RUI: Asymmetric catalytic hydroamination of aminoallenes by chiral tantalum cyclopentadienyl-amide-alkoxide complexes

RUI：手性钽环戊二烯基-酰胺-醇盐络合物对氨基丙二烯的不对称催化氢氨化

• 批准号: 1012445
• 负责人: Adam Johnson
• 金额: $ 21.18万
• 依托单位: Harvey Mudd College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-09-01 至 2014-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1012445&HistoricalAwards=false
• 关键词: RUI; Asymmetric; catalytic; hydroamination; aminoallenes

The Chemical Catalysis Program supports Professor Adam R. Johnson at Harvey Mudd College who will examine enantioselective hydroamination catalysis and stereoselective polymerization of lactide, which are two areas of significant current interest. The proposed research will examine the hydroamination reaction, which is the addition of a nitrogen-hydrogen bond across a carbon-carbon multiple bond. The highly atom-economical method produces substituted amines that are valuable synthetic targets. A number of metals catalyze this reaction but there are no general methods for it. The asymmetric hydroamination of aminoallenes using titanium complexes of bidentate aminoalcohol ligands gives good regioselectivity, but poor stereoselectivity. The corresponding tantalum complexes have recently been shown to be more stereoselective. The PI and his coworkers will synthesize novel chiral ligands tethered to a chiral amino-alcohol and rapidly screen them, synthesize and study titanium and tantalum complexes with these chiral ligands, and perform catalytic hydroaminations with tethered and untethered ligands. The chiral amino-alcohol complexes will also be used to polymerize the biologically derived monomer, lactide. As a biodegradable polymer based on a renewable feedstock, the development of efficient catalysts for the synthesis of polylactide with varying tacticity is of great importance. If successful, both areas of research will have a transformative impact.With the support of the Chemical Catalysis Program in the Chemistry Division at the National Science Foundation, Dr. Adam R. Johnson's continued research on hydroamination will have an impact on teaching at the frontiers of organometallic chemistry and will extend to a wide community of inorganic chemistry educators. The results from this research will affect Professor Johnson's teaching of inorganic and organometallic chemistry at Harvey Mudd College and his participation in the NSF-funded VIPEr project (www.ionicviper.org), an on online teaching and networking site for inorganic chemistry. Undergraduate students will have an opportunity to examine modern problems in synthetic organometallic chemistry, synthesize and purify the ligands and complexes, grow crystals, and perform the catalytic reactions. Students will gain experience in creative problem solving and teamwork, and will present their research results both locally and at a national American Chemical Society Meeting.

化学催化项目支持哈维穆德学院的 Adam R. Johnson 教授，他将研究对映选择性氢胺化催化和丙交酯的立体选择性聚合，这是当前重要的两个领域。拟议的研究将检查加氢胺化反应，该反应是在碳-碳多重键上添加氮-氢键。这种高度原子经济的方法产生的取代胺是有价值的合成目标。许多金属可以催化该反应，但没有通用的方法。使用二齿氨基醇配体的钛配合物对氨基丙二烯进行不对称氢氨化，具有良好的区域选择性，但立体选择性较差。相应的钽配合物最近已被证明具有更高的立体选择性。首席研究员和他的同事将合成与手性氨基醇相连的新型手性配体并快速筛选它们，合成和研究与这些手性配体的钛和钽配合物，并用束缚和非束缚配体进行催化加氢胺化。手性氨基-醇复合物也将用于聚合生物衍生单体丙交酯。作为基于可再生原料的可生物降解聚合物，开发用于合成不同立构规整度聚丙交酯的高效催化剂具有重要意义。如果成功，这两个领域的研究都将产生变革性的影响。在美国国家科学基金会化学部化学催化项目的支持下，Adam R. Johnson 博士对氢氨化的持续研究将对有机金属化学前沿的教学产生影响，并将扩展到广泛的无机化学教育工作者群体。这项研究的结果将影响约翰逊教授在哈维穆德学院的无机和有机金属化学教学，以及他对 NSF 资助的 VIPEr 项目 (www.ionicviper.org) 的参与，该项目是一个无机化学在线教学和网站。本科生将有机会研究合成有机金属化学的现代问题，合成和纯化配体和络合物，生长晶体并进行催化反应。学生将获得创造性解决问题和团队合作的经验，并将在当地和美国化学会全国会议上展示他们的研究成果。