SusChEM: The Use of Ti-C Bonds for RNC Insertions and Dynamic Kinetic Resolutions

SusChEM：使用 Ti-C 键进行 RNC 插入和动态动力学分辨率

• 批准号: 1664566
• 负责人: Jack Norton
• 金额: $ 44万
• 依托单位: Columbia University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-08-01 至 2020-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664566&HistoricalAwards=false
• 关键词: SusChEM; Use; Ti; Bonds; RNC

In this project, funded by the Chemical Structure, Dynamics, & Mechanisms B Program of the National Science Foundation, Professor Jack R. Norton at Columbia University leads a team exploring fundamental issues in organotitanium chemistry. Titanium, inexpensive and nontoxic, offers sustainable ways of carrying out a variety of chemical transformations. This project aims to use inexpensive titanium-based reagents for the synthesis of valuable organic compounds - not only heterocycles but also the enantioenriched compounds essential to the pharmaceutical industry. This project involves a mixture of inorganic, organometallic, and organic chemistry, and is therefore ideal for training young workers for careers in science. Students in the research group are encouraged to interact with both academic and industrial scientists, better preparing themselves for permanent positions on either side of the academic/industrial divide. More specifically, the project addresses three fundamental questions in organotitanium chemistry: (1) The insertion of isonitriles into titanium-carbon (Ti-C) bonds. The insertion of carbon monoxide (CO) into Ti-C bonds has served as a powerful synthetic tool. In principle CO can be replaced by any of the isoelectronic isonitriles (RNC), giving transformations that could be as useful as CO insertion; (2) Dynamic kinetic asymmetric transformations. Chiral titanaaziridines and titanaoxiranes undergo rapid enantiomer interconversion, a property which makes them potentially useful for dynamic kinetic asymmetric transformations. In principle, this approach can generate enantioenriched chemicals from inexpensive racemic starting materials; and (3) Replacement of cyclopentadienyl ligand based Ti reagents with less expensive and more abundant alkoxy ligand based Ti reagents.

本课题由美国国家科学基金会化学结构、动力学、机理B计划资助，哥伦比亚大学的诺顿领导了一个研究小组，探索有机钛化学的基本问题。 钛，廉价和无毒，提供了可持续的方式进行各种化学转化。 该项目旨在使用廉价的钛基试剂合成有价值的有机化合物-不仅是杂环化合物，而且是制药工业所必需的对映体富集化合物。 该项目涉及无机，有机金属和有机化学的混合物，因此非常适合培训年轻工人从事科学事业。 鼓励研究小组的学生与学术和工业科学家进行互动，更好地为学术/工业分界线两侧的永久职位做好准备。更具体地说，该项目解决了有机钛化学中的三个基本问题：（1）将异腈插入钛-碳（Ti-C）键。 一氧化碳（CO）插入Ti-C键已成为一种强有力的合成工具。 原则上，CO可以被任何等电子异腈（RNC）取代，产生与CO插入一样有用的转化;（2）动态动力学不对称转化。 手性titanaaziridines和titanaoxiranes经历快速的对映异构体相互转化，这一性质使它们潜在地用于动态动力学不对称转化。 原则上，这种方法可以从廉价的外消旋起始材料产生对映体富集的化学品;和（3）用更便宜和更丰富的烷氧基配体基Ti试剂代替基于烷氧基配体的Ti试剂。

项目成果

Anti-Markovnikov alcohols via epoxide hydrogenation through cooperative catalysis

• DOI: 10.1126/science.aaw3913
• 发表时间: 2019-05
• 期刊: Science
• 影响因子: 56.9
• 作者: Chengbo Yao;Tobias Dahmen;A. Gansäuer;J. Norton

Insertion of Isonitriles into the M–C Bonds of Group 4 Dialkyl Complexes

将异腈插入第 4 族二烷基配合物的 M−C 键中

• DOI: 10.1021/jacs.8b05377
• 发表时间: 2018
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Chen, Jiawei;Yassin, Nadine;Gunasekara, Thilina;Norton, Jack R.;Rauch, Michael
• 通讯作者: Rauch, Michael

Insertion of Isonitriles into the Zr–CH 3 Bond of Cp* 2 Zr(CH 3 ) 2 and Electrophilic Cleavage of the Remaining Methyl Group

异腈插入 Cp* 2 Zr(CH 3 ) 2 的 Zr–CH 3 键和剩余甲基的亲电裂解

• DOI: 10.1021/acs.organomet.8b00690
• 发表时间: 2018
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Chen, Jiawei;Chen, Tao;Norton, Jack R.;Rauch, Michael
• 通讯作者: Rauch, Michael