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通过基于钴(II)的金属自由基催化实现烯丙基叠氮甲酸酯的不对称自由基环化反应。

Asymmetric Radical Bicyclization of Allyl Azidoformates via Cobalt(II)-Based Metalloradical Catalysis.

机构信息

Department of Chemistry, University of South Florida , Tampa, Florida 33620, United States.

Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.

出版信息

J Am Chem Soc. 2017 Jul 12;139(27):9164-9167. doi: 10.1021/jacs.7b05778. Epub 2017 Jun 29.

DOI:10.1021/jacs.7b05778
PMID:28650659
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5553632/
Abstract

Cobalt(II)-based metalloradical catalysis has been successfully applied to radical bicyclization of allyl azidoformates to construct aziridine/oxazolidinone-fused bicyclic structures. The Co(II) complex of D-symmetric chiral amidoporphyrin 3,5-DiBu-QingPhyrin has been identified as an effective metalloradical catalyst for the intramolecular radical aziridination of this type of carbonyl azides, allowing for high-yielding formation of synthetically useful chiral [3.1.0]-bicyclic aziridines with high diastereo- and enantioselectivity.

摘要

钴(II)基金属自由基催化已成功应用于烯丙基叠氮甲酸酯的自由基双环化反应,构建了氮杂环丙烷/恶唑烷酮稠合双环结构。已确定 D-对称手性酰胺卟啉 3,5-二丁基-QingPhrin 的 Co(II)配合物是此类羰基叠氮化物分子内自由基氮丙啶化的有效金属自由基催化剂,可高产率地形成具有高非对映选择性和对映选择性的合成有用的手性[3.1.0]-双环氮丙啶。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/05db1b213742/nihms889419f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/6f03f5f950d4/nihms889419f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/5305632b53d1/nihms889419f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/7b2086fd543e/nihms889419f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/05db1b213742/nihms889419f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/6f03f5f950d4/nihms889419f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/5305632b53d1/nihms889419f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/7b2086fd543e/nihms889419f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cdbe/5553632/05db1b213742/nihms889419f4.jpg

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