47.1.5.6 Synthesis of Functionalized Alkenes by Metal-Catalyzed Coupling of Carbonyls with Alkynes/Allenes

Z. Lin; R. Tao; Y. Zhao

Abstract

In this review, different coupling methodologies between carbonyls and alkynes or allenes affording highly functionalized alkenes are summarized. Two main strategies are discussed in detail: In the first one, electrophilic carbonyl species are utilized in metal-catalyzed reductive coupling reactions assisted by various reductants such as boranes, silanes, and hydrogen gas. In the second one, nucleophilic carbonyl species are employed in coupling reactions with electrophilic π-allyl intermediates generated in situ, resulting in a formal α-allylation of carbonyls. Various representative examples serve to demonstrate the high versatility of these two general strategies, including applications in the total synthesis of complex natural products. High regio- and stereocontrol can be achieved with excellent yields for most of the selected examples. Reports of decarboxylative coupling and metal-free coupling are also included.

Key words

alkenes - alkynes - allenes - aldehydes - ketones - transition-metal catalysis - cross coupling - reductive coupling - π-allyl intermediates - enantioselectivity - regioselectivity

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