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91.
Inside Cover: Enantiopure Narrow Bite‐Angle POP Ligands: Synthesis and Catalytic Performance in Asymmetric Hydroformylations and Hydrogenations (Chem. Eur. J. 47/2014)
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92.
Enantiopure Narrow Bite‐Angle POP Ligands: Synthesis and Catalytic Performance in Asymmetric Hydroformylations and Hydrogenations
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Dr. Héctor Fernández‐Pérez Dr. Jordi Benet‐Buchholz Prof. Dr. Anton Vidal‐Ferran 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15375-15384
Herein is reported the preparation of a set of narrow bite‐angle P–OP ligands the backbone of which contains a stereogenic carbon atom. The synthesis was based on a Corey–Bakshi–Shibata (CBS)‐catalyzed asymmetric reduction of phosphomides. The structure of the resulting 1,1‐P–OP ligands, which was selectively tuned through adequate combination of the configuration of the stereogenic carbon atom, its substituent, and the phosphite fragment, proved crucial for providing a rigid environment around the metal center, as evidenced by X‐ray crystallography. These new ligands enabled very good catalytic properties in the Rh‐mediated enantioselective hydrogenation and hydroformylation of challenging and model substrates (up to 99 % ee). Whereas for asymmetric hydrogenation the optimal P–OP ligand depended on the substrate, for hydroformylation, a single ligand was the highest‐performing one for almost all studied substrates: it contains an R‐configured stereogenic carbon atom between the two phosphorus ligating groups, and an S‐configured 3,3′‐diphenyl‐substituted biaryl unit. 相似文献
93.
A variety of methyl esters are converted into the corresponding propyl esters upon treatment with l-propanol and chlorotrimethylsilane. Among them acyclic aliphatic esters have the best conversion rate. 相似文献
94.
Alfredo García Ferran Hurtado Clemens Huemer Javier Tejel Pavel Valtr 《Computational Geometry》2009,42(9):913-922
Let S be a set of n4 points in general position in the plane, and let h<n be the number of extreme points of S. We show how to construct a 3-connected plane graph with vertex set S, having max{3n/2,n+h−1} edges, and we prove that there is no 3-connected plane graph on top of S with a smaller number of edges. In particular, this implies that S admits a 3-connected cubic plane graph if and only if n4 is even and hn/2+1. The same bounds also hold when 3-edge-connectivity is considered. We also give a partial characterization of the point sets in the plane that can be the vertex set of a cubic plane graph. 相似文献
95.
Given a pair of matrices (A, B) we study the Lipschitz stability of its controlled invariant subspaces. A sufficient condition is derived from the geometry
of the set formed by the quadruples (A, B, F, S) where S is an (A, B)-invariant subspace and F a corresponding feedback. 相似文献
96.
It is shown that square free set theoretic involutive non-degenerate solutions of the Yang-Baxter equation whose associated permutation group (referred to as an involutive Yang-Baxter group) is abelian are retractable in the sense of Etingof, Schedler and Soloviev. This solves a problem of Gateva-Ivanova in the case of abelian IYB groups. It also implies that the corresponding finitely presented abelian-by-finite groups (called the structure groups) are poly-Z groups. Secondly, an example of a solution with an abelian involutive Yang-Baxter group which is not a generalized twisted union is constructed. This answers in the negative another problem of Gateva-Ivanova. The constructed solution is of multipermutation level 3. Retractability of solutions is also proved in the case where the natural generators of the IYB group are cyclic permutations. Moreover, it is shown that such solutions are generalized twisted unions. 相似文献
97.
98.
Prof. Dr. Anton Vidal‐Ferran Dr. Ignasi Mon Antonio Bauzá Prof. Dr. Antonio Frontera Laura Rovira 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11417-11426
Herein we report the use of polyether binders as regulation agents (RAs) to enhance the enantioselectivity of rhodium‐catalyzed transformations. For reactions of diverse substrates mediated by rhodium complexes of the α,ω‐bisphosphite‐polyether ligands 1 – 5 , a – d , the enantiomeric excess (ee) of hydroformylations was increased by up to 82 % (substrate: vinyl benzoate, 96 % ee), and the ee value of hydrogenations was increased by up to 5 % (substrate: N‐(1‐(naphthalene‐1‐yl)vinyl)acetamide, 78 % ee). The ligand design enabled the regulation of enantioselectivity by generation of an array of catalysts that simultaneously preserve the advantages of a privileged structure in asymmetric catalysis and offer geometrically close catalytic sites. The highest enantioselectivities in the hydroformylation of vinyl acetate with ligand 4 b were achieved by using the Rb[B(3,5‐(CF3)2C6H3)4] (RbBArF) as the RA. The enantioselective hydrogenation of the substrates 10 required the rhodium catalysts derived from bisphosphites 3 a or 4 a , either alone or in combination with different RAs (sodium, cesium, or (R,R)‐bis(1‐phenylethyl)ammonium salts). This design approach was supported by results from computational studies. 相似文献
99.
An asymmetric synthesis for the preparation of both enantiomers of trans-methylpipecolic acids is described. It is based on Sharpless epoxidation as a chirality source, regioselective ring opening with allylamine, and ring-closing metathesis to construct the piperidine ring. The stereogenic center at C-4 is set by stereoselective hydrogenation that is directed by the alcohol functionality of an intermediate and proceeds with good diastereomeric control (trans/cis 16/1). Crystallization of the Boc-protected amino acid afforded the target products with excellent chemical (98% de) and enantiomeric purity (99% ee). 相似文献
100.
The syntheses of the chloro complexes [Ru(eta5-C5R5)Cl(L)] (R = H, Me; L = phosphinoamine ligand) (1a-d) have been carried out by reaction of [(eta5-C5H5)RuCl(PPh3)2] or {(eta5-C5Me5)RuCl}4 with the corresponding phosphinoamine (R,R)-1,2-bis((diisopropylphosphino)amino)cyclohexane), R,R-dippach, or 1,2-bis(((diisopropylphosphino)amino)ethane), dippae. The chloride abstraction reactions from these compounds lead to different products depending on the starting chlorocomplex and the reaction conditions. Under argon atmosphere, chloride abstraction from [(eta5-C5Me5)RuCl(R,R-dippach)] with NaBAr'4 yields the compound [(eta5-C5Me5)Ru(kappa3P,P'-(R,R)-dippach)][BAr'4] (2b) which exhibits a three-membered ring Ru-N-P by a new coordination form of this phosphinoamine. However, under the same conditions the reaction starting from [(eta5-C5Me5)RuCl(dippae)] yields the unsaturated 16 electron complex [(eta5-C5Me5)Ru(dippae)][BAr'4] (2d). The bonding modes of R,R-dippach and dippae ligands have been analyzed by DFT calculations. The possibility of tridentate P,N,P-coordination of the phosphinoamide ligand to a fragment [(eta5-C5Me5)Ru]+ is always present, but only the presence of a cyclohexane unit in the ligand framework converts this bonding mode in a more favorable option than the usual P,P-coordination. Dinitrogen [(eta5-C5R5)Ru(N2)(L)][BAr'4] (3a-d) and dioxygen complexes [(eta5-C5H5)Ru(O2)(R,R-dippach)][BPh4] (4a) and [(eta5-C5Me5)Ru(O2)(L)][BPh4] (4b,d) have been prepared by chloride abstraction under dinitrogen or dioxygen atmosphere, respectively. The presence of 16 electron [(eta5-C5H5)Ru(R,R-dippach)]+ species in fluorobenzene solutions of the corresponding dinitrogen or dioxygen complexes in conjunction with the presence of [BAr'4]- gave in some cases a small fraction of [Ru(eta5-C5H5)(eta6-C6H5F)][BAr'4] (5a), which has been isolated and characterized by X-ray diffraction. 相似文献