TY - JOUR
T1 - Regioselective Rearrangement of 4,4-Disubstituted 2-Hydroxycyclohexa-2,5-Dienones under Deoxyfluorination Conditions
AU - Takubo, Keita
AU - Mohamed, Ahmed
AU - Ide, Takafumi
AU - Saito, Kazuyuki
AU - Ikawa, Takashi
AU - Yoshimitsu, Takehiko
AU - Akai, Shuji
N1 - Funding Information:
This study was supported by JSPS KAKENHI [Grant JP16H01151 (Middle Molecular Strategy)] and the Platform Project for Supporting Drug Discovery and Life Science Research funded by Japan Agency for Medical Research and Development (AMED). We are grateful to Prof. Masayoshi Arai, Dr. Ryosuke Ishida, and Dr. Gamal A. I. Moustafa of Graduate School of Pharmaceutical Sciences, Osaka University (Japan), for measuring 13C NMR (150 MHz) and HMQC.
PY - 2017/12/15
Y1 - 2017/12/15
N2 - The dienone-phenol rearrangement is a useful tool for the synthesis of highly substituted phenols. In our previous study of the rearrangement of 4,4-disubstituted 2-hydroxycyclohexa-2,5-dienone under deoxyfluorination conditions, bond migration proceeded with very poor regioselectivity. In this paper, an acid-mediated rearrangement of O-perfluoroalkylsulfonyl difluorides with regioselective migration toward the β′-carbon is reported. This method allowed the synthesis of a fluorinated analog of allocolchicinoids with improved total yield. Successful application to other substrates was also demonstrated.
AB - The dienone-phenol rearrangement is a useful tool for the synthesis of highly substituted phenols. In our previous study of the rearrangement of 4,4-disubstituted 2-hydroxycyclohexa-2,5-dienone under deoxyfluorination conditions, bond migration proceeded with very poor regioselectivity. In this paper, an acid-mediated rearrangement of O-perfluoroalkylsulfonyl difluorides with regioselective migration toward the β′-carbon is reported. This method allowed the synthesis of a fluorinated analog of allocolchicinoids with improved total yield. Successful application to other substrates was also demonstrated.
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U2 - 10.1021/acs.joc.7b02208
DO - 10.1021/acs.joc.7b02208
M3 - Article
C2 - 29099595
AN - SCOPUS:85038415134
VL - 82
SP - 13141
EP - 13151
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 24
ER -