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51.
仲酰胺经酰胺活化直接合成酮的普适性方法 总被引:2,自引:0,他引:2
本文报道仲酰胺经去胺基烷基化反应直接合成酮的通用性方法. 这一新的C-C 键形成方法是基于Tf2O 对仲酰胺的活化及有机铈试剂对活化所形成活性中间体的加成而实现的. 该方法可用于各种酮的合成, 包括烷基-烷基酮、烷基-芳基酮、芳基-芳基酮、α,β-不饱和酮以及β-氯-α,β-不饱和酮等, 收率65%~90%. 研究表明, 除了有机铈试剂外, 碱性较弱的炔基硼试剂、温和亲核性的烯丙基三甲基硅烷以及低亲核性的苯乙烯均可与仲酰胺的活化中间体进行加成反应, 水解后生成相应的酮. 因此, 该方法具有较好的普适性和重要的合成应用价值. 基于实验结果和验证实验, 提出经由腈鎓中间体的可能反应机理. 本法使仲酰胺成为形式上的酰化试剂, 不但可与有机金属试剂反应, 还可与烯丙基三甲基硅烷和苯乙烯进行还原酰化反应. 相似文献
52.
Two synthetic protocols leading to novel γ-aminophosphonate and phosphine oxide derivatives, by reductive amination of γ-phosphonylketones, are reported. The first method involved a two-step procedure. Imine intermediates were first isolated from the p-toluenesulfonic acid-catalyzed reaction of primary amines with γ-ketophosphonates and phosphine oxides, then reduced with NaBH4 in refluxing ethanol. The second method consists of a one-pot procedure which includes the condensation of γ-ketophosphonates and phosphine oxides with primary amines, in the presence of molecular sieves, followed by reduction with NaBH4. These methods offer significant advantages over prior reports, such as efficiency, generality, and good yields. Furthermore, they are green protocols avoiding hazardous hydrides and solvents. 相似文献
53.
ABSTRACTA widely used method for obtaining silver nanoparticles uses plant extracts for reduction because of the presence of phytochemicals such as terpenoids, tannins, and flavonoids. Extracts of Flores sambuci, Hypericum perforatum, Lavandula angustifolia, Origanum vulgare, Rosmarinus officinalis, and Salvia officinalis were used for generating silver nanoparticles. The ultraviolet–visible spectra of silver nanoparticle solutions were correlated with variations of phytochemical characteristics to evaluate the plant extracts. These parameters were the antioxidant activity, total flavonoids, total tannins, total terpenoids, and total phenolics. Correlations between measurements of extracts’ phytoreductive characteristics were explained using Pearson coefficients. The results showed medium linear positive correlations for total tannins with the spectra of silver nanoparticle solutions. The antioxidant activity and total terpenoids presented medium linear negative correlations. Pearson coefficients between total phenolics and relative areas from ultraviolet–visible spectra from 350 to 600?nm were close to zero indicating no linear correlation. 相似文献
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56.
Stereoselective Csp3–Csp2 Bond‐Forming Reactions by Transition‐Metal‐Free Reductive Coupling of Cyclic Tosylhydrazones with Boronic Acids
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Manuel Plaza Dr. M. Carmen Pérez‐Aguilar Dr. Carlos Valdés 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(18):6253-6257
The reactions between alkenylboronic acids and tosylhydrazones derived from substituted cyclohexanones lead to the construction of disubstituted cyclohexanes with total regio‐ and stereoselectivity. In these transition‐metal‐free processes, a Csp3?Csp2 and Csp3?H bond are formed on the same carbon atom. The stereoselective reaction is general for 2‐, 3‐, and 4‐substituted cyclohexanone tosylhydrazones, as well as for 2‐substituted cyclopentanones. However, no stereoselectivity is observed for acyclic derivatives. DFT computational modeling suggests that the stereoselectivity of the reaction is determined by the approach of the boronic acid to the diazocyclohexane on its most stable chair conformation through an equatorial trajectory. 相似文献
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58.
Bruhat-Chevalley Order in Reductive Monoids 总被引:1,自引:1,他引:0
Mohan S. Putcha 《Journal of Algebraic Combinatorics》2004,20(1):33-53
59.
Colin J. Bushnell Philip C. Kutzko 《Proceedings of the American Mathematical Society》2001,129(2):601-607
In this paper, is a non-Archimedean local field and is the group of -points of a connected reductive algebraic group defined over . Also, is an irreducible representation of a compact open subgroup of , the pair being a type in . The pair is assumed to be a cover of a type in a Levi subgroup of . We give conditions, generalizing those of earlier work, under which the Hecke algebra is the tensor product of a canonical image of and a sub-algebra , for a compact open subgroup of containing .
60.
A. Vasiu 《Mathematische Nachrichten》2010,283(8):1068-1113
Let k be an algebraically closed field of positive characteristic p. We first classify the D ‐truncations mod p of Shimura F ‐crystals over k and then we study stratifications defined by inner isomorphism classes of these D ‐truncations. This generalizes previous works of Kraft, Ekedahl, Oort, Moonen, and Wedhorn. As a main tool we introduce and study Bruhat F ‐decompositions; they generalize the combined form of Steinberg theorem and of classical Bruhat decompositions for reductive groups over k (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献