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Direct Access to α,β‐Unsaturated γ‐Lactams via Palladium‐Catalysed Carbonylation of Propargylic Ureas
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2024-11-04 , DOI: 10.1002/adsc.202401183
Debora Schiroli, Aleksandr Voronov, Francesco Pancrazzi, Nunzio Iraci, Salvatore Vincenzo Giofré, Beatrice Macchi, Valeria Stefanizzi, Raffaella Mancuso, Bartolo Gabriele, Paolo Pio Mazzeo, Luca Capaldo, Nicola Della Ca'

. Additive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant‐free conditions. Our straightforward carbonylative strategy enables access to versatile α,β‐unsaturated γ‐lactams featuring an aminocarbonyl fragment, utilizing readily available propargylic ureas as starting materials. The employment of the PdI2/KI catalytic system allowed complete regioselectivity (5‐endo‐dig), high functional group tolerance, broad substrate scope as well as operational simplicity (oxidant‐free, organic ligand‐free and base‐free protocol). The synthetic utility of these γ‐lactams is showcased through late‐stage functionalizations, such as Giese reactions and peptide couplings.

中文翻译:


通过钯催化的原脲羰基化直接获得 α,β-不饱和 γ-内酰胺



.加成羰基化通常需要强亲核试剂,例如醇或胺。在这项研究中,我们在无氧化剂的条件下羰基化了一种亲核性差的尿素。我们简单的羰基化策略能够利用现成的炔炔基脲作为起始原料,获得具有氨基羰基片段的多功能α,β-不饱和γ-内酰胺。PdI2/KI 催化系统的使用可实现完全的区域选择性 (5-endo-dig)、高官能团耐受性、广泛的底物范围以及操作简单性(无氧化剂、无有机配体和无碱的方案)。这些 γ-内酰胺类化合物的合成效用通过后期官能团化(如 Giese 反应和肽偶联)来展示。
更新日期:2024-11-04
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