论文中英文摘要格式
毕业论文外文翻译(中英文)
译文交通拥堵和城市交通系统的可持续发展摘要:城市化和机动化的快速增长,通常有助于城市交通系统的发展，是经济性，环境性和社会可持续性的体现,但其结果是交通量无情增加，导致交通拥挤。
道路拥挤定价已经提出了很多次，作为一个经济措施缓解城市交通拥挤，但还没有见过在实践中广泛使用，因为道路收费的一些潜在的影响仍然不明。
本文首先回顾可持续运输系统的概念,它应该满足集体经济发展,环境保护和社会正义的目标.然后,根据可持续交通系统的特点，使拥挤收费能够促进经济增长，环境保护和社会正义。
研究结果表明,交通拥堵收费是一个切实有效的方式，可以促进城市交通系统的可持续发展。
一、介绍城市交通是一个在世界各地的大城市迫切关注的话题。
随着中国的城市化和机动化的快速发展,交通拥堵已成为一个越来越严重的问题,造成较大的时间延迟,增加能源消耗和空气污染，减少了道路网络的可靠性．在许多城市,交通挤塞情况被看作是经济发展的障碍.我们可以使用多种方法来解决交通挤塞,包括新的基础设施建设，改善基础设施的维护和操作,并利用现有的基础设施,通过需求管理策略,包括定价机制,更有效地减少运输密度.交通拥堵收费在很久以前就已提出，作为一种有效的措施,来缓解的交通挤塞情况。
交通拥堵收费的原则与目标是通过对选择在高峰拥挤时段的设施的使用实施附加收费,以纾缓拥堵情况．转移非高峰期一些出行路线,远离拥挤的设施或高占用车辆，或完全阻止一些出行,交通拥堵收费计划将在节省时间和降低经营成本的基础上,改善空气中的质量，减少能源消耗和改善过境生产力。
此计划在世界很多国家和地方都有成功的应用。
继在2０世纪70年代初和8０年代中期挪威与新加坡实行收费环,在20０３年2月伦敦金融城推出了面积收费；直至现在,它都是已经开始实施拥挤收费的大都市圈中一个最知名的例子。
然而,交通拥堵收费由于理论和政治的原因未能在实践中广泛使用。
道路收费的一些潜在的影响尚不清楚,和城市发展的拥塞定价可持续性,需要进一步研究。
论文中英文摘要
论文中英文摘要作者姓名：张志飞论文题目：早寒武世澄江化石库腕足动物研究作者简介：张志飞，男，1975年08月出生，2003年9月师从于西北大学舒德干教授，于2006年6月获博士学位，现获得国家自然科学基金资助项目（青年科学基金）1项（40702005），参加国家自然科学基金面上项目3项。
中文摘要腕足动物是一类底栖纤毛环悬浮取食、身裹双壳的海生无脊椎动物，是早古生代海洋生物群落的重要组成部分，也是华南梅树村阶小壳化石之后出现最早的壳体动物化石之一，因此，成为寒武纪生物大爆发和生物矿化机制发生的重要研究对象。
腕足、帚虫和苔藓外肛动物通常统称为触手冠动物（lophophorata）。
形态解剖研究表明腕足动物和帚虫关系紧密，应该隶属于后口动物类群，最近的分子系统研究进一步证实了帚虫和腕足的单系亲缘关系，但却认为它们属于原口动物。
两种分类体系发生分歧的一个重要原因是因为它们只分别讨论了部分或局部的分子性状特征，或过分强调或权重了成体或幼体的个别性状的分类意义。
然而所有的成体形态特征和个体发育特点对动物的系统分类皆可能具有分类意义，问题是怎样对各种性状进行分类，也就是如何判断和厘定哪些性状是门、纲、目等不同分类阶元的关键特征；哪些性状是演化的甚至多次演化的特征，例如体腔（Coelom）通常用作动物高级分类阶元的分类，但学者很少讨论体腔的形成是一次演化形成还是多次演化形成。
形态上解决腕足动物的系统分类问题，一方面要对现生不同类群的腕足动物形态发育和解剖进行全面的分析，更重要的是研究不同地质时期腕足动物的形态特征，确定各组织器官起源和分异的时间，了解并确定各个性状进化的极向（polarity），更准确地判断腕足动物的同源或同型性状，进而识别腕足动物的祖征和衍征，以便恢复和识别干群腕足动物的形态。
澄江化石库以富产多门类软躯体化石而知名，其中包含大量的腕足动物。
其腕足化石不但数量丰富、分异度较高，而且精美保存了各种壳体内部解剖信息，为了解寒武纪大爆发时期腕足动物的形态解剖和性状进化提供了极好的实证材料。
学术论文英文摘要格式
学术论文英文摘要格式学术论文英文摘要格式英文题名和英文摘要是学术类和技术类科技期刊论文的重要组成部分,是国际间传播、学术交流与合作的桥梁和媒介,有其特殊的意义和作用。
好的英文题名和英文摘要对于增加期刊和论文的被检索和引用机会、吸引读者、扩大影响起着不可忽视的作用。
为了帮助读者撰写论文英文题名和英文摘要,本文总结了学术论文英文摘要格式的基本要求及注意事项,以给读者提供参考和指导。
学术论文英文摘要格式一、论文题名1.英文题名撰写的基本要求题名应简明、具体、确切,能概括文章的主旨,符合编制题录、索引和检索的有关原则并有助于选择关键词和分类号。
中文题名一般不超过20个汉字,必要时可加副题名。
题名中应避免使用非公知公用的缩略语、字符、代号以及结构式和公式。
英文题名的首字母及各个实词的首字母应大写。
2.英文题名撰写的注意事项除了以上基本要求,我们在写英文题名时还应注意以下几个问题。
(1)英文题名的结构。
英文题名以短语为主要形式,尤以名词短语最常见,即题名基本由一个或几个名词加上其前置和(或)后置定语构成。
短语型题名要确定好中心词,再进行前后修饰,要注意采用正确的单词顺序,形容词应与其所修饰的名词紧密相邻。
(2)英文题名中的冠词有简化的趋势,凡可用可不用的冠词均可不用。
英文题名开头第一个字不得用the, and, an和a。
(3)英文题名中的大小写有以下3种格式:全部字母大写;每个词的首字母大写,但3个或4个字母以下的冠词、连词、介词全部小写;题名第一个词的首字母大写,其余均小写。
(4)中英文题名的一致性。
同一篇论文,其英文题名与中文题名内容上应一致,但不等于说词语要一一对应。
在许多情况下,个别非实质性的词可以省略或变动。
总之,题名的用词十分重要,它直接关系到读者对文章的取舍态度,务必字字斟酌。
二、论文摘要1.摘要的定义摘要又称概要、内容提要。
摘要是论文主体的高度浓缩,它应该能提炼论文的主要观点,简明地描述论文的内容和范围,简短地进行概括和总结。
完整英文摘要
完整英文摘要第一篇：完整英文摘要lee's culture is located in the west of Long shan mountain, WeiShui river of the ancient county, is one of the cradles of Chinese ancient civilization, and also the birthplace of The lee.With Dunhuang culture, Tianshui fuxi culture, LaBuLengSi Tibetan Buddhism culture is one of four culture of Gansu province.But at present, the cultural development of West gansu is lagging behind, a lot of development and utilization of resources is difficult to get, it has to do withWest gansu geographical position relatively closed, human resources development has a close relationship.Lee's culture as an important form about culture, also suffered a bottleneck in its development, lee's cultural history and contemporary development not well together, especially in the promotion and development of invested is not enough, lead to lee's culture has been difficult to familiar to the general public.Local economic backward culture is difficult to promote the development process.Fully realize the importance of West gansu lee culture, reasonable and effective development of lee's culture, make its internal value have spread wider, deeper reach to culture to promote economic and cultural development dual goal.Cultural characteristicscountermeasuresThe economicdevelopment第二篇：摘要英文摘要温度是生产过程中常见和重要的物理参数。
毕业论文标题中英文摘要关键词和目录的格式
毕业设计（论文）新民本主义：传统民本思想与现代民主理念的契合（字体:黑体小一）专业年级学生学号学生姓名指导老师评阅人二○○年月中国·南京摘要（“摘要”两字的字体为黑体三号,居中。
）正文字体均为：宋体小四号，行距为倍（不低于400字）关键词：民本；民主；新民本主义（“关键词”三字字体为黑体，内容(3-5)个，宋体小四号。
各关键词之间用；）注意：摘要和关键词只能单独一页.Abstract（“Abstract”一词用Times New Roman字体三号,加黑,居中。
）Thought of people as the center is the marrow of our traditional culture and the core of the theory of managing state affairs. It germinates in the early state of antiquity society and is based on patriarchal clan system. It is also a kind of value seeking for the realization of the ethic reason and moral justice. Its basic thinking is that the monarch is defined by people and conversely people are defined by the monarch. At first appearance, its purpose is to value people’s suffering,fate and interest on the ruler’s position. However, its real intention is to fool the people so as to strengthen and consolidate the ruler’s rule. The theory of “people-oriented concept” includes nine topics such as “the theory of people is being the root of the monarch’s rule”, “the theory of people is being more valuable than the monarch”, “the theory of the monarch is being people’s servant”and so on. People –oriented means “value the people ”in essence, which sees “people”as its foundation of politics rule, ranking official, and administration.（正文字体为：Times New Roman字体，小四号，且行距为单倍或倍。
(论文中英文摘要格式)
（论文中英文摘要格式）作者姓名：肖伟烈论文题目：四种药用植物的化学成分和生物活性研究作者简介：：肖伟烈，男， 1976年12月出生，于2002年9月师从中国科学院昆明植物研究所孙汉董院士攻读植物化学博士学位，并于2005年7月获博士学位。
中文摘要本论文由五章组成。
第一章论述了狭叶五味子化学成分及生物活性的研究。
第二章为红花五味子茎叶和果实的化学成分及生物活性的研究。
第三章介绍法落海化学成分及生物活性的研究。
第四章论述了白云花化学成分及生物活性的研究。
论文第五章综述了1999年到2004年间发表的新环阿尔廷三萜类化合物。
通过波谱分析及晶体X-衍射等手段，从上述四种植物中共分离鉴定了129个化合物，32个为新化合物。
已鉴定的化合物类型涉及三萜、三萜皂甙、黄酮、黄酮苷、香豆素、香豆素苷、木脂素、甾体及环烯醚萜苷等化合物类型。
新化合物有三萜、香豆素苷、环烯醚萜、木酯素。
首次发现了一种新奇的五降三萜、一种带有螺环和烯醇式结构片段三萜化合物等结构新奇的降三萜化合物，同时还分离得到一种通过分子间重排而成的环烯醚萜二聚体苷类化合物。
对分离得到的部分化合物进行了抗HIV活性和抗血小板聚集活性筛选的研究发现，部分化合物具有抗HIV活性，5个化合物的抗HIV选择指数(SI)大于43。
这为治疗艾滋病药物的研究拓宽了思路，对于进一步进行结构修饰与改造、半合成或全合成，开发成具有自主知识产权的创新新药具有重要意义。
新奇结构的发现，不仅丰富了天然产物化学的内容，且为进一步合理开发利用云南的传统药用植物资源提供了新的化学物质基础和科学依据。
1 2 3 45 6 7 89 10 11 12图-1 结构新奇的化合物第一章狭叶五味子的化学成分和生物活性研究狭叶五味子(Schisandra lancifolia (Rehd. et Wils.) A. C. Smith)。
全株药用，味微苦、涩、性温，有止血接骨、去淤消肿之功效，用于跌打损伤、骨折、外伤出血等症。
英语论文摘要怎么写
英语论文摘要怎么写，并附上范例一则，希望对大家的英语论文摘要写作有所帮助。
英语专业本科毕业论文论文摘要格式中英文摘要对应，内容要基本保持一致;中文在前，英文在后。
字数为300-500字左右。
1.中文摘要①首行居中打印论文中文标题(宋体四号加粗)②下空一行居中打印摘要二字(宋体小四号加粗)，字间空一字符。
③摘要二字下空一行打印摘要内容(宋体小四号)。
④摘要内容后下空一行打印关键词三字(宋体小四号加粗)，其后接着打印关键词(3-7个，宋体小四号)，各关键词之间用逗号隔开，最后一个关键词后不打标点符号。
2.英文摘要①首行居中打印论文英文标题(Times New Roman四号加粗)②下空一行居中打印英文单词Abstract (Times New Roman 小四号加粗)。
③下空一行打印摘要内容(Times New Roman小四，1.5倍行距，两端对齐)④摘要内容后下空一行打印Key Words ( Times New Roman 小四号加粗)，其后接着打印关键词(3-7个关键词，Times New Roman小四号)。
除了专有名词外，其他单词的首字母不大写。
各关键词之间用分号隔开，最后一个关键词后不打标点符号。
⑤摘要正文各自然段首行空5个字符。
Self-Knowledge of Emma(空1行)Abstract(空1行)Emma lives in a quite simple environment. When she is a little child, her mother dies and she is spoiled by her father. Having such a background, Emma is dominant, aggressive and imaginative. After she experiences the two major affairs in her life----the relationship with Harriet and her emotion towards Mr. Knightley, she realizes her own faults and acquires self-knowledge of both moral faults and emotion.After Emma fails to be a match-maker of Harriet and Mr. Knightley, she comes to know that feelings can not be imagined and that she should not force her own idea on others mind. And this is the very beginning of Emma s self-knowledge.(空1行)Key Words: Emma; characters; match-making; self-knowledge范例：A Brief Discussion on Cultural Difference between Chinese and EnglishAbstractWord is the product of society,which is the history of mankind and which is the crystallization of history and culture.It embodied a nation's social consciousness from generation to generation, history, culture, and other areas all the features of human society. The essence of which is dependent because of their different cultural background, language background and traditional factors above. chinese and english are quite different.such as mode of living,values,atandard of behavior,formality,customs. Language is is both the carrier and the product of culture, the cultural enrichment of information is an important part ofculture, Language reflects the culture of development and changes, but also a direct reflection of the cultural differences.As we all know china and english has different cultural atmosphere .china has a long history and rich culture. English in the contemporary world political, economic, cultural and other fields to play with temporary no other language can replace the role of English in a number of countries in addition to the mother tongue but also as a second language or foreign language in common use in many countries. As a symbol system, English is a kind of language, on their use, in today's world there are all sorts of English and English is in fact the name of a simple terms, we can not hope that justice Literal It is a single, homogeneous phenomenon it is all around the world and under different circumstances the use of the many variants of the English pool. However, due to geographical, historical, cultural, and social customs of different factors such as the impact of today's visit to English furniture has evolved into a wider impact on the two variants of the worldwide English, which is British English and American English. With the development of their own language, their own characteristics of the formation, and there are differences between. In American English and British English, is concernedabout the characteristics of the norms word. In this paper, the British and American English in origin and development of a simple introduction, the United Kingdom and the United States in terms of language study and to explore differences in the two English-speaking characteristics and differences, the right to express and enrich the relevant knowledge of English, improve application English ability.Key word: dependent; culture; atmosphere中西方文化差异摘要词是社会的的结晶，是人类历史和文化的结晶。
论文格式及字体要求
论文格斯及要求目录第一部分：扉页 --------------------------------------------------------------------------------------- 1第二部分：中、英（外）文内容摘要 ------------------------------------------------------------- 2第三部分：目录 --------------------------------------------------------------------------------------- 2一、书写格式 ------------------------------------------------------------------------------------------ 2二、标题 ------------------------------------------------------------------------------------------------ 3三、篇眉和页码 --------------------------------------------------------------------------------------- 4四、图、表和公式------------------------------------------------------------------------------------- 4五、注释 ------------------------------------------------------------------------------------------------ 4第五部分：打印要求---------------------------------------------------------------------------------- 5广州歌剧院与国家大剧院---------------------------------------------------------------------------- 6第一部分：扉页论文题目（黑体二号，居中）；其他填写内容在横线上居中（指导教师不需填写职称），使用宋体三号字。
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附件2作者姓名：顾振华论文题目：2,3-联烯酸(酰胺)与联烯和炔烃的偶联环化反应研究作者简介：：顾振华，男，1979年02月出生，2002年09月师从于中国科学院上海有机化学研究所麻生明教授，于2007年7月获博士学位。
中文摘要联烯是一类含有1,2-丙二烯官能团的化合物。
在联烯的三个碳原子中，末端的两个sp2杂化的碳原子以剩下的未杂化的p轨道与中间的sp杂化的碳原子的两个互相垂直的p-轨道交盖形成两个互相垂直的π轨道。
当联烯末端的同一碳原子上的取代基两两不同时，联烯则具有轴手性，其构型可通过Cahn-Ingold-Prelog规则判定。
联烯化合物独特的反应性一方面来自这种独特的互相垂直交盖π-轨道，另一方面来自联烯末端的两个碳原子（四个取代基）对不同取代基的装载能力。
通过对底物及反应条件的调控，反应可以选择性的发生在联烯的三个不同的碳原子上。
由于其独特的结构及反应性，联烯在天然产物的合成中也有比较广泛地应用。
近年来越来越多的含联烯结构的天然产物被分离和鉴定，到目前为止已有约150个，这也极大地推动了联烯化学的发展。
我们小组在官能化的联烯的环化反应方面也作了一些研究。
最近我们小组发现并发展了官能化联烯的双分子氧化偶联反应，该反应能有效的一步构建双环化合物。
基于这些发现，我的工作就是设计和发展联烯与联烯、联烯与炔烃的偶联环化反应。
主要包括以下三大部分：第一部分：2,3-联烯酸(酰胺)与联烯的偶联环化反应1．我们研究了2,3-联烯酸双分子氧化偶联反应。
在研究过程中我们发展了三套氧化体系(a) n-C3H7I + O2, (b) KI + O2, (c) 苯醌来实现钯物种的催化循环，并且还研究了在这三套氧化体系下的取代基效应。
2．在实现了2,3-联烯酸自身双分子氧化偶联反应之后我们又研究了2,3-联烯酰胺与1,2-联烯基酮的交叉偶联反应。
根据我们小组以前的研究2,3-联烯酰胺有两种环化方式：即氧进攻生成Furanimine结构的化合物，或氮进攻生成内酰胺的产物。
通过X-射线单晶衍射和核磁研究，我们确认了在这一双分子氧化偶联反应中联烯酰胺的关环方式是氧进攻生成Furanimine结构的化合物，并且产物亚胺部分的结构是顺式的。
同时我们还观察到了2,3-联烯酰胺自身双分子偶联环化后部分水解的产物。
3．我们发现了2,3-联烯酸与2,3-联烯醇的交叉偶联反应。
与前面的双分子氧化偶联环化反应相比较，这是一种新的联烯的双分子偶联反应模式，即：(a) 该反应并不需要添加任何氧化剂就实现了钯物种的循环；(b) 只有2,3-联烯酸环化了，而2,3-联烯醇则形成了一个开链的1,3-共轭二烯结构。
研究过程中我们发现当使用二级醇时，我们得到的是高选择性的单一的反式产物，该选择性可以通过立体位阻作用及中间体π-烯丙基钯的σ-π-σ过程加以解释。
使用光学活性2,3-联烯酸为底物，我们得到的是部分消旋的产物；但当向体系中加入适量的质子酸，如三氟醋酸时，产物的消旋能够被很大程度的抑制。
该实验间接证明了反应的一个关键步骤β-羟基消除的一个中间体[PdCl+][OH-]的存在。
我们对产物的衍生化也作了一些研究，如新形成的1,3-共轭二烯能够顺利地与缺电子亲双烯体发生Diels-Alder反应。
4．前面我们实现了不同官能化联烯之间的偶联反应，但如何实现两种性质完全不同的联烯之间的偶联反应是一个比较有挑战性的课题。
这里我们发展了官能化联烯，如2,3-联烯酸与简单的联烯的偶联反应。
在该反应中底物溴化锂的溴负离子能够有效的淬灭π-烯丙基钯中间体，高选择性地得到了Z-式产物，而氯负离子或碘负离子并不能得到预期的烯丙基化合物。
该反应的高选择性可能源于呋喃酮基钯物种与简单联烯靠近时的立体位阻作用。
产物烯丙基溴衍生物在合成中是一个很有用的中间体，我们也进行了对产物的衍生化研究，如它可以选择性地与胺或苯亚磺酸钠发生S N2型的亲核取代反应，与CH3MgBr在CuBr•SMe2催化下高选择性地发生S N2’型的取代反应，同时在NaBH4存在下C-Br键能被还原。
第二部分：2,3-联烯酸与炔烃衍生物的偶联环化反应1．我们发展了2,3-联烯酸与炔丙醇碳酸酯的偶联生成β-联烯基呋喃酮的反应。
在反应过程中新生成的联烯基并没有发生进一步的转化，有效的保留在了呋喃酮的β-位。
通过条件筛选我们确立了该反应的最佳条件：即以醋酸钯/三（2-呋喃基）膦为催化剂，二甲亚砜为溶剂。
研究过程中我们发现该反应有明显的取代基效应，如2,3-联烯酸的α-位和炔丙醇碳酸酯的炔烃末端同时为非氢取代时该反应产率很低，这很可能是由于产物上1,3-共轭二烯结构上取代基的1,3-张力的影响。
我们同时对产物β-联烯基呋喃酮作了衍生化研究：(a)β-联烯基呋喃酮能与缺电子炔烃进行Diels-Alder反应，进一步异构化后能一步有效地构建多取代及全取代苯环衍生物，为这类化合物提供了一个有效的合成方法。
(b)我们还发现β-联烯基呋喃酮能发生高选择性的羟碘化反应，该反应的选择性可能来自亲核试剂进攻碘鎓三元环时的立体位阻效应。
这是少数几例非杂原子导向的高选择性羟碘化反应。
(c)我们还初步研究了β-联烯基呋喃酮的γ-羟基化反应。
在有氧和碱性条件下，2(5H)-呋喃酮能发生γ-羟基化反应生成5-羟基2(5H)-呋喃酮。
当底物是β-联烯基呋喃酮时，γ-羟基化产物在I2存在下能有效的发生碘环化反应，有效地构建了双环化合物。
(d)我们发现了1,2,4(Z),7-四烯(α-烯丙基-β-联烯基呋喃酮)异构环化成八元环的反应。
该反应操作非常简单，只要将1,2,4Z,7-四烯在二甲苯中100 o C搅拌反应6小时即可，产率高达98%。
当向体系中加入亲双烯体，如马来酰胺时我们能得到一系列结构新颖的桥环化合物，反应的立体选择性是单一的，即亲双烯体是以endo方式从位阻较小的一面靠近底物的。
我们对反应的机理作了比较详细的研究，当将α-位烯丙基换成丙基取代基时，中间体发生了进一步地1,7-氢迁移反应，得到一种新的共轭三烯（顺反异构体）；当将α-位烯丙基换成苄基取代基时，中间体则发生了进一步的6π-电环化反应，得到一类五元并六元的双环化合物。
氘代实验显示联烯末端的烷基上的氢与α-位烯丙基上的亚甲基的氢有交换，这说明了联烯末端的烷基上的氢参与了该异构化过程。
最后我们认为该反应可能经历了如下一个比较复杂的过程：首先底物发生1,5-H迁移得到顺反两个中间体，其中一个反式中间体可以通过8π-电环化最终形成八元环产物，而顺式中间体则不能；但是这两个中间体可以通过两次1,7-H迁移相互转化。
2．我们研究了2,3-联烯酸与贫电子炔烃的偶联反应。
当炔烃是丙炔酸甲酯时，产物是1:1加成和1:2加成的混合物，但新形成的C=C双键是单一反式的。
通过条件优化，我们能得到以1:2加成为主的产物，比例为9:1~16:1。
我们还发现2,3-联烯酸与丙炔酸甲酯的1:2加成产物发生了π-键的迁移，通过机理研究我们认为该π-键的迁移可能是通过分子内的两次1,7-H迁移来实现的。
当炔烃是炔酮时，并没有发现1:2加成的产物，但反应得到的是一对顺反异构体。
在n-Bu3P作用下能有效地将顺式产物转化为反式产物，最终高选择地得到以反式为主的产物。
在这一部分的工作中我们发现以呋喃酮为母体的这一类结构中较普遍地存在着的氢迁移反应，而氢迁移得到的中间体（含两个环外双键的呋喃酮）并不稳定，它会进一步发生氢迁移或电环化反应得到开链或环状的共轭烯烃衍生物。
第三部分：钯和胺共催化的有机碘化物与联烯-醛的偶联反应有机小分子催化是近年来备受有机化学家关注的领域，如何结合有机小分子催化剂及过渡金属催化剂，在同一反应中发挥它们各自不同的功能是一个十分有意义的课题。
这里我们初步研究了过渡金属钯和有机小分子胺共催化的有机碘化物与联烯-醛的偶联反应。
在该反应中联烯的钯碳化反应得到π-烯丙基钯中间体，其接受被胺活化了的醛的 -位的进攻得到环状化合物。
通过条件筛选发现，二异丙胺和脯氨酸都能有效的催化该反应，顺反比为1:7~1:11。
对比实验表明钯和胺在该催化反应中缺一不可。
关键词：联烯、钯、交叉偶联、1, n-氢迁移、电环化The Coupling Cyclization Reaction Between 2,3-Allenoic Acids (or Amides)and Allene or AlkynesZhenhua GuABSTRACTAllenes are a class of compounds with a 1,2-diene functionality possessing two mutally perpendicular π-orbitals. This type of molecules has chirality when the two subsituents on both of the two terminal carbons are different to each other. Their configuration can be assigned based on Cahn-Ingold-Prelog rule. The unique reactivity of allenes is due to the presence of the two perpendicular π-orbitals as well as the substituent-loading capability. The reaction site may selectively be any carbon atom of the three-carbon unit via the tuning of the reaction conditions and its substituents. In many cases, it is advantageous to use the allene unit as a retrosynthetic fragment. In addition, about 150 natural products containing an allenic or cumulenic structure are also known, which greatly stimulates the development of allene chemistry.The research program in our group is mainly on the cyclization of functionalized allenes. Recently, we have discovered an oxidative dimeric cyclization reaction of functionalized allenes, which would easily afford bicyclic compounds in one step. In this dissertation, I have focused on the design and development of the cross-coupling cyclization between two allenes, or allene and alkyne. Thus, the dissertation can be divided into three parts:Part I: The Coupling Cyclization Reaction between Two Allenes1.We have studied the oxidative dimeric cyclization of 2,3-allenoic acids. Three different setsof reaction conditions: (a) n-C3H7I + O2, (b) KI + O2, and (c) benzoquinone, have been developed to regenerate the catalytic active Pd(II) species. We also studied the substituent effects of the oxidative dimeric cyclization reaction under these three systems.2.We realized the heterodimerization reaction of 2,3-allenamides and 1,2-allenyl ketones.Based on the previous study on the coupling-cyclization reaction of 2,3-allenamides with organic halides in this group, there are two cyclization patterns: one is the N-attack to form γ-lactams and the other is the O-attack to form furanimines. The NMR and X-ray diffraction studies show that the reaction only afforded furanimine-type structures, the O-attack products. We also observed the formation of the homodimerization monohydrolysis productof 2,3-allenamides, whose structure was also determined by the X-ray diffraction analysis.3.We discovered and studied the cyclization of 2,3-allenoic acids in the presence of2,3-allenols. It is a new reaction pattern between two different type of functionalized allenes, in which (1) the catalytically active Pd(II) species would be regenerated “automatically”after the reaction and (2) two allenes function differently, i.e., 2,3-allenoic acids form the butenolide skeletons while the 2,3-allenols introduce the 1,3-diene substituent to the β-position of the butenolides formed. It is interesting when secondary alcohols were used the reaction afforded exclusively the E-products, which might be explained via a σ-π-σprocess of the π-allylic palladium intermediate. When optically active 2,3-allenoic acid was used as a substrate, the reaction afforded the product with partial racemization. Interestingly, the addition of an carboxylic acid, i.e., trifluoroacetic acid, could greatly inhibit the racemization of the products, which indirectly supported the formation of [PdCl+][OH-] during the β-hydroxide elimination process. We also studied the Diels-Alder reaction of the products with dienophiles.4.We have developed a cyclization reaction of 2,3-allenoic acids in the presence of simpleallenes. The allenes used in the above three cyclization reactions are all functionalized ones.It is a challenge to couple with two allenes with completely different nature, such as 2,3-allenoic acids and simple allenes. In the presence of LiBr, we successfully realized the coupling-cylization between 2,3-allenoic acids and simple allenes affording highly selectively gave the Z-isomer. A plausible mechanism based on face-selective coordination of allenes was proposed to explain this Z-selectivity.The newly formed allylic bromide derivatives are useful synthetic intermediates, which could be further elaborated via the S N2 nucleophilic substitution with amine or sodium benzenesulfinate, the reduction of C-Br bond by NaBH4 and the CuBr•SMe2-catalyzed S N2’-substitution with CH3MgBr.Part II: The Coupling Cyclization Reactions Between 2,3-Allenoic Acids and Alkynes1.We have established a protocol of the palladium-catalyzed coupling reaction of2,3-allenoic acids with propargylic carbonates forming β-allenyl butenolides, in which the newly formed allene moiety does not undergo further transformation under the current coupling cyclization conditions. A survey of ligands showed that tri-(2-furyl)phosphine is the best for this reaction. It was observed there are serious substituent effects, i.e., the reaction of 2,3-allenoic acids with non-hydrogen substituents of α-position withnon-terminal propargylic carbonates would give the preducts in very poor yields probably due to the high 1,3-strain of the products. We also studied the synthetic application of these β-allenyl butenolides:(a)It is a challenge to synthesize poly- and fully- substituted benzene derivatives. Theβ-allenyl butenolides would highly selectively react with electron-deficient alkynes to give poly- and fully- substituted benzene derivatives.(b)We studied the highly regio- and stereoselective iodohydroxylation of β-allenylbutenolides. Electrophilic additions of allenes are synthetically attractive since two functionalities are introduced in one step. However, the poor regio- and stereoselectivity greatly inhibit the application of this reaction. It is interesting to observed that the β-allenyl butenolides would high selectively afford 4-[3’-hydroxy-2’-iodoalk-1’(Z)enyl]-2(5H)-furanones in the presence of I2 and H2O. The regio- and stereoselectivity of this reaction may be controlled by the electronic and steric effects of the furanone ring.(c)We studied the γ-hydroxylation reaction of β-allenyl butenolides. The γ-hydroxylationproducts could be easily cyclized in the presence of I2.(d)We have discovered a cycloisomerization reaction of 1,2,4(Z),7-tetraenes, i.e.α-allyl-β-allenyl butenolides, for the synthesis of eight-membered bicyclic compounds.The procedures are straightforward, the conditions (xylene, 100 o C, 6 h) are mild, and the yields are high (up to 98% yield). In the presence of dienophile, i.e., 1H-pyrrole-2,5-dione, the reaction would highly selectively afford poly-cyclic products. When a propyl group was induced to α-position instead of the alllylic one, the reaction would give a new triene.When a benzyl group was induced to α-position, the intermediate would afford a new six-membered ring via 6π-electrocyclization. The deuterium-labeling studies show that the hydrogen of the alkyl group at allenyl terminal involved in the isomerization process. We proposed that 1,5-H shift of the starting material would afford both E- and Z-intermediates. The E-intermediates would afford the eight-membered ring compounds via 8π-electrocyclization, while the Z-isomer could not. However, these two intermediates could be interconverted to each other via a double 1,7-H shift.2.We have studied the coupling cyclization reaction of 2,3-allenoic acids in the presence ofelectron-deficient alkynes. When methyl propiolate was used as substrate, the newly formed C=C double bond in the products was exclusively in their E-forms. However, both1:1 and 1:2 adducts were formed. After optimizing the reaction condition, 1:2 adductswere formed as the major products with the ratio up to 16:1. It is interesting that “π-bondmigration” was observed in the 1:2 adducts. After some mechanistic studies we believedthat the “π-bond migration” product may be formed via double 1,7-H shifts of the normal1:2 adducts. When 1-alkynyl ketones were used as substrates, no 1:2 adduct was observed.Instead, the reaction afforded a mixture of Z/E isomers of the 1:1 adduct. In the presenceof a catalytic n-Bu3P, the Z/E mixtures would highly selectively be converted to theE-isomers.Part III: The Cross-Coupling Reaction between Allene-Aldehyde and Organic Halides under the Cocatalysis of Pd(OAc)2/TFP and the Secondary AminesRecently, the use of organic molecule as catalyst has attracted much attention of organicchemists. It is a challenge to develop a reaction co-catalyzed by transition metal andorganic molecule, in which two catalysts functioned differently. In this part, we havestudied the cross-coupling reaction of allene-aldehydes with organic halides under thecocatalysis of Pd(OAc)2/TFP and the secondary amines. The π-allylic palladiumintermediate could be trapped by the nucleophlic attack of α-carbon of aldehyde, whichwas activated by the secondary amine. After some survey, we found two sets of conditions:Pd(OAc)2/TFP/diisopropylamine and Pd(OAc)2/TFP/proline/K2CO3. The ratio of cis/transis 1:7~1:11. The reaction would not take place in the absence of either the palladiumcomplex or an amine.Key words: allene •palladium •cross-coupling •1,n-hydrogen shift •electrocyclization。