C-O AND C-N BOND FORMATION USING METAL-BASED REAGENTS

使用金属基试剂形成 C-O 和 C-N 键

• 批准号: 3273040
• 负责人: ROBERT G BERGMAN
• 金额: $ 16.96万
• 依托单位: UNIVERSITY OF CALIFORNIA BERKELEY
• 依托单位国家: 美国
• 财政年份: 1978
• 资助国家: 美国
• 起止时间: 1978-08-01 至 1991-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3273040
• 关键词: alkenes; alkylation; alkynes; carbon; chemical addition; chemical synthesis; ligands; molybdenum; nickel; nitro compounds; nitrogen compounds; nitroso compounds; organometallic compounds; respiratory oxygen; sulfur compounds; tungsten

This proposal is aimed at developing the basic organometallic chemistry necessary for utilizing transition metal-based reagents to form new carbon-oxygen (C-O) and carbon-nitrogen (C-N) bonds in organic molecules. Initial experiments outlined are designed to yield general methods for the preparation of metal-alkoxy, -hydroxy and amido complexes. It is then proposed to induce such species to undergo transformations (e.g., insertion, oxidative addition, reductive elimination) analogous to those known for metal alkyl complexes, and use these basic reactions to develop ways to transfer the electronegative ligands to organic and small-molecule substrates such as alkenes, alkynes and CO. Special attention is paid to the study of alkylideneamido complexes, which are capable of bearing chiral ligands and thus can be used to prepare optically active amines from achiral substrates. Plans are also outlined to prepare and examine the role of oxa- and azametallacycles in alkene oxidation processes, and to explore the possibility of developing new metal-based organic oxidation reagents by examining the reactions of low-valent metal complexes with controlled amounts of oxidizing agents such as O2, peroxides and peracids.

这项建议旨在发展基础金属有机化学。 利用过渡金属基试剂形成新的 有机分子中的碳-氧(C-O)和碳-氮(C-N)键。 初步实验的设计是为了给出一般的方法 金属-烷氧基、-羟基和氨基配合物的制备。那就是了 建议用来诱导这些物种经历转化(例如， 插入、氧化加成、还原消除)类似于 以金属烷基络合物而闻名，并利用这些碱性反应来开发 电负性配体向有机小分子转移的途径 底物，如烯烃、炔烃和CO。特别注意的是 具有手性的亚烷基酰胺类化合物的研究 配体，因此可用于制备光学活性的胺 非手性衬底。还概述了准备和审查的计划 氧杂环和氮杂环在烯烃氧化过程中的作用 探索开发新型金属有机氧化材料的可能性 通过研究低价金属络合物与 控制氧化剂的数量，如O2、过氧物和过氧酸。