TY - JOUR
T1 - Oxy-Borylenes as Photoreductants
T2 - Synthesis and Application in Dehalogenation and Detosylation Reactions
AU - Lenz, Philipp
AU - Oshimizu, Ryo
AU - Klabunde, Sina
AU - Daniliuc, Constantin G.
AU - Mück-Lichtenfeld, Christian
AU - Tendyck, Jonas C.
AU - Mori, Tatsuya
AU - Uhl, Werner
AU - Hansen, Michael Ryan
AU - Eckert, Hellmut
AU - Yamaguchi, Shigehiro
AU - Studer, Armido
N1 - Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2022/10/17
Y1 - 2022/10/17
N2 - While the range of accessible borylenes has significantly broadened over the last decade, applications remain limited. Herein, we present tricoordinate oxy-borylenes as potent photoreductants that can be readily activated by visible light. Facile oxidation of CAAC stabilized oxy-borylenes (CAAC)(IPr2Me2)BOR (R=TMS, CH2CH2C6H5, CH2CH2(4-F)C6H4) to their corresponding radical cations is achieved with mildly oxidizing ferrocenium ion. Cyclovoltammetric studies reveal ground-state redox potentials of up to −1.90 V vs. Fc+/0 for such oxy-borylenes placing them among the strongest organic super electron donors. Their ability as photoreductants is further supported by theoretical studies and showcased by the application as stoichiometric reagents for the photochemical hydrodehalogenation of aryl chlorides, aryl bromides and unactivated alkyl bromides as well as the detosylation of anilines.
AB - While the range of accessible borylenes has significantly broadened over the last decade, applications remain limited. Herein, we present tricoordinate oxy-borylenes as potent photoreductants that can be readily activated by visible light. Facile oxidation of CAAC stabilized oxy-borylenes (CAAC)(IPr2Me2)BOR (R=TMS, CH2CH2C6H5, CH2CH2(4-F)C6H4) to their corresponding radical cations is achieved with mildly oxidizing ferrocenium ion. Cyclovoltammetric studies reveal ground-state redox potentials of up to −1.90 V vs. Fc+/0 for such oxy-borylenes placing them among the strongest organic super electron donors. Their ability as photoreductants is further supported by theoretical studies and showcased by the application as stoichiometric reagents for the photochemical hydrodehalogenation of aryl chlorides, aryl bromides and unactivated alkyl bromides as well as the detosylation of anilines.
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U2 - 10.1002/anie.202209391
DO - 10.1002/anie.202209391
M3 - Article
C2 - 36005897
AN - SCOPUS:85138047798
SN - 1433-7851
VL - 61
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 42
M1 - e202209391
ER -