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基于非血红素亚胺的铁配合物催化HO对脂肪族和芳香族氨基酸衍生物的氧化官能团化反应。

Oxidative functionalization of aliphatic and aromatic amino acid derivatives with HO catalyzed by a nonheme imine based iron complex.

作者信息

Ticconi Barbara, Colcerasa Arianna, Di Stefano Stefano, Lanzalunga Osvaldo, Lapi Andrea, Mazzonna Marco, Olivo Giorgio

机构信息

Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza" and Istituto CNR di Metodologie Chimiche (IMC-CNR), Sezione Meccanismi di Reazione, c/o Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza" P.le A. Moro 5 I-00185 Rome Italy

Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi 17071 Girona Spain.

出版信息

RSC Adv. 2018 May 23;8(34):19144-19151. doi: 10.1039/c8ra02879f. eCollection 2018 May 22.

DOI:10.1039/c8ra02879f
PMID:35539690
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9080596/
Abstract

The oxidation of a series of -acetyl amino acid methyl esters with HO catalyzed by a very simple iminopyridine iron(ii) complex 1 easily obtainable by self-assembly of 2-picolylaldehyde, 2-picolylamine, and Fe(OTf) was investigated. Oxidation of protected aliphatic amino acids occurs at the α-C-H bond exclusively (-AcAlaOMe) or in competition with the side-chain functionalization (-AcValOMe and -AcLeuOMe). -AcProOMe is smoothly and cleanly oxidized with high regioselectivity affording exclusively C-5 oxidation products. Remarkably, complex 1 is also able to catalyze the oxidation of the aromatic -AcPheOMe. A marked preference for the aromatic ring hydroxylation over Cα-H and benzylic C-H oxidation was observed, leading to the clean formation of tyrosine and its phenolic isomers.

摘要

研究了由一种非常简单的亚氨基吡啶铁（II）配合物1催化的一系列α-乙酰基氨基酸甲酯与HO的氧化反应，该配合物1可通过2-吡啶甲醛、2-吡啶甲胺和Fe(OTf)的自组装轻松获得。受保护的脂肪族氨基酸的氧化仅发生在α-C-H键处（α-乙酰丙氨酸甲酯），或与侧链官能化竞争（α-乙酰缬氨酸甲酯和α-乙酰亮氨酸甲酯）。α-乙酰脯氨酸甲酯能顺利且干净地被氧化，具有高区域选择性，仅生成C-5氧化产物。值得注意的是，配合物1还能够催化芳香族α-乙酰苯丙氨酸甲酯的氧化。观察到对芳香环羟基化的明显偏好超过Cα-H和苄基C-H氧化，从而干净地生成酪氨酸及其酚类异构体。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/44800d256b33/c8ra02879f-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/eff5682fe037/c8ra02879f-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/7cfab17e102e/c8ra02879f-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/21de33e54519/c8ra02879f-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/8cffc83e656d/c8ra02879f-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/0eb5c85dd4d2/c8ra02879f-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/44800d256b33/c8ra02879f-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/eff5682fe037/c8ra02879f-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/7cfab17e102e/c8ra02879f-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/21de33e54519/c8ra02879f-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/8cffc83e656d/c8ra02879f-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/0eb5c85dd4d2/c8ra02879f-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eb6a/9080596/44800d256b33/c8ra02879f-f3.jpg

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