Imine Directed Cp*RhIII -Catalyzed N-H Functionalization and Annulation with Amino Amides, Aldehydes, and Diazo Compounds.
Imine Directed Cp*RhIII -Catalyzed N-H Functionalization and Annulation with Amino Amides, Aldehydes, and Diazo Compounds.
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亚胺导向的 Cp*RhIII 催化 N-H 官能化和氨基酰胺、醛和重氮化合物的环化。
DOI：
10.1002/anie.202210822
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Ellman,JonathanA
中科院分区：
文献类型：
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作者：
Zoll,AdamJ;Molas,JennaC;Mercado,BrandonQ;Ellman,JonathanA
公开了通过亚胺导向的Cp*RhIII催化的N-H官能化进行的多组分成环。该转化提供了显示一系列官能度的哌嗪酮，并且是过渡金属催化的多组分N-H官能化的第一个例子。广泛的容易获得的α-氨基酰胺，包括来自甘氨酸、α-取代和α，α-二取代氨基酸的那些，是有效的输入，并且能够以最小的外消旋掺入各种氨基酸侧链。支链和非支链的烷基醛和各种稳定的重氮化合物也是有效的反应物。通过高效的转化，对哌嗪酮产物进行了进一步的修饰。机制研究，包括具有催化活性的五元罗达霉素与亚胺和酰胺氮螯合的X射线晶体学表征，为所提出的机制提供了支持。
A multicomponent annulation that proceeds by imine directed Cp*RhIII‐catalyzed N−H functionalization is disclosed. The transformation affords piperazinones displaying a range of functionality and is the first example of transition metal‐catalyzed multicomponent N−H functionalization. A broad range of readily available α‐amino amides, including those derived from glycine, α‐substituted, and α,α‐disubstituted amino acids, were effective inputs and enabled the incorporation of a variety of amino acid side chains with minimal racemization. Branched and unbranched alkyl aldehydes and various stabilized diazo compounds were also efficient reactants. The piperazinone products were further modified through efficient transformations. Mechanistic studies, including X‐ray crystallographic characterization of a catalytically competent five‐membered rhodacycle with imine and amide nitrogen chelation, provide support for the proposed mechanism.