We have developed a palladium‐catalyzed cross‐coupling reaction of isocyanides with α‐diazoacetates to form active ketenimines and following a 1,4‐diazabicyclo[2.2.2]octane (DABCO) catalyzed aza‐Mannich type reaction with various 2‐mercaptoimidazoles for the synthesis of 1,3‐bis(β‐aminoacrylate)‐substituted 2‐mercaptoimidazole derivatives with structural diversity. In addition, the use of 1H‐benzo[d]imidazol‐2‐ol as the reaction partner also allowed the formation of 1,3‐bis(β‐aminoacrylate)‐substituted 2‐benzimidazolinone derivatives with moderate yields (34–52%). In the aza‐Mannich reaction, the regioselective N‐attack rather than S‐attack or O‐attack at the electrophilic central carbon of ketenimines was observed. This tandem sequence is efficient since two C=C and two C−N bonds are consecutively created in one‐pot.

中文翻译：

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一锅串联方案合成1,3-双（β-氨基丙烯酸酯）取代的2-巯基咪唑支架

我们开发了钯催化的异氰酸酯与α-重氮乙酸酯的交叉偶联反应，以形成活性酮亚胺，然后在1,4-二氮杂双环[2.2.2]辛烷（DABCO）催化下的氮杂-曼尼希型反应与各种2-巯基咪唑反应制得1,3-双（β-氨基丙烯酸酯）取代的2-巯基咪唑衍生物的合成，具有结构多样性。此外，使用1 H-苯并[ d ]咪唑-2-醇作为反应伙伴还可以形成1,3-双（β-氨基丙烯酸酯）取代的2-苯并咪唑啉酮衍生物，产率适中（34-52 ％）。在aza-Mannich反应中，区域选择性N攻击而非S攻击或O观察到了酮亚胺的亲电子中心碳的攻击。此串联序列是有效的，因为在一个锅中连续创建了两个C = C和两个CN键。