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A desire to elucidate this reaction, and the analogous alkyne metathesis reaction, led to the discovery and development of high oxidation state complexes that contain a M=C or M C bond, so-called alkylidene and alkylidyne complexes, respectively.

为了阐述复分解反应,发现和发展了含有双键和三键的金属有机化合物,分别被称谓杂金属烯烃和杂金属炔烃。

In this thesis, based on the preceding research of our laboratory, a new type of cagelike cyclophanes, in which 1,1 '-binaphthyl unit ,the source of chirality and three different linkers(2,6-dibromopyridine, 1,4-diiodobenzene, 4,4'-diiodobiphenyl) connected by ethynyl was designed and synthesized successfully and their optical properties were preliminarily researched.

本论文在大量的文献调研和本实验室过去研究结果的基础上,设计了由2,2'-二取代-1,1'-联萘和2,6-二取代吡啶,1,4-二取代苯,4,4'-二取代联苯三种不同连接桥通过炔键链接构筑的拓扑有趣的光学活性环芳化合物-四联萘笼状分子。

The invention discloses a process for preparing N-Boc derivative or N-Cbz derivative of chiral alpha, alpha'-double substituent pyrrolidine which contains ethylenic link and acetylenic link substituent.

本发明公开了一种制备含烯键和炔键取代基的手性α,α'-二取代吡咯烷的N-Boc衍生物或N-Cbz衍生物的方法。

Optically active cyclophane s, such as helical molecules and three-dimensional, cagelike cyclophanes have been the subject of extensive investigation from the standpoints of structural chemistry and material science.

本论文在大量的文献调研和本实验室过去研究结果的基础上,设计了由2,2'-二取代-1,1'-联萘和2,6-二取代吡啶,1,4-二取代苯,4,4'-二取代联苯三种不同连接桥通过炔键链接构筑的拓扑有趣的光学活性环芳化合物-四联萘笼状分子。

for preparing n-boc or n-cbz derivatives of chiral alpha,alpha'-disubstituted pyrrolidines containing olefinic bond and acetylene bond

一种制备含烯键和炔键取代基的手性α,α'-二取代吡咯烷的n-boc或n-cbz衍生物的方法

The dissertation mainly consists of two parts:1. The Reaction Chemistry of Alkynes under Palladium Catalysis Part 1 studies the reaction α,β-unsaturated carbonyl compounds with alkenylpalladium intermediate generated by nucleopalladation, and discovered 1 the Pd-catalyzed tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls,2 the four-component tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls, 3 the tandem intramolecular oxypalladation-conjugate additionreaction of alkynoic acids with α,β-enals. These new reactions provide notonly efficient highly stereoselective methods for the synthesis of γ,δ-unsaturated,polyunsaturated carbonyl compounds and γ-lactonic aldehydes, but also thebasic transformations for a number of C-C bond formation reactions which can be usedto design synthesis of many acyclic, cyclic or polycyclic compounds.

本论文的主要工作分为两个部分:一、钯催化下炔烃的反应化学在本小组前人工作的基础上,我们详细研究了炔烃亲核钯化产生的烯基钯中间体与α,β-不饱和羰基化合物的反应,发现两价钯催化下卤离子-炔烃-α,β-不饱和醛酮的串联加成反应、卤离子-炔烃-α,β-不饱和醛酮的西组分串联加成及炔酸分子内氧钯化-串联Michael型加成反应;由此发展了γ,δ-不饱和醛酮、多不饱和羰基化合物和带有醛酮基侧链的γ-丁内酯衍生物的高立体选择性合成方法,这一过量卤离子存在下的烯基钯对α,β-不饱和羰基化合物共轭加成反应的发现,为大量碳-碳键形成反应的实现提供了基础,使我们能够从这一基本反应出发,设计和开发多种分子内、分子间的碳碳成键反应,以好的立体、区域选择性组建开链、环状及多环类型的化合物。

The asymmetric alkynylation of carbonyls is proved to be one of the most powerful procedures for organic synthetic chemistry,where the formation of one carbon-carbon bond and one chiral center of propargylic alcohol can be achieved in one step,and has attracted organic chemists\' most attentions.Plenty of works have been reported in recent years.

由于催化末端炔对羰基化合物的不对称加成在制备手性炔丙醇的同时,能够构建一个碳碳键和一个手性中心,因而该领域的研究受到了研究者的广泛关注,有大量的研究工作见报道。

In the fifth part, asymmetric synthesis of β,γ-trans-alkenyl α-amino esters was achieved by chiral phosphoric acid catalyzed transfer hydrogenation of β,γ-alkynyl α-imino esters. Utilizing Hantzsch ester as the hydrogen donor, both the alkyne and imine moieties of β,γ-alkynyl α-imino esters were reduced to yield β,γ-trans-alkenyl α-amino esters with up to 96% ee.

第五部分工作中,使用手性磷酸作为催化剂,Hantzsch酯作为氢源,β,γ-炔烃取代的α-酮酸酯亚胺中的炔键和亚胺官能团均被还原,以中等的收率和优秀的对映选择性(up to 96% ee)得到β,γ-反式烯烃取代的α-氨基酸衍生物。

According to the geometric evolution of the substitutedcumulenes from the cumulenic-like resonance form to the acetylenic-like (charge-separated) resonance form, it is obtained that there are two kinds ofresonance form of the substituted cumulene.

根据取代累接双键烃几何构型从累接双键烃共振结构逐渐演变到多炔共振结构的过程,给出了取代累接双键烃的两种共振形式。

According to the geometric evolution of the substituted polyynes from theacetylenic-like resonance form to the cumulenic-like (charge-separated)resonance form, it is obtained that there are two kinds of resonance form of thesubstituted polyyne.

根据取代多炔几何构型从多炔烃共振结构逐渐演变到累接双键烃共振结构的过程,表明取代多炔存在着两种共振形式。

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