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Site‐Selective C(sp 3 )–H Functionalization of Fluorinated Alkanes Driven by Polar Effects Using a Tungstate Photocatalyst
Author(s) -
Fukuyama Takahide,
Nishikawa Tomohiro,
Ryu Ilhyong
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201901135
Subject(s) - chemistry , surface modification , alkylation , selectivity , tungstate , alkyl , medicinal chemistry , photochemistry , catalysis , organic chemistry
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 α‐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 α‐C–H bonds. Radical polar effects in the S H 2 transition states could explain this avoidance of α‐C–H functionalization.