全文获取类型
收费全文 | 239篇 |
免费 | 4篇 |
国内免费 | 10篇 |
专业分类
化学 | 251篇 |
物理学 | 2篇 |
出版年
2023年 | 30篇 |
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 1篇 |
2019年 | 4篇 |
2018年 | 11篇 |
2017年 | 5篇 |
2016年 | 6篇 |
2015年 | 1篇 |
2014年 | 9篇 |
2013年 | 12篇 |
2012年 | 5篇 |
2011年 | 17篇 |
2010年 | 13篇 |
2009年 | 12篇 |
2008年 | 12篇 |
2007年 | 19篇 |
2006年 | 10篇 |
2005年 | 11篇 |
2004年 | 22篇 |
2003年 | 4篇 |
2002年 | 3篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 9篇 |
1996年 | 4篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有253条查询结果,搜索用时 19 毫秒
1.
Ridge Michael P. Ylagan Eric Jaewon Lee Dr. Daniela E. Negru Dr. Paolo Ricci Bohyun Park Haram Ryu Prof. Dr. Mu-Hyun Baik Prof. Dr. P. Andrew Evans 《Angewandte Chemie (International ed. in English)》2023,62(23):e202300211
An enantioselective rhodium(I)-catalyzed Pauson–Khand reaction (PKR) using 1,6-chloroenynes that contain challenging 1,1-disubstituted olefins is described. In contrast to the previous studies with these types of substrates, which are only suitable for a single type of tether and alkyne substituent, the new approach results in a more expansive substrate scope, including carbon and heteroatom tethers with polar and non-polar substituents on the alkene. DFT calculations provide critical insight into the role of the halide, which pre-polarizes the alkyne to lower the barrier for metallacycle formation and provides the proper steric profile to promote a favorable enantiodetermining interaction between substrate and chiral diphosphine ligand. Hence, the chloroalkyne enables the efficient and enantioselective PKR with 1,6-enynes that contain challenging 1,1-disubstituted olefins, thereby representing a new paradigm for enantioselective reactions involving 1,6-enynes. 相似文献
2.
Si-Yong Yin Qiansujia Zhou Dr. Chen-Xu Liu Prof. Dr. Qing Gu Prof. Dr. Shu-Li You 《Angewandte Chemie (International ed. in English)》2023,62(37):e202305067
Enantioselective synthesis of N−N biaryl atropisomers is an emerging area but remains underexplored. The development of efficient synthesis of N−N biaryl atropisomers is in great demand. Herein, the construction of N−N biaryl atropisomers through iridium-catalyzed asymmetric C−H alkylation is reported for the first time. In the presence of readily available Ir precursor and Xyl-BINAP, a variety of axially chiral molecules based on indole-pyrrole skeleton were obtained in good yields (up to 98 %) with excellent enantioselectivity (up to 99 % ee). In addition, N−N bispyrrole atropisomers could also be synthesized in excellent yields and enantioselectivity. This method features perfect atom economy, wide substrate scope, and multifunctionalized products allowing diverse transformations. 相似文献
3.
Marina Briand Elsa Anselmi Guillaume Dagousset Emmanuel Magnier 《Chemical record (New York, N.Y.)》2023,23(9):e202300114
Over the last years, methods devoted to the synthesis of asymmetric molecules bearing a perfluoroalkylated chain have been limited in number. Among them, only a few can be used on a large variety of scaffolds. This microreview aims at summarizing these recent advances in enantioselective perfluoroalkylation (−CF3, −CF2H, −CnF2n+1) and highlights the need for new enantioselective methods to easily synthesize chiral fluorinated molecules which would be useful for the pharmaceutical and agrochemical industries. Some perspectives are also mentioned. 相似文献
4.
5.
Since the discovery of left-handed G-quadruplex (L-G4) structure formed by natural DNA, there has been a growing interest in its potential functions. This study utilised it to catalyse enantioselective Diels-Alder reactions, considering its different optical rotation compared to an ordinary G4. It was determined that when L-G4 was used with a combination of copper(II) ions, there was a good enantioselectivity (?52% ee) without further addition of ligands. When further consideration was given by adding G4 ligands, G4 was further stabilised, even obtaining a better enantioselectivity (up to ?80% ee). Moreover, when using ligands that have regulatory effects on G4, the ee value can be adjusted. In this work, a minimal left-handed G4 was reported. A follow-up study was also conducted, which recovers that the minimal left-handed G4 remains its catalytic effect and enantioselectivity, but is not so effective as the former case. This indicates that a complete G4 structure is relatively conducive to chiral catalysis. 相似文献
6.
A ferrocene-derived P,N-heterodonor ligand was effectively used in a Cu(OAc)2·H2O-catalysed asymmetric 1,3-dipolar cycloaddition of azomethine ylides with maleate derivatives, affording cycloadducts with high yields (up to 96%), diastereoselectivities (>99 dr), and enantioselectivities (up to 99% ee). 相似文献
7.
Ivanna Rivera Juan Carlos Mateos Alain Marty Georgina Sandoval Sophie Duquesne 《Tetrahedron letters》2013
Besides the well-known papain, lipolytic activity is another interesting enzymatic activity present in latex from Carica papaya. This lipolytic activity is strongly attached to the latex solid phase, resulting in a naturally immobilized biocatalyst. In this work we describe the kinetic resolution of (R,S)-2-bromophenylacetic acid octyl ester by Carica papaya crude latex and two partially purified latex fractions. Several parameters, such as substrate concentration and solvent effects were studied. The best results were obtained using decane as solvent with 50 mM of substrate and 50 mg/mL enzyme/reaction medium; under these conditions, a high enantioselectivity (E >200) was obtained with crude latex. A twofold increase of the initial rate maintaining E >200 was obtained using purified fractions without protease and without esterase. Lipase from Carica papaya latex is the most enantioselective wild-type enzyme ever described for the studied reaction. 相似文献
8.
In this paper we report the first chemoselective asymmetric hydrogenation of (1-bromo-1-alkenyl)boronic esters, which constitutes a new route to (α-bromoalkyl)boronic esters. The study demonstrates that excellent chemoselectivities along with full conversions can be obtained for hydrogenation of alkyl substituted derivatives with iridium–PˆN complexes. Moreover, acyclic alkyl derivatives afford (α-bromoalkyl)boronic esters in good enantioselectivities ranging from 64 to 73% ee. A cyclic alkyl derivative was obtained only in a nearly racemic form. The (1-bromo-1-alkenyl)boronic esters appear to be less reactive towards homogenous hydrogenation conditions than their chloro analogues as demonstrated by the higher catalyst loadings required to achieve full conversions for alkyl derivatives and lower conversions observed for the aryl substituted derivatives. 相似文献
9.
Alexander N. ZaykovZachary T. Ball 《Tetrahedron》2011,67(24):4397-4401
A phosphite additive that can act as an axial ligand for a dirhodium tetracarboxylate catalyst improves the enantioselectivity of silane insertion of a diazo substrate. A kinetic study enables measurement of the catalytic rate constant for the catalyst bound to an axial ligand. Although a single axial ligand has an inhibitory effect on reactivity at the distal rhodium center, axially-bound catalysts are the predominant active species in solution for phosphite concentrations above 6 mol % under our reaction conditions. We examine changes in product enantioselectivity as a function of ligand to shed light on the structure and kinetics of product formation steps. 相似文献
10.
Chiral derivatives of trans-1,2-diaminocyclohexane with different N,N-dialkyl groups in well-defined orientations have been synthesized, and applied as catalysts for the asymmetric aldol reaction between a variety of aldehydes and ketones. Enantiomeric catalyst 1j catalyzed the reaction in ethanol and provided excellent diastereoselectivity and enantioselectivity. Significantly, simple replacement of organic solvents with water switched the products of the aldol reactions from anti to syn configuration. Such catalytic reactions led to the products with anti to syn diastereoselectivity up to 99:1 in ethanol, while in water gave the products with syn to anti diastereoselectivity up to 99:1. 相似文献