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Understanding Selectivity of Lithiated Intermediates for Synthesis

了解锂化中间体的合成选择性

基本信息

批准号：
164195656
负责人：
Professor Dr. Carsten Strohmann
金额：
--
依托单位：
Forschungsgebiet Anorganische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2010
资助国家：
德国
起止时间：
2009-12-31 至 2017-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/164195656?language=en
关键词：
Understanding Selectivity Lithiated Intermediates Synthesis

项目摘要

Lithium chemistry is positioned at the interface of Organic and Inorganic Chemistry with organolithium compounds frequently employed as versatile chemical tools for the synthesis of pharmaceuticals, agrochemicals, flavours, fragrances and other synthetic intermediates. The project focuses on the in-depth mechanistic understanding of the observed chemo-, regio- and stereo-selectivity in organolithium carbometallation reactions and deprotonations with Schlossers Base Mixtures. While the use of organolithiums as strong bases is ubiquitous in synthetic chemistry, their application for addition reactions with unactivated alkenes is relatively unexplored and is rarely utilised. Part A of the project focuses on these carbometallations and studies the intermediates of aminometallation, prepared by deprotonation. The understanding of competing addition and deprotonation reactions of organolithiums, -sodiums and -potassiums with alkenes (with amino functions) and their potential for general synthetic usage will be studied. Schlossers Base Mixtures were important reagents in the first period of the project. Based on the first structural characterization of a Schlossers Base and the important reactivity pattern for the studied metallated intermediates in part A, part B of the proposal will focus on the structure/reactivity pattern of Schlossers Base Mixtures for part A related studies and general synthetic usage. Herein we propose a comprehensive understanding of competing carbometallation reactions and deprotonations through the combined efforts of computational, structural and synthetic chemistry. Key goals will be to map reactivity profiles, gain computational and structural evidence for reaction pathways and transition states and apply this knowledge to perfecting asymmetric variants.

锂化学处于有机化学和无机化学的交界面，有机锂化合物经常被用作合成药物、农用化学品、香精、香料和其他合成中间体的多功能化学工具。该项目的重点是深入了解有机锂碳金属化反应和Schlossers碱混合物脱质子反应中观察到的化学、区域和立体选择性的机理。虽然有机锂作为强碱的使用在合成化学中是普遍存在的，但它们在与非活化烯烃加成反应中的应用却相对未被探索，很少被利用。项目A部分重点研究这些碳金属化，并研究脱质子制备的氨基金属化中间体。将研究有机锂、钠和钾与烯烃（具有氨基功能）的竞争性加成和去质子化反应及其在一般合成应用中的潜力。Schlossers碱混合物是项目初期的重要试剂。基于Schlossers碱的第一个结构表征和a部分所研究的金属中间体的重要反应模式，提案的B部分将重点关注Schlossers碱混合物的结构/反应模式，用于a部分的相关研究和一般合成用途。在此，我们建议通过计算化学、结构化学和合成化学的共同努力，对相互竞争的碳金属化反应和去质子化反应进行全面的了解。关键目标将是绘制反应性曲线，获得反应途径和过渡态的计算和结构证据，并将这些知识应用于完善不对称变体。