不对称合成化学
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化学物理研究所研究员、催化基础国家重点实验室 主任，中法催化联合实验室中方主任，中国科学院 大连化学物理研究所学位委员会主任。中国化学会 催化委员会主任、中国物理学会光散射委员会主任、 国际催化学会理事会副主席、英国皇家化学会 Fellow。2003年当选中国科学院院士、2005年当选 第三世界科学院院士。中国科学院大连化学物理研 究所和日本东京工业大学联合培养理学博士。曾先 后在比利时新鲁汶大学、美国西北大学、英国利物 浦大学、日本东京大学和美国里海大学进行博士后 及短期访问教授的工作。主要从事催化材料、催化 反应和催化光谱表征研究工作。
Different grafting ways
Interaction Absorption
The confinement effect of the pore and surface
Various factors
Others
离子液体 反应控制相转移 温控相转移 等等
The examples in detail
P.-N. Liu, P.-M. Gu, J.-G. Deng, Y.-Q. Tu, Y.-P. Ma, Eur. J. Org. Chem. 2005, 15, 3221-3227
A Recyclable Fluorous (S)Pyrrolidine Sulfonamide Promoted Direct, Highly Enantioselective Michael Addition of Ketones and Aldehydes to Nitroolefins in Water
Asymmetric Iridium-Catalyzed Allylic Alkylation
A. Alexakis, D. Polet, Org. Lett. 2004, 6, 3529-3532
催化剂的固载
Materials-supported catalysts
男，1960年1月生，理学博士,中国科学院大连
在国内外学术刊物发表正式论文近300篇，其中200余篇发表在国际学术刊物上 。在国际 Elsevier Science B.V. 系列中主编论文集一本。申请中国发明专利35件（12件已授权）。国内 外学术会议邀请报告40余次。2004年在法国巴黎举行的第13届国际催化大会上(2100人) 做60 分钟大会特邀报告。已培养硕士、博士和博士后40余名。获得国家发明二等奖、中国科学院自 然科学二等奖、香港求是科技基金杰出青年学者奖、中国青年科学家奖等。2004年获得“国际 催化奖”（四年一次，每次一人），2005年获得何梁何利科学技术进步奖、中国科学院杰出科 技成就奖。任 “Journal of Catalysis”，“Journal of Molecular Catalysis A”， “Chemistry: An Asian Journal” 和“Catalysis Surveys from Asia”等7种国际刊物编委。任国内“中国科学 B”、“化学进展”、和“催化学报”等9种刊物编委，兰州大学、大连理工大学、中国科学技 术大学和北京大学等14所大学兼职教授和荣誉教授。被法国巴黎皮埃尔玛丽居里大学聘请为 2002/2003年度外聘教授。
1995年11月-1998年11月 郑州大学化学系教授
Synthesis on Catalysts Immobilized in Microporous and Mesoporous Materials
Assembling Ligands from Smaller Species Inside the Nanopores
(Ship-in-Bottle Method)
Immobilization of Mn(III)(salen) complex in zeolite Y by encapsulation
The further development
Intercalation of Layered Materials
For example
水滑石 Hydrotalcite-like Layered double hydroxides LDHs
Asymmetric Allylic Alkylation
B. M. Trost, G. Dong, J. Am. Chem. Soc. 2006, 128, 6054-6055
Famous chiral ligands
About the center metals
Among the metals that are used for this reaction, palladium is the most widely studied. However, despite the high enantioselectivities obtained with many other substrates, this metal gives preference to the linear instead of the branched product. The situation is different for complexes of Ir, Mo, Ru and W, which give regioselectivities in favor of branched products.
Li, X.; Wu, X.; Chen, W.; Hancock, F. E.; King, F.; Xiao, J. Org. Lett 2004; 6(19); 3321-3324
Water showed the accelerated role in the reaction!
The second example
NuH
R
OCOOMe
Nu
R
+R
Nu
branch
linear
Possible complexes of unsymmetrical systems
Pd-catalyzed AAA (Model reaction)
1. Asymmetric Allylic Substitution Reactions
Main points
Catalysts supported in Polymers Water-soluble catalysts Catalysts supported in organic or inorganic materials Catalysts Immobilized in Microporous and
1987年9月-1990年6月 南京大学化学系，理学博士。
其中1993年9月-1994年9月 日本龙谷大学理工学部博士后。
其中1997年9月-1998年9月 日本东京工业大学UNESCO研究员。
工作经历 Experience:
1990年10月-1992年6月 郑州大学化学系讲师
1992年11月-1995年 郑州大学化学系副教授
N,O-bis(trimethylsilyl)acetamide (BSA) 2. Pd-Catalyzed Asymmetric Allylic Amination Reactions
An example about Pd-c H.-F. Duan, B.-M. Fan, X. Cheng, L.-X. Wang, Q.-L. Zhou, Adv. Synth. Catal. 2004, 346, 625-637
Mesoporous Materials others
About polymer material
About water-soluble catalysts
Supported in inorganic materials
Encapsulation in Porous Supports
How to prepare the heterogeneous catalysts
丁奎岭研究员
1966年出生，中共党员，研究员。课题组长，1998年入选中科院“百人计划”,2000
年入选上海市“启明星”计划，获得2003年度国家杰出青年基金资助。
教育 Education:
1981年9月-1985年6月 郑州大学化学系，理学学士。
1985年9月-1987年6月 郑州大学化学系硕士研究生。
Born in Philadelphia, PA, in 1941 where he began his university training at the University of Pennsylvania (BA, 1962), Barry M. Trost obtained a Ph.D. degree in Chemistry just three years later at the Massachusetts Institute of Technology (1965). He directly moved to the University of Wisconsin where he was promoted to Professor of Chemistry in 1969 and subsequently became the Vilas Research Professor in 1982. He joined the faculty at Stanford as Professor of Chemistry in 1987. Professor Trost made a major contribution early in his career with the isolation, structure determination, and synthesis of the insect juvenile hormone which initiated the concept of insect growth regulants as an alternative to pesticides. Developing the tools, i.e., the reactions and reagents, that enhance selectivity and impart “atom economy” is the first stage. He has pursued this goal in many ways with a major thrust being the rational design of selective catalysts which may make them the “chemists’ enzymes”. Inserting sulfur substituents to impart synthetic versatility has created the concept of organosulfones as chemical chameleonssi.e., serving as both nucleophiles and electrophiles depending upon the environment. Over 100 total syntheses of divergent molecules ranging from antitumor agents to electrical conductors have been completed.
不对称合成化学
asymmetric synthetic chemistry
毛金成 苏州大学化学化工学院
第十三章 不对称烯丙基烷基化反应
Chapter 13 Asymmetric Allylic Alkylation Reactions (AAA)
B. M. Trost, D. L. V. Vranken, Chem. Rev. 1996, 96, 395-422.
Different grafting ways
Interaction Absorption
The confinement effect of the pore and surface
Various factors
Others
离子液体 反应控制相转移 温控相转移 等等
The examples in detail
P.-N. Liu, P.-M. Gu, J.-G. Deng, Y.-Q. Tu, Y.-P. Ma, Eur. J. Org. Chem. 2005, 15, 3221-3227
A Recyclable Fluorous (S)Pyrrolidine Sulfonamide Promoted Direct, Highly Enantioselective Michael Addition of Ketones and Aldehydes to Nitroolefins in Water
Asymmetric Iridium-Catalyzed Allylic Alkylation
A. Alexakis, D. Polet, Org. Lett. 2004, 6, 3529-3532
催化剂的固载
Materials-supported catalysts
男，1960年1月生，理学博士,中国科学院大连
在国内外学术刊物发表正式论文近300篇，其中200余篇发表在国际学术刊物上 。在国际 Elsevier Science B.V. 系列中主编论文集一本。申请中国发明专利35件（12件已授权）。国内 外学术会议邀请报告40余次。2004年在法国巴黎举行的第13届国际催化大会上(2100人) 做60 分钟大会特邀报告。已培养硕士、博士和博士后40余名。获得国家发明二等奖、中国科学院自 然科学二等奖、香港求是科技基金杰出青年学者奖、中国青年科学家奖等。2004年获得“国际 催化奖”（四年一次，每次一人），2005年获得何梁何利科学技术进步奖、中国科学院杰出科 技成就奖。任 “Journal of Catalysis”，“Journal of Molecular Catalysis A”， “Chemistry: An Asian Journal” 和“Catalysis Surveys from Asia”等7种国际刊物编委。任国内“中国科学 B”、“化学进展”、和“催化学报”等9种刊物编委，兰州大学、大连理工大学、中国科学技 术大学和北京大学等14所大学兼职教授和荣誉教授。被法国巴黎皮埃尔玛丽居里大学聘请为 2002/2003年度外聘教授。
1995年11月-1998年11月 郑州大学化学系教授
Synthesis on Catalysts Immobilized in Microporous and Mesoporous Materials
Assembling Ligands from Smaller Species Inside the Nanopores
(Ship-in-Bottle Method)
Immobilization of Mn(III)(salen) complex in zeolite Y by encapsulation
The further development
Intercalation of Layered Materials
For example
水滑石 Hydrotalcite-like Layered double hydroxides LDHs
Asymmetric Allylic Alkylation
B. M. Trost, G. Dong, J. Am. Chem. Soc. 2006, 128, 6054-6055
Famous chiral ligands
About the center metals
Among the metals that are used for this reaction, palladium is the most widely studied. However, despite the high enantioselectivities obtained with many other substrates, this metal gives preference to the linear instead of the branched product. The situation is different for complexes of Ir, Mo, Ru and W, which give regioselectivities in favor of branched products.
Li, X.; Wu, X.; Chen, W.; Hancock, F. E.; King, F.; Xiao, J. Org. Lett 2004; 6(19); 3321-3324
Water showed the accelerated role in the reaction!
The second example
NuH
R
OCOOMe
Nu
R
+R
Nu
branch
linear
Possible complexes of unsymmetrical systems
Pd-catalyzed AAA (Model reaction)
1. Asymmetric Allylic Substitution Reactions
Main points
Catalysts supported in Polymers Water-soluble catalysts Catalysts supported in organic or inorganic materials Catalysts Immobilized in Microporous and
1987年9月-1990年6月 南京大学化学系，理学博士。
其中1993年9月-1994年9月 日本龙谷大学理工学部博士后。
其中1997年9月-1998年9月 日本东京工业大学UNESCO研究员。
工作经历 Experience:
1990年10月-1992年6月 郑州大学化学系讲师
1992年11月-1995年 郑州大学化学系副教授
N,O-bis(trimethylsilyl)acetamide (BSA) 2. Pd-Catalyzed Asymmetric Allylic Amination Reactions
An example about Pd-c H.-F. Duan, B.-M. Fan, X. Cheng, L.-X. Wang, Q.-L. Zhou, Adv. Synth. Catal. 2004, 346, 625-637
Mesoporous Materials others
About polymer material
About water-soluble catalysts
Supported in inorganic materials
Encapsulation in Porous Supports
How to prepare the heterogeneous catalysts
丁奎岭研究员
1966年出生，中共党员，研究员。课题组长，1998年入选中科院“百人计划”,2000
年入选上海市“启明星”计划，获得2003年度国家杰出青年基金资助。
教育 Education:
1981年9月-1985年6月 郑州大学化学系，理学学士。
1985年9月-1987年6月 郑州大学化学系硕士研究生。
Born in Philadelphia, PA, in 1941 where he began his university training at the University of Pennsylvania (BA, 1962), Barry M. Trost obtained a Ph.D. degree in Chemistry just three years later at the Massachusetts Institute of Technology (1965). He directly moved to the University of Wisconsin where he was promoted to Professor of Chemistry in 1969 and subsequently became the Vilas Research Professor in 1982. He joined the faculty at Stanford as Professor of Chemistry in 1987. Professor Trost made a major contribution early in his career with the isolation, structure determination, and synthesis of the insect juvenile hormone which initiated the concept of insect growth regulants as an alternative to pesticides. Developing the tools, i.e., the reactions and reagents, that enhance selectivity and impart “atom economy” is the first stage. He has pursued this goal in many ways with a major thrust being the rational design of selective catalysts which may make them the “chemists’ enzymes”. Inserting sulfur substituents to impart synthetic versatility has created the concept of organosulfones as chemical chameleonssi.e., serving as both nucleophiles and electrophiles depending upon the environment. Over 100 total syntheses of divergent molecules ranging from antitumor agents to electrical conductors have been completed.
不对称合成化学
asymmetric synthetic chemistry
毛金成 苏州大学化学化工学院
第十三章 不对称烯丙基烷基化反应
Chapter 13 Asymmetric Allylic Alkylation Reactions (AAA)
B. M. Trost, D. L. V. Vranken, Chem. Rev. 1996, 96, 395-422.