TY - JOUR
T1 - Catalytic reductive ring opening of epoxides enabled by zirconocene and photoredox catalysis
AU - Aida, Kazuhiro
AU - Hirao, Marina
AU - Funabashi, Aiko
AU - Sugimura, Natsuhiko
AU - Ota, Eisuke
AU - Yamaguchi, Junichiro
N1 - Funding Information:
This work was supported by JSPS KAKENHI grant numbers JP19H02726 and JP21H05213 (Digitalization-driven Transformative Organic Synthesis) (to J.Y.), JP20K15290 (to E.O.), Sumitomo Foundation (to E.O.), Fukuoka Naohiko Memorial Foundation (to E.O.), Satomi Foundation (to E.O.), and JXTG Nippon Oil & Energy Corporation (curr. ENEOS Corporation) (to E.O.). This work was partly supported by JST ERATO grant number JPMJER1901 (to J.Y.). We thank Prof. Robert Knowles for helpful comments. Materials Characterization Central Laboratory in Waseda University is acknowledged for the support of HRMS measurement. The computation was performed using Research Center for Computational Science, Okazaki, Japan (Project: 21-IMS-C223).
Funding Information:
This work was supported by JSPS KAKENHI grant numbers JP19H02726 and JP21H05213 (Digitalization-driven Transformative Organic Synthesis) (to J.Y.), JP20K15290 (to E.O.), Sumitomo Foundation (to E.O.), Fukuoka Naohiko Memorial Foundation (to E.O.), Satomi Foundation (to E.O.), and JXTG Nippon Oil & Energy Corporation (curr. ENEOS Corporation) (to E.O.). This work was partly supported by JST ERATO grant number JPMJER1901 (to J.Y.). We thank Prof. Robert Knowles for helpful comments. Materials Characterization Central Laboratory in Waseda University is acknowledged for the support of HRMS measurement. The computation was performed using Research Center for Computational Science, Okazaki, Japan (Project: 21-IMS-C223). J.Y. and E.O. directed the projects and designed the experiments. K.A. M.H. and A.F. performed experiments. All authors contributed to data analysis. J.Y. and E.O. wrote the manuscript with feedback from the other authors. The authors declare no competing interests.
Publisher Copyright:
© 2022 The Author(s)
PY - 2022/6/9
Y1 - 2022/6/9
N2 - The reductive ring opening of epoxides is a powerful transformation to convert readily accessible epoxides into a diverse array of valuable alcohols, including pharmaceuticals, agrochemicals, and functional polymers. Although significant progress has been made, the established methods were limited to titanocene-catalyzed reactions. Herein, we report an unprecedented zirconocene-catalyzed ring opening of epoxide enabled by photoredox catalysis. Compared with the conventional ring-opening methods, the present protocol exhibited reverse regioselectivity to afford more substituted alcohols via putative less-stable radicals. This reaction is remarkably mild and smoothly cleaves C–O bonds in molecules with a variety of functional groups, including natural products. We believe that the finding that changing the metal center in metallocene influences the energy profile of ring opening is a significant advance and provides a new perspective in radical chemistry with group IV metals.
AB - The reductive ring opening of epoxides is a powerful transformation to convert readily accessible epoxides into a diverse array of valuable alcohols, including pharmaceuticals, agrochemicals, and functional polymers. Although significant progress has been made, the established methods were limited to titanocene-catalyzed reactions. Herein, we report an unprecedented zirconocene-catalyzed ring opening of epoxide enabled by photoredox catalysis. Compared with the conventional ring-opening methods, the present protocol exhibited reverse regioselectivity to afford more substituted alcohols via putative less-stable radicals. This reaction is remarkably mild and smoothly cleaves C–O bonds in molecules with a variety of functional groups, including natural products. We believe that the finding that changing the metal center in metallocene influences the energy profile of ring opening is a significant advance and provides a new perspective in radical chemistry with group IV metals.
KW - SDG3: Good health and well-being
KW - SDG9: Industry innovation and infrastructure
KW - epoxide
KW - photoredox catalysis
KW - reverse regioselectivity
KW - ring opening
KW - zirconocene
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U2 - 10.1016/j.chempr.2022.04.010
DO - 10.1016/j.chempr.2022.04.010
M3 - Article
AN - SCOPUS:85133305460
SN - 2451-9308
VL - 8
SP - 1762
EP - 1774
JO - Chem
JF - Chem
IS - 6
ER -