Centre for Synthesis and Chemical Biology, School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Dublin, Ireland.
Chem Soc Rev. 2011 Oct;40(10):5122-50. doi: 10.1039/c1cs15101k. Epub 2011 Jun 15.
The asymmetric inter- and intramolecular Heck and related reactions are comprehensively reviewed, from their original development to recent advances in terms of substrate scope, reactivity, regio- and enantioselectivity. Their reaction mechanisms/catalytic cycles are discussed in order to understand the concepts underpinning the significant recent developments of these processes. The design and application of new chiral ligands has been pivotal to reaction enhancements and, for each Heck and related process, we classify ligands by the nature of the denticity, chirality and donor atoms involved. In this manner, the continued development of ligand architectural design and application can be more easily monitored for each process. Significant improvements in reaction times, a disadvantage in many Heck reactions, have been addressed through a combination the use of microwave-assisted protocols and ligand design. The asymmetric Fujiwara-Moritani and oxidative boron Heck-type reactions, recent additions to Heck type processes, will also be discussed in this critical review (149 references).
不对称的分子间和分子内 Heck 反应及相关反应被全面综述，内容涵盖从最初的发展到最近在底物范围、反应性、区域和对映选择性方面的进展。讨论了它们的反应机制/催化循环，以便理解这些过程最近显著发展所依据的概念。新的手性配体的设计和应用对于反应的增强至关重要，对于每个 Heck 和相关的过程，我们根据齿合度、手性和涉及的供体原子的性质对手性配体进行分类。通过这种方式，可以更轻松地监测每个过程中配体结构设计和应用的持续发展。通过结合使用微波辅助协议和配体设计，许多 Heck 反应的一个缺点——反应时间的显著缩短，已经得到了解决。不对称的 Fujiwara-Moritani 和氧化硼 Heck 型反应，作为 Heck 型反应的最新进展，也将在这篇综述中进行讨论（引用了 149 篇参考文献）。
