在碱金属/液氨作用下两类还原反应的机理探讨

碱金属/液氨溶液具有很强还原性,在有机合成中有着广泛的运用。在高等教育出版社出版的由邢其毅、裴伟伟、徐瑞秋以及裴坚等人编著的《基础有机化学》(第3版)中描述了在碱金属/液氨作用条件下的两类还原反应:炔烃被还原为烯烃的反应和Birch还原反应。一般认为这两种反应均生成了自由基负离子中间体。本文结合近几年的文献报道,对它们的机理进行进一步的探讨。     

On the unsymmetrical deformation and reverse snapping of a spinning non-flat disk

In this paper we study the steady state deflection and reverse snapping phenomenon of a spinning non-flat disk. Both the initial and the deformed shapes of the disk are allowed to have axisymmetrical and unsymmetrical components. For the analysis of a rotating axisymmetrical disk, we conclude that there is no need to include the unsymmetrical assumed modes in the solution because all the unsymmetrical steady state deformations are unstable. In addition, the stability of the axisymmetrical positions will not be affected by the inclusion of the unsymmetrical assumed modes. In the case when the initial shape of the disk contains a dominant axisymmetrical component and a smaller unsymmetrical component, attention is focused on the effect of this unsymmetrical component on the overall deformation and stability of the spinning disk. It is found that the unsymmetrical component with one nodal diameter tends to slightly defer the occurrence of the reverse snapping phenomenon. On the other hand, all other unsymmetrical components with more than one nodal diameter tend to reduce dramatically the reverse snapping speed. Experiment is conducted on a non-flat brass disk containing an axisymmetrical component and an unsymmetrical component with two nodal diameters. The experimental measurement confirms the theoretical prediction.     

Synthesis of unsymmetrically substituted pyrene derivatives through (6-bromo-3,8-dibutylpyren-1-yl)trimethylsilane

A straightforward route to unsymmetrically functionalized pyrene derivatives is described involving the synthesis of key precursor (6-bromo-3,8-dibutylpyren-1-yl)trimethylsilane 1. In a first step bromide 1 was successful in Suzuki-Miyaura, Sonogashira, and Buchwald-Hartwig cross-coupling reactions. Subsequent transformation of the trimethylsilyl group to bromide enabled the introduction of a second variable functional group onto the pyrene skeleton.     

Highly enantioselective fluorescent recognition of amino acid derivatives by unsymmetrical salan sensors

Novel unsymmetrical salan fluorescent sensors 2a and 2b have been designed and synthesized. The chiral recognition of N-Boc-protected amino acids by 2a and 2b has been investigated. Sensor 2a possesses higher sensitivity and enantioselectivity than sensor 2b does. Job analysis and nonlinear regression results show that 2a can form a 1:1 stoichiometric complex with a N-Boc-protected amino acid. The obtained response selectivities and the association constants indicate that 2a is a highly enantioselective and sensitive fluorescent sensor toward N-Boc-protected amino acids.     

An effective synthetic route to ortho-difluoromethyl arylphosphosphonates: studies on the reactivity of phosphorus- and fluorine-containing functions

Herein, we report a new and convenient methodology for the synthesis of ortho-XCF₂ arylphosphonates via Diels-Alder reaction of selected 1,3-butadienes with XCF₂-≡-P(O)(OEt)₂, followed by the aromatization of the cyclic vinylphosphonates obtained using the KMnO₄/Al₂O₃ system. The reactivity of ortho-XCF₂ arylphosphonates was then examined to give the respective dichlorides that were converted to the corresponding phosphonic acids, phosphine oxides or a carboxylic acid (upon hydrolysis of the CF₂Br group). When ortho-XCF₂ arylphosphonates (X=Br) were treated with Zn/CuBr and an electrophile, the dimeric product ArCFCFAr was isolated only. The lithiation of the CF₂H group (X=H) allowed however to obtain products of nucleophilic substitution with various electrophiles.     

Library-friendly synthesis of fluorinated ketones through functionalized hydration of alkynes and investigation of the reaction mechanism

A library-friendly synthesis of α-substituted-α-fluoroketones through functionalized hydration of alkynes in one pot under mild conditions is reported. The ready availability of alkynes and organoboronic acids makes this reaction quite attractive. We also studied the key intermediate—a fluorinated cationic gold species—using in situ NMR spectroscopy and ESI-high resolution mass spectrometry.     

Iridium-catalyzed hydroiodination of functionalized alkynes

The efficiency of an Ir(I)/HI system has been studied. The association of hydroiodic acid with iridium has been tested in the catalytic hydroiodination of alkynes. The use of [Ir(cod)Cl]₂ dimer led to clean hydroiodination reactions and afforded the corresponding vinyliodides as a mixture of derivatives, where the Markovnikov type adduct was found to be the major product (80/20 to 93/7 ratio), in good yields. The mechanism was investigated and two main pathways seemed to be involved, one based on an initial oxidative addition of HI to the Ir(I) complex and the other one based on a π-activation of the alkyne moiety. The corresponding vinyliodides were engaged in Pd-catalyzed cross-coupling (Sonogashira and Suzuki-Miyaura) reactions under organoaqueuous conditions.     

第I种非对称三态叠加多模叠加态光场的高次和压缩——第一正交分量的N次方H压缩效应

构造了第孙中禹种强度不等的非对称三态叠加多模叠加态光场|ψ₁^(ABC)〉_q.利用多模压缩态理论研究了态|ψ₁^(ABC)〉_q第一正交分量高次和压缩.结果发现:①当构成态|ψ₁^(ABC)〉_q的三个多模相干态光场的强度不相等时,在一定条件下,态|ψ₁^(ABC)〉_q的第一正交分量可出现任意幂次的高次和压缩.②当上述的三个多模相干态光场强度相等时,态|ψ₁^(ABC)〉_q的第一正交分量的高次和压缩现象消失.在这种情况下,态|ψ₁^(ABC)〉_q的第一正交分量恒处于NH最小测不准态.     

Alkyne‐Mediated Approach to the Synthesis of (4R,5R)‐5‐Hydroxy‐4‐decanolide and (−)‐Muricatacin

The asymmetric synthesis of two naturally occurring 5‐hydroxy‐γ‐butyrolactones, (4R,5R)‐5‐hydroxy‐4‐decanolide ( 1a ) and (?)‐muricatacin ( 2 ), is described using a general alkyne‐mediated strategy. The key steps involved are Sonogashira coupling for the desired carbon‐chain extension followed by Sharpless asymmetric dihydroxylation to construct the hydroxy‐lactone framework.     

Efficient synthesis of enynes by tetraphosphine-palladium-catalysed reaction of vinyl bromides with terminal alkynes

Through the use of [PdCl(C₃H₅)]₂/cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as catalyst, a range of vinyl bromides undergoes Sonogashira cross-coupling reaction with a variety of alkynes, leading to the corresponding 1,3-enynes in good yields. The reaction tolerates several alkynes such as phenylacetylene, dec-1-yne, 2-methylbut-1-en-3-yne a range of alk-1-ynols, 3,3-diethoxyprop-1-yne and a propargyl amine. Higher reactions rates were observed in the presence of phenylacetylene, dec-1-yne, but-3-yn-1-ol, pent-4-yn-1-ol, 3,3-diethoxyprop-1-yne or 1,1-dipropyl-2-propynylamine than with propargyl alcohol, 3-methoxy-prop-1-yne or 2-methylbut-1-en-3-yne. This catalyst can be used at low loading even for reactions of sterically hindered vinyl bromides such as bromotriphenylethylene or 2-bromo-3-methyl-but-2-ene.