Irradiation-induced palladium-catalyzed decarboxylative desaturation enabled by a dual ligand system
Irradiation-induced palladium-catalyzed decarboxylative desaturation enabled by a dual ligand system
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双配体系统实现辐照诱导的钯催化脱羧去饱和
DOI：
10.1038/s41467-018-07694-w
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发表时间：
2018-12-06
影响因子：
16.6
通讯作者：
Fu, Yao
中科院分区：
文献类型：
--
作者：
Cheng, Wan-Min;Shang, Rui;Fu, Yao
通过烷烃羧酸酯的脱羧烯烃化生成烯烃具有重要的合成价值，因为各种羧酸容易获得和烯烃的合成通用性。在本文中，我们报告了钯催化剂在蓝光LED（440 nm）照射下催化各种脂肪族羧酸酯的脱羧去饱和，以在温和条件下生成脂肪族烯烃、苯乙烯、烯醇醚、酰胺和肽酰胺。双膦配体体系的选择是该反应成功发展的关键。利用钯催化的脱羧去饱和反应，从简单的起始原料以68%的总收率实现了软骨素酰胺A和软骨素酰胺C的三步发散合成。机理研究表明，与热条件下的钯催化不同，辐射诱导钯催化涉及辐射诱导的单电子转移和动态配体解离/缔合过程，使两个膦配体协同作用。
Generation of alkenes through decarboxyolefination of alkane carboxylates has significant synthetic value in view of the easy availability of a variety of carboxylic acids and the synthetic versatility of alkenes. Herein we report that palladium catalysts under irradiation with blue LEDs (440 nm) catalyze decarboxylative desaturation of a variety of aliphatic carboxylates to generate aliphatic alkenes, styrenes, enol ethers, enamides, and peptide enamides under mild conditions. The selection of a dual phosphine ligand system is the key enabler for the successful development of this reaction. The Pd-catalyzed decarboxylative desaturation is utilized to achieve a three-step divergent synthesis of Chondriamide A and Chondriamide C in overall 68% yield from simple starting materials. Mechanistic studies suggest that, distinct from palladium catalysis under thermal condition, irradiation-induced palladium catalysis involves irradiation-induced single-electron transfer and dynamic ligand-dissociation/association process to allow two phosphine ligand to work synergistically.