金属有机化学国家重点实验室2000年年度进展报告.doc
金属有机化学国家重点实验室2000年年度进展报告.doc
二 000 年重大事记 一. 完成 2000－2001 年基金申请 共资助了 27 个项目，其中有机所 12 个，外单位 17 个，资助总额 72.6 万 。 二．实验室换届工作 根据中国科学院厅局文件关于印发<<中国科学院开放实验室主任、学术委员会 主任聘任办法>>的通知和关于 2000 年开放实验室换届工作的通知，在院、所领导 支持下和上一届全体学术委员的配合下，我们顺利地完成了今年的换届工作。本届 实验室主任为麻生明研究员，学术委员会主任为钱长涛研究员。 三. 引进年轻的跨世纪学术带头人 为了建立一支稳定流动的高水平的青年人才队伍, 开放室在人才引进工作上一 直采取专家推荐与实验室主动联系的方式积极引进人才。为了实验室的进一步发 展，今年又分别从国外和国内引进 2 名青年学术带头人张兆国博士和许旭博士。 四. 知识创新工程的实施和检查 我室今年在有机所领导的支持下, 知识创新工程的各项工作进展良好。为了进 一步推进知识创新工程全面、深入的开展，中科院高技术局实验室处邢如云处长、 李刚同志于 9 月 7 日到有机所，调研我们所金属有机化学开放实验室在创新工程中 有关科技目标的凝练和改革方案中节点目标的执行情况。到会的有有机所所长郑崇 直、副所长吕龙、科研处处长姚祝军、副处长陈维明、财务处处长傅丽英以及金属 有机开放室的陆熙炎院士、戴立信院士等全体学科带头人。 首先实验室主任麻生明研究员汇报了开放实验室知识创新工程执行情况。接着 全体到会人员就实验室的知识创新工作进行了热烈具体的讨论。所领导肯定了实验 1 室全体人员的努力，同时表明有机所在知识创新工程中将继续支持开放室的进一步 发展。院领导主要了解了开放室知识创新工作中科技目标的凝练和结构的调整，了 解我们开放室创新经费的使用情况，尤其是如何建立合适的分配激励制度，最大限 度发挥每个学术带头人的专长和工作积极性。大家就目前遇到的问题进行充分的交 流，达成共识，为下一步知识创新工作的更好完成打下扎实的基础。 10 月 18 日, 侯雪龙副主任又到北京参加中科院召开的“重点实验室试点工作 总结交流会”, 并代表金属开放室在会上作了实验室工作汇报。会上到会的各进入 知识创新工程的实验室进行了充分交流, 讨论如何做好下一步的知识创新工作。 五. 973 项目的启动 经过努力, 由我室麻生明研究员作为首席科学家之一的 973 项目“创造新物质 的分子工程学研究”于今年正式启动, 11 月 4-5 日在上海有机所召开了项目的启动 会议, 年底由我们开放室成员参与的两个子课题的经费已经到位。我们将努力高质 量的完成我们承担的任务。 六.添置大型仪器设备 去年 8 月份, 由于我们 99 年全国实验室评估中被评为优秀实验室, 中科院批 文中国科学院将投资 400 万元建设金属有机化学国家重点实验室, 今年经费已到位 。按照我们在 1999 年 11 月份召开的升为国家重点实验室的升级论证会上的计划, 我们将利用这笔经费购置 300 兆核磁共振仪(DPX300)一台, Weissenberg 面探仪一 台, 手套箱两套。目前经过紧张的商谈招标, 就这些仪器与供应商的订购签订了合 同, 将于今年年底明年年初到货安装调试。为实验室升级为国家重点实验室的验收 会作好准备。 2 七.实验室及走廊的装修 在院和所的大力支持下，开放室今年对 3 号楼 4 楼实验室进行了全面装修, 将 4 楼的剩余未装修的 15 间实验室进行了装修。这样 3 号楼 3 楼 4 楼已全部装修 完毕, 成为金属有机化学实验室的一块实验基地，为实验室的升级验收做好了硬件 准备。 3 金属有机化学开放实验室学术委员会 第四届第一次会议简报 金属有机化学开放实验室学术委员会第四届第一次会议于今年 12 月 4－5 日在 上海有机所召开。十六位委员中有两位因另有会议等原因未能到会，会议还邀请了 国家基金委化学部有机化学学科杜灿屏主任参加。会议由学术委员会主任钱长涛教 授主持。首先由有机所郑崇直所长讲话，他代表所领导欢迎各位委员的到来，并感 谢全体委员对开放室工作的一贯支持、配合和指导，感谢国家基金委对我们基础学 科的大力支持, 他认为开放室现在的成绩是所内外各界人士共同努力的结果，希望 今后继续得到各位的指导和支持。然后钱长涛研究员介绍了本次学委会换届的原因 和整个换届过程, 感谢退下来的三位老委员多年来对实验室工作的支持和帮助, 希 望本次换届后新老委员继续支持实验室的发展。这次会议的议程是 1) 室主任汇报 实验室一年来的工作情况，2) 专家学术报告和交流，3) 部分课题组工作进展汇报 ，4) 国际学术会议介绍，5)今后工作讨论。 一.实验室主任麻生明研究员汇报了开放室一年来的工作 麻生明主任首先欢迎并感谢各位专家的到会，指出我们实验室的学术委员会会 议不仅是各位专家对实验室工作的指导和督促，也是国内金属有机化学界同行的一 次聚合和交流，起到团结全国金属有机化学界同行的作用。会上麻生明主任从实验 室一年来如何筹建国家重点实验室和承担中科院知识创新试点工程项目两方面向与 会专家汇报了实验室一年来在研究方向、队伍建设与人才培养、运行机制、对外开 放等方面所进行的主要工作。 二．专家学术报告和交流 会上由南京大学忻新泉教授作了题目为“室温固相合成化学”的学术报告，在 探讨固－固相化学反应机理的同时，着重从原子簇与三阶非线性光学；纳米材料及 组装和绿色化学三个方面介绍了室温的固相合成化学。结合自己课题组的大量工 作，讲述了室温固相反应的发生及特点。 4 三. 课题组工作进展汇报和讨论 这次会上共有五个课题组进行工作汇报，分别由施敏研究员(不对称催化反应) 、唐勇研究员(主族元素化合物化学)、张兆国研究员(手性配体的设计与合成)、江 焕峰研究员(超临界流体中自由基参与的羰基化反应)、席振峰教授(新一代物质转 化途径)到会汇报。委员们认真听取了他们的进展情况和今后工作设想，并就研究 工作中的问题提出了中肯的意见，参加汇报的同志都认为收益非浅。与会同志认为 这不仅仅是课题检查，更是学术交流，对汇报的课题组今后工作帮助很大。 四．国际学术会议介绍和讨论 本次会上共介绍了五个国际会议的内容： 1. 上海有机所的唐勇、张兆国研究员介绍了 2000 年 7 月在上海召开的第 6 届华人 有机会议的情况, 此会由有机所主办，世界各地的华人均可参加，会上还颁发了 “华人青年有机化学奖”。本次会议共有五个大会报告、十六个邀请报告和十一个 口头报告，会上来自世界各地的青年华人有机化学家进行了充分的交流。 2. 上海有机所的麻生明研究员介绍了今年 5 月在美国 Boston 召开的 Inductrical Synthesis of Optically Active Compounds 和 Chiral USA 2000 的会议，前一个会议主 要讨论了手性的起源、合成方法学，主要是工业上的一些手性合成问题；后一个会 议是学术交流性质的。麻生明还介绍了今年 7 月在波兰华沙召开的 13th International Conference on Organic Synthesis，会上有多位著名有机化学科学家做了精彩的大会报 告。 3. 上海有机所的钱长涛研究员介绍了今年 7 月在上海召开的第 19 届 IUPAC 国际金 属有机化学会议的情况。此次会议由上海有机所及金属有机化学开放实验室联合主 办。钱老师先介绍了大会的概况，然后指出此次会议的学术交流重点是：1.烯烃聚 合催化剂新发展；2.金属有机催化的不对称合成方法；3.金属有机用于材料科学。 着重介绍了 6 个大会特邀报告的内容 5 通过这些介绍和讨论，使到会委员们及时了解国际上金属有机化学研究的热 点，掌握目前文献还来不及报道的热门资料，大家一致认为收益非浅。 五．今后工作讨论 会上大家结合目前国内外科学研究的趋势，联系我们实验室的学科发展方向进 行了热烈的讨论。大家认为基础研究必须要深入扎实，要长期坚持才能出大成果。 学科方向应该面对新的形势不断调整，但又必须立足于自己的特长，发扬优势。各 专业之间要真正交叉，必须要有导向性的强强联合型合作，而不是名义上或某些学 术名词上的交叉。 总之，本次学委会会议讨论热烈，交流充分，学术气氛浓厚，与会者都认为收 获较大。最后大家一致希望金属开放室在新世纪成为一个一流的国家重点实验室， 成为中国的金属有机化学研究基地，为国家解决重大科学问题，发展金属有机化 学，在世界金属有机化学研究领域占有一定的地位。 6 2000～2001 资助课题一览表 序 号 姓 名 单 位 题 目 2000-01 陆熙炎 上海有机所 二价钯的不对称催化反应 2000-02 钱长涛 上海有机所 单原子桥联芴基环戊二烯基稀土配合物的 合成、结构及催化活性研究 2000-03 麻生明 上海有机所 金属参与的碳-碳键形成反应研究 2000-04 侯雪龙 上海有机所 氮杂环丙烷化合物的去对称化反应及在有 机合成中的应用 2000-05 沈延昌 上海有机所 金属有机参与的高选择性合成方法学研究 2000-06 陈家碧 上海有机所 (杂)烯炔配位的金属卡宾和卡拜络合物及其 在合成中应用 2000-07 邓敏智 上海有机所 手性环丙基硼化物的新反应及其在天然产 物合成中的应用 2000-08 姜 标 上海有机所 手性配体的制备及其在不对称反应中的应用 2000-09 施 敏 上海有机所 膦酰胺类手性配体的设计合成及其在不对称 催化反应中的应用 2000-10 丁奎岭 上海有机所 基于 NOB 衍生物为配体的金属络合物催化的 不对称反应研究 2000-11 唐 勇 上海有机所 可溶性高聚物负载叶立德的合成及其在有机 合成中的应用 2000-12 廖世键 大化所 1、通过金属有机中间体合成纳米尺寸的稀土 金属和稀土氢化物粉末 2、高选择性有机合成反应中双金属催化的协 同效应 2000-13 宋礼成 南开大学 两类单蝶状铁硫络盐的新反应及其在合成多蝶 状簇合物中的应用研究 7 2000-14 黄 宪 -杂原子或金属取代的、-不饱和砜及膦酸 浙江大学 脂的合成及其在立体选择合成反应中的应用 2000-15 沈 琪 苏州大学 稀土和后过渡金属化合物的合成及催化聚合活 性的研究 2000-16 康北笙 中山大学 含咪唑基三角架型氮杂化合物的亲金属性研究 2000-17 沈之荃 浙江大学 钐化合物催化极性单体聚合研究 2000-18 张永敏 浙江大学 稀土金属和过渡金属试剂在有机合成中的应用 2000-19 张良辅 成都有机所 多相不对称催化反应的研究 2000-20 刘汉范 北化所 纳米金属簇催化酮酸酯及二酮的不对称氢化 其对催化反应的影响 2000-21 王积涛 南开大学 金属有机试剂在-氨基酸手性合成中的的应用 2000-22 徐善生 南开大学 单桥及双桥连二环戊二烯基双核过渡金属 化合物的研究 2000-23 周其林 南开大学 螺旋型手性催化剂的设计合成及其应用 性研究 2000-24 曹卫国 上海大学 胂叶立德在高选择性合成中的应用――立体 选择性合成γ-丁内酯及γ-丁内酰胺类化合物 2000-25 周锡庚 复旦大学 炔丙基稀土金属有机物的合成、结构及其反应 2000-26 席振峰 北京大学 过渡金属促进的利用二氧化碳作为碳源的新型 碳－碳键形成反应 2000-27 江焕峰 广化所 过渡金属化合物在超临界二氧化碳介质中的 催化行为研究 2000-28 庞 震 复旦大学 含半活性配位基团的金属有机配合物的合成及 其对催化反应的影响 2000-29 张兆国 上海有机所 亚胺及烯胺的氢甲酰化反应 8 二 000 年论文目录 课题负责人：陆熙炎 1. 课题编号： 2000-01 An Efficient Preparation of -Alkylidene--formylmethyl--lactams via Pd(II)Catalyzed Intramolecular Alkyne-Unsaturated Carbonyl Coupling Xie, X.; Lu, X.* Synlett 2000, 707-709. 2. 32 Role of Halide Ions in Palladium(II) Catalyzed Nucleophile Alkyne-a,b-Unsaturated Carbonyl Coupling Reactions Lu, X.; Wang, Z. Polyhderon 2000, 19, 577-579. 3. 35 Effect of Halide Ligands on the reactivity of Carbon-Palladium Bonds: Implications for Designing Catalytic Reactions Wang, Z.; Zhang, Z.; Lu, X.* Organometallics 2000, 19, 775-780. 4. 38 A Facile Highly Regio- and Stereo-selective Preparation of N-Tosyl Allylic Amines from Allylic Alcohols and Tosyl Isocyanate via Palladium(II)-Catalyzed Aminopalladation--Heteroatom Elimination Lei, A.; Lu, X.* Org. Lett. 2000, 2, 2357-2360. 5. 44 Palladium(II)-Catalyzed Tandem Intramolecular Aminopalladation of Alkynes and Conjugate Addition. Synthesis of Oxazolidinones, Imidazolidinones and Lactams Lei, A.; Lu, X.* Org. Lett. 2000, 2, 2699-2702. 48 9 6. Highly Enantioselective Palladium(II)-Catalyzed Cyclization of (Z)-4'-Acetoxy-2'butenyl 2-Alkynoates. An Efficient Synthesis of Optically Active -Butyrolactones Zhang, Q.; Lu, X.* J. Am. Chem. Soc. 2000, 122, 7604-7605. 课题负责人：钱长涛 52 课题编号： 2000-02 1. Coordinatively Unsaturated Neodymium Hydrides,Stability in Solution Visseaux Marc, Baudry Denise, Dormond Alain, Qian Changtao J. Organomet. Chem., 1999, 574(2), 213-218 54 2. [2+2] Cycloaddition Reactions of Imines with Alkynyl Selenides Catalyzed by Scandium Triflate Yun Ma and Changtao Qian Tetrahedron Letters, 2000, 41, 945-947 60 3. Asymmetric Hetero-Diels-Alder Reaction of Glyoxylate Esters and Danishefsky's Diene Catalyzed by Chiral Bis(oxazoline)-Lanthanide Complexes Changtao Qian and Longcheng Wang Tetrahedron Letters, 2000, 41, 2203-2206 63 4. First Application of Amino-TADDOL Derivatives in Enantioselective Addition of Diethylzinc to Aryl Aldehydes: Effect of Substituents on the Nitrogen Atom Changtao Qian, Fei-Feng Gao and Sun Jie Tetrahedron: Asymmetry, 2000, 11, 1733-1740 67 5. Asymmetric Glyoxylate-Ene Reaction Catalyzed by C2-symmetric Chiral Bis(Oxazoline)- Lanthanide Complexes. Changtao Qian and Longcheng Wang Tetrahedron: Asymmetry, 2000, 11, 2347-2357 10 75 6. Addition of Silyl Ketene Acetals to Nitrones Catalyzed by Lanthanide Triflates Changtao Qian and Longcheng Wang Tetrahedron, 2000, 56, 7193-7197 86 7. Lanthanide Triflate Catalyzed Biginelli Reaction. One-Pot Synthesis of Dihydropyrimidinones under Solvent-Free Conditions. Yun Ma, Changtao Qian, Limin Wang and Min Yang J. Org. Chem., 2000, 65, 3864-3868 91 8. Cs-Symmetric ansa-Lanthanocenes Designed for Stereospecific Polymerization of Methyl Methacrylate, Synthesis and Structural Characterization of Silylene-Bridged Fluorenyl Cyclopentadienyl Lanthanide Halides, Amides and Hydrocarbyls. Changtao Qian, Wanli Nie and Jie Sun Organometallic, 2000, 19, 4134-4140 96 9. Stereoselective Synthesis and Structural Characterization of rac-Planar Chiral Bis(2methoxyethylindenyl)lanthanum and Yttrium Tetrahydroborates. Chang-Tao Qian, Gang Zou, Wan-Li Nie, Jie Sun, Dmitri A. Lemenovskii and Maxim V. Borzov Polyhedron, 2000, 19, 1955-1959 103 10. Synthesis and Strcture of Barium Complex Containing 2,2,6,6-Tetramethyl-3,5heptanedionate and 1,10-Phenanthroline Ligands Xie Mei-Hua,Qian Chang-Tao,Gao Li-Jun,Sun Jie Chinese J.Struct.Chem., 2000, 19, 419-422 108 11. Synthesis of Furo[3,2-c]and Pyrano[3,2-c] Quinolines by Lanthanide Triflate Catalyzed Imino-Diels-Alder Reaction Yun Ma, Changtao Qian, Mei-Hua Xie and Sun Jie Chin. J. Chem., 2000, 18, 377-383 112 11 12. 后过渡金属催化剂催化乙烯聚合 邹丰楼，李阳，邹晓天，宋玉春， 钱长涛， 陈瑞芳，陆汉章 合成树脂及塑料，2000，17(1), 60 课题负责人：麻生明 119 课题编号： 2000-03 1. Stepwise -Bromination of 1,1-Dihaloalkenes Shengming Ma*, Bin Xu, and Shimin Zhao Synthesis 2000, 139-143. 121 2. Pd(0)-catalyzed Cyclization Reaction of Aryl or 1-Alkenyl Halides with 1,2-Dienyl Ketones. A General and Efficient Synthesis of Polysubstituted Furans Shengming Ma* and Junliang Zhang Chem. Commun. 2000, 117-118. 126 3．Unusual Regioselectivity of Pd(0)-Catalyzed Coupling Reaction of Electron-deficient Alkenyl Halides with Allenic/Propargylic Zinc Reagents. Highly Selective Synthesis of 6-Phenylhex-5-yn-2(or 3)-enoates/enitriles and 4-Phenyl-6-substitutedhexa-2,4,5trienoates Shengming Ma*, Aibin Zhang, Yihua Yu, and Wei Xia J. Org. Chem. 2000, 65, 2287-2291. 128 4. AlX3-H2O-promoted Hydrohalogenation Reaction of 1,2-Allenic Sulfoxides Shengming Ma* and Qi Wei Eur. J. Org. Chem. 2000, 1939-1943. 133 5. Palladium(II)-Catalyzed Cyclization Reaction of Allylic Bromides with 1,2-Dienyl Ketones. An Efficient Synthesis of 3-Allylic Polysubstituted Furans Shengming Ma* and Lintao Li Organic Letters 2000, 2, 941-944. 138 12 6. Palladium(0)-catalyzed Cyclization Reaction of Polymer-Supported Aryl Iodides with 1,2-Allenyl Carboxylic Acids. A Facile Solid Phase Synthesis of Butenolides Shengming Ma,* Dehui Duan, and Zhangjie Shi Organic Letters 2000, 2, 1419-1422. 142 7．Reverse of Regioselectivity in Intramolecular Nucleophilic Substitution of –Allyl Palladium Species. Highly Selective Formation of Vinylic Cyclopropanes via the Pd(0)–Catalyzed Coupling-Cyclization Reaction of Organic Iodides with 2-(2’,3’Dienyl)malonates Shengming Ma* and Shimin Zhao Organic Letters 2000, 2, 2495-2497. 146 8. Efficient Synthesis of 4-(2'-Alkenyl)-2,5-dihydrofurans via PdCl2-catalyzed Coupling-Cyclization Reaction of 2,3-Allenols with Allylic Halides Shengming Ma* and Wenzhong Gao Tetrahedron Lett. 2000, 41, 8933-8936. 149 9. Studies on the Oxidative Addition Reaction of 1,1-Dibromo-1-alkenes, Dehalopalladation, and the Intramolecular Bis(carbopalladation) Reaction of Alkenes. An Efficient Entry to Fused Bicycles Shengming Ma*, Bin Xu, and Bukuo Ni J. Org. Chem. 2000, 65, 8532-8543. 153 10. Unique Selectivity of Iodohydroxylation Reaction of Allenyl Phenyl Sulfoxides in Aqueous MeCN. A Stereodefined Synthesis of (E)-2-Iodo-3-hydroxy-1-alkenyl Sulfoxides Shengming Ma*, Qi Wei, and Haiming Wang Organic Letters 2000, 2, 3893-3895. 165 13 11. Unexpected Facile Sequential Halolactamization-Hydroxylation of 2,3-Allenamides with CuX2 for the Efficient Synthesis of 4-Halo-5-hydroxypyrrol-2(5H)-ones Shengming Ma* and Hexin Xie Organic Letters 2000, 2, 3801-3803. 168 12. Review: Recent Progress in Carbolithiation Reaction (碳锂化反应的研究进展) Bin Xu and Shengming Ma* Chin. J. Org. Chem. (有机化学) 2000, 20, 54-63. 171 13. Synthesis and Structure of the First Propeller-shaped Helical Coordination Polymer of Ag+ with Bis(oxazoline) Ligands Shengming Ma* and Shulin Wu Chin. J. Chem. 2000, 18, 444-446. 181 14. Review: Recent Advances in Meta-mediated Synthesis of Substituted Furans (金属催化合成呋喃衍生物的最新进展) Lintao Li and Shengming Ma* Chin. J. Org. Chem. (有机化学) 2000, 20, 701-711. 184 15. Synthesis and Reaction of 1,2-Allenyl Ketones (1,2-联烯基酮的合成与反应) Lintao Li and Shengming Ma* Chin. J. Org. Chem. (有机化学) 2000, 20, 850-860. 课题负责人：侯雪龙 195 课题编号： 2000-04 1. Ring-opening of N-Tosylaziridines with TMSN3 and TMSCN Triggered by TBAF: An Efficient and Convenient Route to Vicinal Diamines and -Aminoacid Jie Wu, Xue-Long Hou and Li-Xin Dai J. Org. Chem. 2000, 65, 1344-1348. 206 14 2. On the Role of Planar Chirality: a Tunable Enantioselectivity in Palladium-Catalyzed Allylic Alkylation with Planar Chiral 1,1’-P,N-ferrocene Ligands Wei-Ping Deng, Xue-Long Hou, Li-Xin Dai, Yi-Hua Yu and Wei Xia Chem. Commun. 2000, 285-286. 3. 211 Synthesis of 2-(a-Substituted N-Tosylaminomethyl)-2,5-Dihydrofurans by Reaction of N-Sulfonylimines with Arsonium or Sulfonium 4-Hydroxyl-cis-2-butenylides Wei-Ping Deng, An-Hu Li, Li-Xin Dai , and Xue-Long Hou Tetrahedron 2000, 56, 2967-2974. 4. 213 Synthesis of Planar Chiral Selenide Derivatives of Ferrocenyl-oxazoline and Their Application in Enantioselective Palladium Catalyzed Allylic Substitution Reaction Shu-Li You, Xue-Long Hou and Li-Xin Dai Tetrahedron: Asymmetry 2000, 11, 1495-1500. 5. 221 A Stereoselective Michael-imino Aldol Tandem Reaction Triggered by Thiolate Anions Xiao-Fang Yang, Xue-Long Hou and Li-Xin Dai Tetrahedron Lett. 2000, 41, 4431-4434. 6. 227 Novel N,S- and N,Se-Planar Chiral [2,2]Paracyclophane Ligands: Synthesis and Application in Pd-Catalyzed Allylic Alkylation Xue Long Hou, Xun Wei Wu and Li Xin Dai Chem. Commun. 2000, 1195-1196. 7. 231 Efficient Planar Chiral 1,1’-P,N-2-Substituted Ferrocene Ligands for Asymmetric Heck Reaction: Control of Enantioselectivity and Configuration by Planar Chiral Substituent Wei Ping Deng, Xue Long Hou and Li Xin Dai Chem. Commun. 2000, 1483-1484. 233 15 8. Novel Bis-N-[2-(diphenylphosphino)ferrocenylcarbonyl]-diaminocyclohexane Ligands: Application in Asymmetric Allylic Alkylation of Imino Ester with Simple Allyl Carbonate Shu-Li You, Xue-Long Hou, Li-Xin Dai, Bo-Xun Cao and Jie Sun Chem. Commun. 2000, 1933-1934. 9. 235 硫叶立德途径立体控制合成乙烯基型环氧化合物 周永贵，李安虎，戴立信，侯雪龙 化学学报 2000, 58, 473-480. 237 10. Fructose Derived Pyridyl Alcohol Ligands: Synthesis and Application in the Asymmetric Diethylzinc Addition to Aldehydes Yong-Gui Zhou, Li-Xin Dai and Xue Long Hou Chinese J. Chem. 2000, 18, 121-123. 课题负责人：沈延昌 245 课题编号： 2000-05 1. Novel Base-catalyzed Olefination Methodology. Stereoselective Synthesis of (E)--benzenesulfinyl Vinylphosphonates Yanchang Shen, Guo-Fang Jiang Synthesis, 2000, 99-102. 248 2. Sequential Transformations of Phosphonates. "One-pot Synthesis of Ethoxycarbonyl Allyl Substituted Oxime Ethers Yanchang Shen, Guo-Fang Jiang Synthesis, 2000, 502-504. 252 3. Stereocontrolled Synthesis of Fluorinated E- or Z- Allylic Phosphonates Yanchang Shen, Yuming Zhang, Zenghong Zhang Synthesis, 2000, 1535-1538. 255 16 4. Stereoselective Synthesis (E)-4-Cyano--Unsaturated Nitriles Yanchang Shen, Zenghong Zhang Synth. Commun. 2000, 30, 445-453. 259 5. A Convenient Synthesis of (E)--Cyano and (E)--ethoxycarbonyl vinylphosphonates Yanchang Shen, Guo-Fang Jiang J. Chem. Res. (s) 2000, 140-141. 268 6. New Synthetic Methodologies for Carbon-Carbon Multiple Bond Formation Shen Yan-chang Acta Chimica Sinica, 2000, 58, 253-261. 课题负责人：陈家碧 270 课题编号：2000-06 1．Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Carbonylmetal Anions Containing Cyclopentadienyl, PPh3, and NO Ligands. A Route to Dimetal Bridging Carbene and Carbyne Complexes Yongjun Tang, Jie Su, Jiabi Chen* Organometallics, 2000, 19, 72-80. 279 2．Reactions of Cationic Bridging Carbyne Complexes of Bis(-cyclopentadienyl)diiron Tricarbonyl with Nucleophiles. A Route to Diiron Bridging Carbene Complexes Yajun Liu, Ruito Wang,, Jie Su, Jiabi Chen* Organometallics, 2000, 19, 3498-3506. 288 3. Unusual Reactions of Cationic Bridging Carbyne Complexes of Bis(5cyclopentadienyl)diiron Tricarbonyl with Carbonylmetal Anions. A Route to Diiron Bridging Carbyne Complexes Yajun Liu, Ruitao Wang, Jie Sun, and Jiabi Chen* 17 Organometallics, 2000, 19, 3784-3791. 297 4. Remarkable Transformtion of Thiophene Ligands in Their Pentamethylcyclopentadienyl Iridium (Cp*Ir) Coplexes Jiabi Chen,* Robert J. Angelici Coordination Chemistry Reviews, 2000, 206, 63-99. 304 5. Reactions of Di--carbonyl-cis--(1-5-:1-5--dicyclopentadienyldimethylsilane)bis(carbonyliron) with Aryllithium Reagents. Crystal Structures of [Fe2(-CO){-C(OC2H5)C6H5}(CO)2{(5-C5H4)2Si(CH3)2}] and [Fe2(-CO){C(OC2H5)C6H4OCH3-p}(CO)2{(5-C5H4)2Si(CH3)2}] Ruitao Wang, Jie Sun, Jiabi Chen* J. Organomet. Chem., 2000, 617, 1-9. 课题负责人：邓敏智 341 课题编号： 2000-07 1. Silver Oxide Mediated Palladium-catalyzed Cross-coupling Reaction of Cyclopropylboronic Acids with Allylic Bromides Han Chen and Min-zhi Deng J. Org. Chem. 2000, 65, 4444 ~ 4446. 350 2. Facile Approach to 4-substituted 2(5)H-furanones Min-Liang Yao and Min-zhi Deng J. Org. Chem. 2000, 5034 ~ 5036. 353 3. A Novel Stereocontrolled Synthesis of 1,2-trans Cyclopropyl Ketones via Suzuki-type Coupling of Acids Chlorides with Cyclopylboronic Acids Han Chen and Min-zhi Deng Organic Letters 2000, 2 (12), 1649 ~ 1651. 18 356 4. A Practical Approach to Stereodefined Cyclopropyl-substituted Heteroarenes using Suzuki-type Reaction Min-Liang Yao and Min-zhi Deng New. J. Chem. 2000, 24, 425 ~428. 359 5. Palladium-catalyzed Cross-coupling Reaction of Cyclopropylboronic Acids with Aryl Triflates Min-Liang Yao and Min-zhi Deng. Synthesis 2000, 8, 1095 ~ 1100. 363 6. A Novel Route to Stereodefined Cyclopropyl-substituted Alkenes Shao-Man Zhou and Min-zhi Deng Tetrahedron Letters 2000, 41, 3951 ~ 3954. 369 7. Palladium-catalyzed Cross-coupling of Cyclopropylboronic Acids with Alkenyl Triflates Min-Liang Yao and Min-zhi Deng Tetrahedron Letters 2000, 41, 9083 ~ 9087. 373 8. A Novel and Convenient Method to 4-Substituted Coumarins Min-Liang Yao and Min-zhi Deng Heteroatom Chemistry 2000, 11 (6), 380 ~ 382. 378 9. A Novel Suzuki-type Cross-coupling Reaction of Cyclopropylboronic Esters with Benzyl bromides Han Chen and Min-zhi Deng J. Chem. Soc. Perkin Trans I 2000, 1609 ~ 1613. 381 10. Nickle-catalyzed Allylation of Lithium 1-Alkynyl(trialkoxy)borates with 1,3Substituted Allyl Carbonates Han Chen and Min-zhi Deng J. Organomet. Chem. 2000, 603, 189 ~ 193. 19 386 课题负责人：姜 标 课题编号： 2000-08 1. Stereocontrolled Synthesis 22E, 24(S)-Trifluoromethyl Sidechain of Steroid and Its Application in Synthessis of Fluorinated Analugues Natural Occuring Sterols B. Jiang, Y. Liu, Zhou Weishang, J. Org. Chem, 2000, 65, 6231-6236. 391 2. 1,3-Dipolar Cyloaddtion of Chially Modified Vinylboronic Ester with Ntrile Oxides Biao Jiang, Ao Zhang, Ying Kan, Gui-ling Zhao and Biao Jiang Tetrahedron, 2000, 56, 965-970. 397 3. C2-Symmetric Bisphoshoine and a Bisaminophosphine as New Chiral Ligands for Pd-catalyzed Asymmetric Allylic Substitution Ao Zhang, Yan Feng, Biao Jiang Tetrahedron: Asymmetry, 2000, 11, 3123-3130. 403 4. Solid Phase Asymmtric Synthesis of 2-Isoxazoline Ning Zhou, Biao Jiang, J. Com.. Chem., 2000, 2(1), 6-7 411 5. Syntheses and Cytotoxicity Evaluation of Bis(indolyl)thiazole, Bis(indoly)pyrazinone and Bis(indolyl)pyrazine: Analogues of Cytotoxic Marine Bis(indole) Alkaloid Biao Jiang* and Xiao-Hui Gu Bioorganic & Medicinal Chemistry, 2000, 8, 363-371. 413 6. Syntheses of Indoylpyrimidine via Cross Coupling of Indolylboronic Acid with Chloropyrimidines: Facile Synthesis of Merdianin D Biao Jiang, Caiguang Yang Heterocycles, 2000, 53(7), 1559-1568. 422 20 7. Syntheses of Bis(3-indolyl)pyrazinone Biao Jiang, Xiao-Hui Gu Heterocycles, 2000, 53(7), 1489-1498. 432 8. Highly Enatiooselective Reduction of Achral with NaBH4/Me3SiCl Catalyyzed by (S)-diphenylpyrrolidinemethyanol Biao Jiang, Yan Feng, Jian Zheng Tetrahedron Letters, 2000, 52, 10281-10283. 442 9. Synthesis of Novel Compatibilizers and Their Application in PP/nylon-66 Blends.I. Synthesis and Characterization De-Liang Xiea,*, Da Chenb, Biao Jianga, Chang-Zheng Yangc Polymer, 2000, 41, 3599-3607. 445 10. In situ NMR Study of Asymmetric Borane Reduction Reaction-an Abnormal Factor in the Temperature Effect on the Bis-oxazaborolidine Catalust and the Relationship between the Catalyst Structure and Selectivity Jinkai Zhao,a Xinhe Bao,a,* Xiumei Liu,a and Biao Jiangb Tetrahedron: Asymmetry, 2000, 11, 3351-3359. 454 11. Asymmetric 1,3-dipolar Cyloaddtion of Nitrile Oxides to Acryloyl Esters Dearing Glucofuranose as Auxiliary Biao Jiang, Ao Zhang,Ying Kan, Chin. J. Chem., 2000, 18(2), 200-224. 463 12. 新型海洋双吲哚类生物碱的研究进展 谷晓辉 姜标* 有机化学, 2000, 20, 168-177. 468 21 13. 羟基酸引发-己内酯开环聚合的研究 解德良,姜标 高分子学报, 2000, 5, 532-537. 478 14. The Mechanism of Asymmetric Reduction of by Catalytyzed by A C2-Symmetric is Amino Alcohol Catalyst Jinkai Zhao, Xiuwen Han, Xiumaei Liu, Xinhe Bao, Jian Feng Hang,and Biao Jiang Science in China, 2000, 43, 1 41-150. 课题负责人：施 敏 484 课题编号： 2000-09 1. An Unexpected Carbon Dioxide Insertion in the Reaction of Trans-2,4-Disubstituted Azetidine, Trans-2,5-Disubstituted Pyrrolidine, or Trans-2,6-Disubstituted Piperidine with Diphenylthiophosphinic Chloride and Diphenylselenophosphinic Chloride. Min Shi,* Jian-Kang Jiang, Yu-Mei Shen, Yan-Shu Feng, and Gui-Xin Lei J. Org. Chem., 2000, 65, 3443-3448. 495 2. The Crystallographic Structure of a Novel Camphanic Amide. Min Shi* and Gui-Xin Lei J. Chem. Crystallography, 1999, 29, 1211-1213. 501 3. Chiral Diphenylthiophosphoramides: A New Class of Chiral Ligands for the Silver (I)Promoted Enantioselective Allylation of Aldehydes. Min Shi* and Wen-Sheng Sui Tetrahedron:Asymmetry, 2000, 11, 773-779. 504 4. Chiral Diphenylselenophosphoramides: a New Class of Chiral Ligands for the Titanium(IV) Alkoxide-promoted Addition of Diethylzinc to Aldehydes. Min Shi* and Wen-Sheng Sui Tetrahedron:Asymmetry, 2000, 11, 835-841. 22 511 5. A Facile Route to Bulladecin Type Acetogenins. Total Synthesis of Asimilobin and Correction of Its Tetrahydrofuran Segment' s Configuration. Zhi-Min Wang,* Shi-Kai Tian and Min Shi* Eur. J. Org. Chem., 2000, 349-356. 518 6. Amendment in Titanium(IV) Chloride and Chalcogenide-Promoted Baylis-Hillman Reaction of Aldehydes with -Unsaturated Ketones. Min Shi* and Jian-Kang Jiang Tetrahedron, 2000, 56, 4793-4797 . 526 7. Synthesis of a Novel Chiral Ruthenium Complex and Its Crystal Structure. Min Shi,* Kazuya Kobiro, Tomomi Fujita J. Organometal. Chem., 2000, 605, 134-138. 531 8. Titanium(IV) Chloride and Amine-promoted Baylis-Hillman Reaction. Min Shi,* Jian-Kang Jiang and Yan-Shu Feng Org. Lett., 2000, 2, 2397-2400. 536 9. A Simple Synthetic Method for Chiral 1,2-Epoxides and the Total Synthesis of a Chiral Pheromone Epoxide. Zhi-Bo Zhang, Zhi-Min Wang,* Yu-Xiu Wang, Huan-Quan Liu, Gui-Xin Lei and Min Shi, J. Chem. Soc., Perkin Trans 1, 2000, 53-57. 540 10. Total Synthesis of Gigantetrocin A. Zhi-Min Wang,* Shi-Kai Tian and Min Shi.* Chirality, 2000, 12, 581-589. 545 11. Trifluoromethanesulfonamide, Diphenylphosphoramide and Diphenyl-thiophosphoramide of (R)-(+)-1,1'-Binaphthyl-2,2'-diamine as Chiral Catalyst Ligands for the Titanium(IV) Alkoxide-Promoted Addition of Diethylzinc to Aldehydes. 23 Min Shi* and Wen-Sheng Sui Chirality, 2000, 12, 574-580. 554 12. The Crystallographic Structure of 4-hydroxy-3-methylene-4-(p-nitrophenyl)butan-2one. Min Shi* and Jian-Kang Jiang J. Chem. Crystallography, 1999, 29, 1295-1297. 561 13. A New Class of Chiral Pyrrolidine Ligands for Homogeneous Catalytic Enantioselective Cyclopropanation of Styrene Min Shi* and Jian-Kang Jiang Chin. J. Chem., 2000, 3, 407-410. 课题负责人：丁奎岭 564 课题编号： 2000-10 1. Reduction of 1,1’-Binaphthyls to Octahydro-1,1’-binaphthyl Derivatives with Raney Ni-Al alloy in Aqueous Solution Hui Guo, Kuiling Ding Tetrahedron Lett., 2000, 41, 10061-10064 568 2. Practical Method and Novel Mechanism for Optical Resolution of BINOL by Molecular Complexation with N-benzylcinchonium Chloride Y. Wang, J. Sun, Kuiling Ding Tetrahedron, 2000, 56，4447-4451 572 3. Synthesis of Novel N, P Chiral Ligands for Palladium-catalyzed Asymmetric Allylation: The Effect of Binaphthyl Backbone on the Enantioselectivity Yi Wang, Hui Guo, Kuiling Ding Tetrahedron: Asymmetry, Lett. 2000, 11, 4153-4162. 24 577 4. The Synthesis of Novel Non-C2 Symmetric H4-BINOL Ligand and Its Application to Titanium-catalyzed Enantioselective Addition of Diethylzinc to Aldehydes X. Shen, H. Guo, K. Ding Tetrahedron: Asymmetry, 2000, 11, 4321-4327. 587 5. 催化不对称反应新进展—不对称活化（综述与进展） 丁奎岭、林国强 有机化学， 2000，20， 1-10 594 6. 催化不对称反应新进展—组合化学方法之应用（综述与进展） 丁奎岭 有机化学，2000，20，613-622 课题负责人：唐 勇 604 课题编号： 2000-11 1. Switching of Stereoselectivity: Dramatic Effects of HMPA on the Stereoselectiviy of Cyclopropanation Reaction of Silylated Tellronium Allylide with ,-Unsaturated Esters and Amides Ye, S.; Tang, Y.*; Dai, L. X J. Org. Chem., 2000, 6257-6260. 课题负责人： 廖世健 614 课题编号： 2000-12 1. 水滑石选择性催化合成三乙二醇单丁醚 刘金龙，王永杰，廖世健, 王复东, 徐杰，魏同成 催化学报. 2000, 21, 283-285. 618 2. PVP-Pd 催化六氯苯加氢脱氯中两种氢源的贡献 高燕，廖世健, 徐杰, 上官勇刚, 顾志祥，蹇锡高 催化学报. 2000, 21, 378-380. 621 25 课题负责人： 宋礼成 课题编号： 2000-13 1. Synthesis of Double and Quadruple Butterfly Fe/SCluster Complexes via a Novel Type of Reaction of Anions (-RS)(-S-)[Fe2(CO)6]2(4-S) with Succinyl Chloride. Li-Cheng Song , Guo-Liang Lu, Qing-Mei Hu, and Jie Sun Organmetallics 1999, 18, 5429-5431. 课题负责人： 黄 宪 624 课题编号： 2000-14 1. Hydrozirconation of Alkynyl Sulfoxides: the Reactions of Zirconated Vinyl Sulfoxide Intermediates Ping Zhong, Xian Huang, Meng-Ping Guo Tetrahedron, 2000, 56, 8921-8925. 课题负责人： 沈 琪 627 课题编号： 2000-15 1. Synthesis of Indenyllanthanide Amides: the Effective Initiators for Polymerization of Methyl Methacrylate. Zhao Qun, Yao Ying-Ming, Shen Qi Chin. J. Chem., 2000, 18(6), 877-881. 课题负责人： 康北笙 632 课题编号： 2000-16 1. Chemistry of Aroylhydrazones II. Enol-form Coordination of 4,5-Diazafluorene-9-one salicyloylhydrazone (H2L) to Transition Metals and Crystal Structures of H2L, Mn(HL)2(H2O)2 and Co(HL)2(DMF)2 Xiao, W., Lu, Z. L., Wang, X. J., Su, C. Y., Yu, K. B., Liu, H. Q., Kang, B. S. Polyhedron, 2000, 19(13), 1295-1304. 637 2. 4,5-Diazafluorene-9-one Acylhydrazones and their Lead Complexes and the Crystal 26 Structure of Hydrated 4,5-Diazafluorene-9-one 3-methoxybenzoylhydrazone Supported by Extensive Hydrogen Bonds and Aromatic Ring Stacking Interactions Xiao, W., Lu, Z. L., Deng, L. R., Su, C. Y., Tong, Y. X., Liu, H. Q., Kang, B. S. Polish J. Chem., 2000, 74, 1211-1220. 647 3. Bivalent Transition Metal Complexes of 4,5-Diazofluorenone Benzoylhydrazone (HL) and the Characterization of Weak Interactions in CoL2 . 2H2O Xiao, W., Lu, Z. L., Su, C. Y., Yu, K. B., Deng, L. R., Liu, H. Q., Kang, B. S. J. Mol. Stru., 2000, 553, 91-99. 657 4. NMR Studies on 4,5-Diazafluorenone 2-Naphthalylhydrazone and its Lead Complex Xiao, W., Lu, Z. L., Kang, B. S., Liu,, H. Q., Su, C. Y. J. Chi. Magnetic Resonance, 2000, 17(4), 265-269. 课题负责人： 沈之荃 课题编号： 2000-17 课题负责人： 张永敏 课题编号： 2000-18 666 1. Samarium Diiodide Induced Reductive Cyclization of Nitro Compounds with Ketones: A Novel Synthesis of 3,4-Dihydro-(2H)-1,2,4-Benzothiadiazine-1,1Dioxides. Weihui Zhong, Xiaoyuan Chen, Yongmin Zhang* J. Chem. Res. (S), 2000, (6), 292-293. 671 2. A New Route to 2,3-Dihydro-1,5-Benzothiazepines from Niteodisulfides and α,βUnsaturated Ketones by SmI2. Xiaoyuan Chen, Weihui Zhong, Yongmin Zhang J. Chem. Res. (S), 2000, (8), 386-387. 673 3. Samarium Diiodide Mediated Simultaneous reduction of Nitro Group and the Azide 27 Group in o-Nitrophenylazide: A New Access to 2,3-Dihydro-1H-1,5-Benzodiazepines Weihui Zhong, Yongmin Zhang* and Xiaoyuan Chen J. Chem. Res. (S), 2000, 532-534. 675 4. A Novel Method for Pinacolic Coupling of Aromatic Aldehydes and Ketones with a Sm-ZnCl2 System Hongyun Guo, Yongmin Zhang J. Chem. Res. (S), 2000, (6), 284-286. 678 5. A Novel Reduction of o-Nitrophenoxy Compounds Promoted by Low-Valent Titanium: An Access To 2H-1,4-Benzoxaine Derivatives Yongmin Ma, Yongmin Zhana J. Chem. Res. (S), 2000, (8), 388-389. 681 6. Sm/SmI2/TiCl4 (cat.) System Promoted Direct Alkylidenating Reaction of Ketones with gem-Dibromomethyl Sulfones: A New Method for Preparation of Alkylidene Sulfones YunKui Liu, Yongmin, Zhang*, Xi Liu J. Chem. Res. (S), 2000, 472-373. 683 7. Facile Synthesis of Amidines via Intermolecular Reductive Coupling of Nitriles with Azobenzene Promoted by Samarium Diiodide. Zhi Fang LI, Ping LU, Yong Min ZHANG Chin. Chem. Lett., 2000, 11(6): 495-498. 685 8. Low-valent Titanium Induced Reductive Cyclization of Nitro Compounds and Aliphatic Ketones: Facile Synthesis of 3,4-Dihdro-(2H)-1,2,4-Benzothiadiazine-1,1Dioxides Wei-Hui Zhong, Xiao-Yuan Chen, Yong-Min Zhang Chin. J. Chem., 2000, 18(5), 786-788. 689 课题负责人： 张良辅 课题编号： 2000-19 28 课题负责人： 刘汉范 课题编号： 2000-20 课题负责人： 王积涛 课题编号： 2000-21 课题负责人： 徐善生 课题编号： 2000-22 1. 1, 1’-双(四甲基环戊二烯基)二茂铁与五羰基铁和三乙腈三羰基钼的反应 邓小斌，徐善生，王佰全, 周秀中 高等学校化学学报，2000, 21, 898-902. 课题负责人： 周其林 课题编号： 2000-23 课题负责人： 曹卫国 课题编号： 2000-24 692 1. An Efficient and Highly Stereoselective Synthesis of-trans--Benzoyl--aryl-butyrolactones Cao Weiguo, Ding Weiyu, Chen Yali and Qiu Mengyao Synthetic Communications, 2000, 30(20), 3793-3799. 2. 697 An Efficient and Highly Stereoselective Synthesis of cis-1-Acetyl-2-aryl-6,6dimethyl-5,7-dioxo-spiro-[2,5]-4,8-octadiones and -trans--Acetyl--aryl-butyro lactones Cao Weiguo, Ding Weiyu, Chen Yali and Gao Jinsen Synthetic Communications, 2000, 30(24), 4523-4530 29 704 3. Study on the Reaction of cis-1-Acetyl-2-aryl-6,6-dimethyl-5,7-dioxo-spiro-[2,5]-4,8octadiones with Methanol Cao Weiguo, Ding Weiyu, Chen Yali and Gao Jinsen Synthetic Communications, 2000, 30(24), 4531-4541 712 4. 1,2,3-三取代环丙烷衍生物与甲醇反应的研究 曹卫国 丁维钰 童玮琦 刘欣 邱梦遥 高等学校化学学报, 2000, 21(5), 740-742. 课题负责人： 周锡庚 课题编号： 2000-25 课题负责人： 席振峰 课题编号： 2000-26 723 1. Efficient Synthesis of Cyclopentadienone Derivatives by the Reaction of Carbon Dioxide with 1,4-Dilithio-1,3-dienes Zhenfeng Xi* and Qiuling Song J. Org. Chem. 2000, 65, 9157-9159. 726 课题负责人： 江焕峰 课题编号： 2000-27 课题负责人： 庞 震 课题编号： 2000-28 1. Synthesis, Characterization and Electrochemical Properties of Substituted Halfsandwich Cobalt(I) Complexes Zhen Pang*, Xiufeng Hou, Zuen Huang, Ruifang Cai and Ruyi Ruan Synth. React. Inorg. Met.-Org. Chem, 2000, 8, 1459-1476. 30 729 2. The Crystal Structure and Reactivity of (5-C5H4COOCH2C6H5)Co(CO)I2 Zhen Pang*, Xiu-feng Hou, Rui-fang Cai, Xi-gen Zhou and Zu-en Huang Synth. React. Inorg. Met.-Org. Chem., 2000, 5, 877-895. 747 3. Synthesis and Structure of E-Z-(2,4,6-tri-tert-butylphenylphosphinyl)-2-[N- (tertbutyldimethylsilyl)-N-(p-chrolophenyl)]amino-1-(2,4,6-tri-tert-butyl-phenyl) phosphaethylene 张立新, 庞震*, 周锡庚, 蔡瑞芳, 黄祖恩 结构化学, 2000, 2, 86-90. 课题负责人： 张兆国 766 课题编号： 2000-29 31