Organic Synthesis with Bimetallic Systems
Organic Synthesis with Bimetallic Systems
复制标题
双金属系统有机合成
DOI：
10.1002/3527603557.ch1
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
Yoshinori Yamamoto
中科院分区：
文献类型：
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作者：
S. Kamijo;Yoshinori Yamamoto
近年来，在有机合成中应用活化剂体系的研究取得了很大进展，其中以催化量的活化剂促进反应的研究取得了很大进展。交叉偶联反应是这种类型的转化的代表性实例。在研究的早期阶段，大多数研究集中在过渡金属（TM）催化的反应使用主族有机金属化合物（R-M）。有机金属化合物（R-M）被用作底物（R-X）的偶联伴侣;交叉偶联反应可以被认为是由双金属体系（cat. TM/化学计量的R-M）促进的转化（图1.1a）。不仅交叉偶联反应（1.2.1节），而且π-烯丙基钯络合物的反应（1.2.4节）和镍催化的三组分偶联（TCC）反应（1.2.5节）也可归为a类。在催化量的铜盐存在下，有机镁和锂试剂与迈克尔受体的共轭加成也属于这一类，但这类有机铜反应在本章中没有提及，因为近年来已经发表了许多关于这些主题的优秀评论和专著[1]。这些交叉偶联反应的另一个特征是在另外的金属盐（MX）存在下经常观察到反应速率的提高。在催化量的TM和化学计量量的MX存在下，R-X和R-M之间的偶联反应进行得非常顺利（图1.1b）。Wacker反应（第1.2.2节）、Heck反应（第1.2.3节）、大多数涉及π-烯丙基钯络合物的反应（第1.2.4节）和Nozaki-Hiyama-Kishi（NHK）反应（第1.2.6节）属于这一类B。我们将在第一部分讨论由催化量和化学计量量的金属（a类和B类）的组合促进的反应。最近的研究表明，由过渡金属和另外的金属盐（cat. TM/cat. MX）组成的多种双金属催化体系有效地催化有机转化，例如交叉偶联反应
The application of bimetallic systems to organic synthesis has emerged dramatically in recent years, and great progress has been made in research aimed at developing reactions promoted with catalytic amounts of activating reagents. The cross-coupling reaction is a representative example of this type of transformation. In the early stages of the investigations, most studies were focused on transition metal (TM)catalyzed reactions using main group organometallic compounds (R–M). The organometallic compound (R–M) was used as a coupling partner of the substrate (R–X); the cross-coupling reactions can be regarded as transformations promoted by a bimetallic system (cat. TM/stoichiometric R–M) (Figure 1.1a). Not only crosscoupling reactions (Section 1.2.1), but also reactions of π-allylpalladium complexes (Section 1.2.4) and nickel-catalyzed three-component coupling (TCC) reactions (Section 1.2.5) can be classified as belonging to category a. The conjugate addition of organomagnesium and -lithium reagents to Michael acceptors in the presence of catalytic amounts of copper salts also belongs to this category, but such organocopper reactions are not mentioned in this chapter since many excellent reviews and monographs have been published on these topics in recent years [1]. Another characteristic feature of these cross-coupling reactions is that an enhancement of the reaction rate is often observed in the presence of an additional metal salt (MX). The coupling reaction between R–X and R–M proceeds very smoothly in the presence of catalytic amounts of TM and stoichiometric amounts of MX (Figure 1.1b). Wacker reactions (Section 1.2.2), Heck reactions (Section 1.2.3), most of the reactions involving π-allylpalladium complexes (Section 1.2.4), and Nozaki– Hiyama–Kishi (NHK) reactions (Section 1.2.6) belong to this category b. We will discuss the reactions promoted by a combination of catalytic and stoichiometric amounts of metals (categories a and b) in the first section. Recent studies have revealed that a wide variety of bimetallic catalytic systems composed of a transition metal and an additional metal salt (cat. TM/cat. MX) efficiently catalyze organic transformations, such as the cross-coupling reaction