Skipped dienes is one of the most prevalent motifs in vast array of natural products, medicinal compounds, and fatty acids. Herein, we disclose a straightforward one-step reductive protocol under Co/PC for the synthesis of diverse 1,4-dienes with excellent regio- and stereoselectivity. The protocol utilize allenyl carbonate as 1,3-butadiene surrogate and providing a synthetic tool to access skipped diene in one step with alkyne under dual-catalytic approach. Further, large variety of alkynes including terminal alkynes, propargylic alcohols and internal alkynes were employed. The homologation of natural terpenols into synthetic terpenols by iterative allylation of four-carbon allyl units resulted in bio-mimetic synthetic terpenes derived from propargylic alcohols. Under this approach the programmed skipped diene can be accessed with predictable stereochemistry and might be a useful synthetic method for targeted synthe-sis. The experimental studies, control experiments and detailed DFT studies revealed that the 1,3-diene generated in situ from allenyl carbonate, diisopropyl ammonium act as proton source, Co(II)-π-allyl species involved in the catalytic cycle and the mechanism proceed through Co(II)−Co(I)−Co(III) pathway.

中文翻译：

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通过钴催化炔烃和烯基碳酸酯的还原偶联有效获得跳过二烯和三烯

跳过二烯是大量天然产物、药用化合物和脂肪酸中最普遍的基序之一。在此，我们公开了一种在 Co/PC 下简单的一步还原方案，用于合成具有优异区域选择性和立体选择性的多种 1,4-二烯。该方案利用碳酸丙二烯酯作为 1,3-丁二烯替代物，并提供了一种合成工具，可在双催化方法下用炔一步获得跳过的二烯。此外，使用了多种炔烃，包括末端炔烃、炔丙醇和内炔烃。通过四碳烯丙基单元的迭代烯丙基化将天然萜醇同系为合成萜醇，产生了源自炔丙醇的仿生合成萜烯。在这种方法下，可以通过可预测的立体化学来获得编程的跳跃二烯，并且可能是用于靶向合成的有用的合成方法。实验研究、对照实验和详细的DFT研究表明，碳酸丙二烯原位生成1,3-二烯，二异丙基铵充当质子源，Co(II)-π-烯丙基物种参与催化循环，并且机理进行通过 Co(II)−Co(I)−Co(III) 途径。