Organic Chemistry Institute, University of Münster, Corrensstraße 36, 48149 Münster, Germany.
Molecules. 2021 Nov 16;26(22):6902. doi: 10.3390/molecules26226902.
Mukaiyama aldol, Mannich, and Michael reactions are arguably amongst the most important C-C bond formation processes and enable access to highly relevant building blocks of various natural products. Their vinylogous extensions display equally high potential in the formation of important key intermediates featuring even higher functionalization possibilities through an additional conjugated C-C double bond. Hence, it is much desired to develop highly selective vinylogous methods in order to enable unconventional, more efficient asymmetric syntheses of biologically active compounds. In this regard, silyl-dienolates were discovered to display high regioselectivities due to their tendency toward -additions. The control of the enantio- and diastereoinduction of these processes have been for a long time dominated by transition metal catalysis, but it received serious competition by the application of organocatalytic approaches since the beginning of this century. In this review, the organocatalytic applications of silyl-dienolates in asymmetric vinylogous C-C bond formations are summarized, focusing on their scope, characteristics, and limitations.
Mukaiyama 羟醛、Mannich 和 Michael 反应可以说是最重要的 C-C 键形成过程之一，它们可以获得各种天然产物的重要构建块。它们的 vinylogous 延伸同样具有很高的潜力，可以通过额外的共轭 C-C 双键形成具有更高功能化可能性的重要关键中间体。因此，人们非常希望开发高选择性的 vinylogous 方法，以实现具有生物活性化合物的非常规、更有效的不对称合成。在这方面，由于其倾向于 -加成，硅基二烯醇酯被发现具有高区域选择性。这些过程的对映选择性和非对映选择性的控制长期以来一直由过渡金属催化主导，但自本世纪初以来，有机催化方法的应用严重挑战了这一主导地位。在这篇综述中，总结了硅基二烯醇酯在不对称 vinylogous C-C 键形成中的有机催化应用，重点介绍了它们的范围、特点和局限性。
