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共催化溴二氟乙酰胺的原子转移自由基加成反应,拓展了自由基二氟烷基化的范围。

Co-Catalyzed atom transfer radical addition of bromodifluoroacetamides, expanding the scope of radical difluoroalkylation.

作者信息

Yamamoto Yoshihiko, Suzuki Harufumi, Kuroyanagi Eisuke, Yamada Keiji, Yasui Takeshi

机构信息

Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Chikusa, Nagoya 464-8601, Japan.

出版信息

Org Biomol Chem. 2022 Apr 6;20(14):2867-2872. doi: 10.1039/d2ob00437b.

Abstract

The atom transfer radical addition (ATRA) of bromodifluoroacetamides to arylalkynes and terminal alkenes was conducted using von Wangelin's Co catalyst system (CoBr/1,2-bis(diphenylphosphino)benzene/Zn) in acetone/HO at 30 °C to afford the corresponding functionalized difluoroacetamides in 33-89% yields. Moreover, the Co catalyst was successfully applied to the tandem addition/cyclization of 1,6-diene and -enyne substrates and intramolecular ATRA of -allyl and -propargyl bromodifluoroacetamides, significantly expanding the scope of radical difluoroalkylation.

摘要

在30℃下,使用冯·万格林的钴催化剂体系(CoBr/1,2-双(二苯基膦基)苯/Zn),在丙酮/水体系中,将溴二氟乙酰胺与芳基炔烃和末端烯烃进行原子转移自由基加成(ATRA)反应,以33% - 89%的产率得到相应的官能化二氟乙酰胺。此外,该钴催化剂成功应用于1,6-二烯和烯炔底物的串联加成/环化反应以及烯丙基和炔丙基溴二氟乙酰胺的分子内ATRA反应,显著扩展了自由基二氟烷基化的范围。

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