic Centers 下载免费PDF全文
Prof. Dr. Yujiro Hayashi Yuya Kawamoto Masaki Honda Daichi Okamura Shigenobu Umemiya Yuka Noguchi Takasuke Mukaiyama Prof. Dr. Itaru Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12072-12082
The asymmetric Michael reaction of nitroalkanes and β,β‐disubstituted α,β‐unsaturated aldehydes was catalyzed by diphenylprolinol silyl ether to afford 1,4‐addition products with an all‐carbon quaternary stereogenic center with excellent enantioselectivity. The reaction is general for β‐substituents such as β‐aryl and β‐alkyl groups, and both nitromethane and nitroethane can be employed. The addition of nitroethane is considered a synthetic equivalent of the asymmetric Michael reaction of ethyl and acetyl substituents by means of radical denitration and Nef reaction, respectively. The short asymmetric synthesis of (S)‐ethosuximide with a quaternary carbon center was accomplished by using the present asymmetric Michael reaction as the key step. The reaction mechanism that involves the E/Z isomerization of α,β‐unsaturated aldehydes, the retro‐Michael reaction, and the different reactivity between nitromethane and nitroethane is discussed. 相似文献
313.
Direct Asymmetric Michael Reaction of α,β‐Unsaturated Aldehydes and Ketones Catalyzed by Two Secondary Amine Catalysts 下载免费PDF全文
Prof. Dr. Yujiro Hayashi Nariyoshi Umekubo 《Angewandte Chemie (International ed. in English)》2018,57(7):1958-1962
A direct asymmetric Michael reaction of α,β‐unsaturated aldehydes and ketones proceeded in the presence of two pyrrolidine‐type catalysts, a diphenylprolinol silyl ether and hydroxyproline, to afford synthetically useful δ‐keto aldehydes with excellent diastereo‐ and enantioselectivity. Although there are several iminium ions and enamines in the reaction mixture, the iminium ion generated by the former catalyst reacts preferentially with the enamine generated by the latter catalyst. 相似文献
314.
Honda K Konishi M Kawai M Yamada A Takahashi Y Hoshino Y Inoue S 《Natural product communications》2012,7(4):459-462
Optically active 1,3-bridged cyclobutanes 10 of the bicyclo[3.1.1]heptane ring system and 1,2-bridged cyclobutanes 11 of the bicyclo[3.2.0]heptane ring system were produced by UV irradiation of alpha,beta,gamma,delta-unsaturated esters 9a and 9c-f. The preference of endo-stereochemistry at C-6 bridged head was observed in cross-adducts 10. On the other hand, irradiation of conjugated dienol 9b led via only parallel cycloaddition to 1,2-bridged cyclobutane 11. 相似文献
315.
Shuji Yamashita Akito Naruko Yuki Nakazawa Le Zhao Yujiro Hayashi Masahiro Hirama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(29):8658-8661
Limonoids are highly oxygenated C13α‐triterpenes and common secondary metabolites. Several hundred congeners have been isolated to date. The first total synthesis of (±)‐limonin, the flagship congener of the limonoids, is now reported and features 1) a tandem radical cyclization generating the BCD ring system with the C13α configuration that is essential to the limonoids and a Robinson annulation to construct the limonoid androstane framework, 2) a singlet‐oxygen cycloaddition and a Baeyer–Villiger oxidation to synthesize the highly oxidized D ring, and 3) a Suárez reaction to construct the unique AA′ ring system. 相似文献
316.
317.
318.
319.