Ullmann 反应百年纪念及近期复兴——兼及碳-杂原子键的形成  

Ullmann Reaction, A Centennial Memory and Recent Renaissance —— Related Formation of Carbon-Heteroatom Bond

作　　者：戴立信[1] Lixin Dai(State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China)

机构地区：[1]中国科学院上海有机化学研究所金属有机化学国家重点实验室

出　　处：《化学进展》2018年第9期1257-1297,共41页Progress in Chemistry

摘　　要：1901年Ullmann报道了一个形成sp^2C—C键的偶联反应,1903年报道了苯胺的N-芳基化反应,1905年又报道了苯酚的O-芳基化的缩合反应。这些经典的反应进入催化领域且范围又有扩展,但由于反应条件苛刻等缺点,也限制了反应的应用。20世纪末,在多位科学家的努力下,发现具有一定结构的化合物——配体,对于铜催化的Ullmann缩合反应(或交叉偶联反应)具有配体加速催化反应(LAC)的效果,于是引发了对这一反应的研究热潮。本文对于各种配体的选用,特别是草酰二胺类,对于无机碱,特别是有机离子性碱的选用以及铜源、配体的负载化、溶剂的考量和绿色化等方面进行了较为详细的讨论。鉴于在2004年已有单篇论文提出了Ullmann反应的复兴, Beletskaya则提出了精辟的问题:这就是复兴吗?在金属催化的交叉偶联反应中,铜催化是否已成为钯催化的有力竞争者?Beletskaya在历数了铜催化的优点之后,也深刻地列出了铜催化的五大不足之处。经过了十余年众多化学家的成功发展,本文对此给出了明确的回答。In 1901, F. Ullmann reported a new coupling reaction for the formation of sp^2C—sp^2C bond between two molecules of aryl iodide. In 1903, another paper of the N-arylation of aniline with aryl iodide was published. In 1905, the O-arylation of aryl bromide with the potassium salt of phenol was disclosed. These reactions, one coupling reaction and two condensations（or cross coupling reactions） played great roles in the development of aromatic chemistry during the turning from 19^（th） to 20^（th） century, especially in the field of dyestuff industry. Despite of these applications, the very harsh reaction condition, high temperature（～200 ℃） for long reaction time（one or two days） of the classical reaction of Ullmann condensation usually limited their applications.By the efforts of several chemists in the end of last century, the acceleration effect of the Cu catalyzed Ullmann condensation by compounds with certain structure units or ligands was found. Thereafter, a surge of research interest was directed to this reaction. In this paper, the selection of various types of ligands, especially the oxalyldiamide type, the consideration of bases to be used especially the organic ionic bases, the immobilization of cooper sources and ligands and the green chemistry in Ullmann condensation are reviewed.In 2004, Irina Beletskaya queried incisively and adequately a question： Is this a renaissance？ Or ＂In the field of metal catalyzed cross coupling reactions, is the copper catalyzed reaction already a strong competitor to the palladium catalyzed reaction？＂ Beletskaya pointed out profoundly the five major drawbacks of copper catalyzed reaction. After more than ten years oxtensive investigation, a clear cut answer to this question was made as a result of several hundreds research papers dealing with the Ullmann cross coupling reactions.

关 键 词：缩合反应 交叉偶联反应 铜催化的反应 配体加速的催化反应 咪唑的N-芳基化反应 

分 类 号：O621[理学—有机化学]