Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark (NJ), USA.
Chem Commun (Camb). 2021 Apr 27;57(34):4071-4088. doi: 10.1039/d1cc00596k.
Alkenes bearing four carbon-based groups are ubiquitous motifs in chemical sciences due to their various applications from medicinal to materials chemistry, and as chemical platforms for the synthesis of complex, chiral molecules. As such, tremendous research efforts are currently ongoing in order to develop general procedures for the challenging stereoselective synthesis of all-carbon tetrasubstituted alkenes, especially for acyclic structures. Since classical approaches to carbon-carbon double bonds are not suitable for the high steric demand around tetrasubstituted alkenes, a variety of unique approaches to access these privileged functional groups have been developed in recent years. This review article highlights the most significant developments in the field from 2007 to 2020, with an emphasis on the mechanisms and remaining limitations of these contemporary methods. Specifically, recent advances in internal alkyne carbofunctionalizations, in multicomponent couplings or other cross-couplings from nucleophilic or electrophilic alkenyl partners, and in the development of miscellaneous methods, are discussed.
由于其在从医学到材料化学等各个领域的广泛应用，以及作为合成复杂手性分子的化学平台，承载四个碳基的烯烃是化学科学中无处不在的主题。因此，目前正在进行大量的研究工作，以开发用于挑战性的全碳四取代烯烃的立体选择性合成的一般程序，特别是对于无环结构。由于经典的碳-碳双键方法不适合四取代烯烃周围的高空间需求，近年来已经开发了多种独特的方法来获得这些特权官能团。本文综述了 2007 年至 2020 年该领域最重要的发展，重点介绍了这些现代方法的机制和仍然存在的局限性。具体而言，讨论了内部炔烃碳官能化、亲核或亲电烯基试剂的多组分偶联或其他交叉偶联以及各种方法发展方面的最新进展。
