Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications

Chiral α-amino-β2,2-amino acid is an ubiquitous fragment that presents in natural products, pharmaceuticals, and bioactive molecules. However, the catalytic enantioselective synthesis of α-amino-β2,2-amino acids with structural complexity and diversity remains a significant challenge. Herein, a high...

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Autores principales:	Xue Tian, Xinfang Xu, Tongfei Jing, Zhenghui Kang, Wenhao Hu
Formato:	article
Lenguaje:	EN
Publicado:	KeAi Communications Co. Ltd. 2021
Materias:	Asymmetric catalysis Metal carbene Cooperative catalysis Chiral α,β-diamino acids Ammonium ylide Chemical technology TP1-1185 Biochemistry QD415-436
Acceso en línea:	https://doaj.org/article/821f54f41be3412c8d1940f64d794a20
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spelling	oai:doaj.org-article:821f54f41be3412c8d1940f64d794a202021-12-02T05:03:59ZEnantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications2666-554910.1016/j.gresc.2021.10.007https://doaj.org/article/821f54f41be3412c8d1940f64d794a202021-11-01T00:00:00Zhttp://www.sciencedirect.com/science/article/pii/S2666554921000880https://doaj.org/toc/2666-5549Chiral α-amino-β2,2-amino acid is an ubiquitous fragment that presents in natural products, pharmaceuticals, and bioactive molecules. However, the catalytic enantioselective synthesis of α-amino-β2,2-amino acids with structural complexity and diversity remains a significant challenge. Herein, a highly enantioselective formal C–N bond insertion of aminals with metal carbene species that was generated in situ from diazo compound has been developed by employing a cooperative catalysis of achiral dirhodium complex with chiral phosphonic acid, providing a practical and efficient protocol for expeditious access to optically pure α-amino-β2,2-amino acid derivatives bearing an α-tetra-substituted stereo center with broad substrate scope. The reaction was proposed to proceed through an enantioselective reassembly of enolate intermediate generated in situ from rhodium carbene with methylene iminium ion via chiral ionic pair interaction. Further synthetic applications of these generated poly-functionalized products furnish different types of key intermediates for the formal synthesis of many bioactive molecules. In addition, these amino acid derivatives could also serve as novel potential tail chains of resorcinol dibenzyl ether type PD-1/PD-L1 small molecule inhibitors.Xue TianXinfang XuTongfei JingZhenghui KangWenhao HuKeAi Communications Co. Ltd.articleAsymmetric catalysisMetal carbeneCooperative catalysisChiral α,β-diamino acidsAmmonium ylideChemical technologyTP1-1185BiochemistryQD415-436ENGreen Synthesis and Catalysis, Vol 2, Iss 4, Pp 337-344 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Asymmetric catalysis Metal carbene Cooperative catalysis Chiral α,β-diamino acids Ammonium ylide Chemical technology TP1-1185 Biochemistry QD415-436
spellingShingle	Asymmetric catalysis Metal carbene Cooperative catalysis Chiral α,β-diamino acids Ammonium ylide Chemical technology TP1-1185 Biochemistry QD415-436 Xue Tian Xinfang Xu Tongfei Jing Zhenghui Kang Wenhao Hu Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications
description	Chiral α-amino-β2,2-amino acid is an ubiquitous fragment that presents in natural products, pharmaceuticals, and bioactive molecules. However, the catalytic enantioselective synthesis of α-amino-β2,2-amino acids with structural complexity and diversity remains a significant challenge. Herein, a highly enantioselective formal C–N bond insertion of aminals with metal carbene species that was generated in situ from diazo compound has been developed by employing a cooperative catalysis of achiral dirhodium complex with chiral phosphonic acid, providing a practical and efficient protocol for expeditious access to optically pure α-amino-β2,2-amino acid derivatives bearing an α-tetra-substituted stereo center with broad substrate scope. The reaction was proposed to proceed through an enantioselective reassembly of enolate intermediate generated in situ from rhodium carbene with methylene iminium ion via chiral ionic pair interaction. Further synthetic applications of these generated poly-functionalized products furnish different types of key intermediates for the formal synthesis of many bioactive molecules. In addition, these amino acid derivatives could also serve as novel potential tail chains of resorcinol dibenzyl ether type PD-1/PD-L1 small molecule inhibitors.
format	article
author	Xue Tian Xinfang Xu Tongfei Jing Zhenghui Kang Wenhao Hu
author_facet	Xue Tian Xinfang Xu Tongfei Jing Zhenghui Kang Wenhao Hu
author_sort	Xue Tian
title	Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications
title_short	Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications
title_full	Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications
title_fullStr	Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications
title_full_unstemmed	Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications
title_sort	enantioselective formal carbene insertion into c–n bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications
publisher	KeAi Communications Co. Ltd.
publishDate	2021
url	https://doaj.org/article/821f54f41be3412c8d1940f64d794a20
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Enantioselective formal carbene insertion into C–N bond of aminal as a concise track to chiral α-amino-β2,2-amino acids and synthetic applications

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