Site-Selective C(sp3)-H Functionalization of Fluorinated Alkanes Driven by Polar Effects Using a Tungstate Photocatalyst
Site-Selective C(sp3)-H Functionalization of Fluorinated Alkanes Driven by Polar Effects Using a Tungstate Photocatalyst
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DOI：
10.1002/ejoc.201901135
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发表时间：
2019-09-09
影响因子：
2.8
通讯作者：
Ryu, Ilhyong
中科院分区：
文献类型：
--
作者：
Fukuyama, Takahide;Nishikawa, Tomohiro;Ryu, Ilhyong
研究了tbadt催化的全氟苯基和全氟烷基取代烷烃的C(sp(3))- h功能化，以确定含氟取代基对位点选择性的影响。与烷基苯不同，烷基取代全氟苯的烷基化避免了-C-H键，允许远离芳环的C-H键的选择性功能化。具有全氟烷基的烷烃的烷基化也避免了-碳氢键。S(H)2过渡态中的自由基极性效应可以解释这种避免α - c -H官能化的现象。
The TBADT-catalyzed C(sp(3))-H functionalization of perfluorophenyl- and perfluoroalkyl-substituted alkanes was studied to determine how the fluorous substituents affect site-selectivity. Alkylation of alkyl-substituted perfluorobenzene avoids alpha-C-H bonds, unlike their alkylbenzene counterparts, allowing site-selective functionalization of C-H bonds remote to the aromatic ring. Alkylation of alkanes having a perfluoroalkyl group also avoided alpha-C-H bonds. Radical polar effects in the S(H)2 transition states could explain this avoidance of alpha-C-H functionalization.