Regioselective Rearrangement of 4,4-Disubstituted 2-Hydroxycyclohexa-2,5-Dienones under Deoxyfluorination Conditions

Keita Takubo; Ahmed Mohamed; Takafumi Ide; Kazuyuki Saito; Takashi Ikawa; Takehiko Yoshimitsu; Shuji Akai

doi:10.1021/acs.joc.7b02208

Regioselective Rearrangement of 4,4-Disubstituted 2-Hydroxycyclohexa-2,5-Dienones under Deoxyfluorination Conditions

Keita Takubo, Ahmed Mohamed, Takafumi Ide, Kazuyuki Saito, Takashi Ikawa, Takehiko Yoshimitsu, Shuji Akai

Research output: Contribution to journal › Article

Abstract

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.

Original language	English
Pages (from-to)	13141-13151
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	82
Issue number	24
DOIs	https://doi.org/10.1021/acs.joc.7b02208
Publication status	Published - Dec 15 2017
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

Access to Document

10.1021/acs.joc.7b02208

Fingerprint Dive into the research topics of 'Regioselective Rearrangement of 4,4-Disubstituted 2-Hydroxycyclohexa-2,5-Dienones under Deoxyfluorination Conditions'. Together they form a unique fingerprint.

Cite this

Takubo, K., Mohamed, A., Ide, T., Saito, K., Ikawa, T., Yoshimitsu, T., & Akai, S. (2017). Regioselective Rearrangement of 4,4-Disubstituted 2-Hydroxycyclohexa-2,5-Dienones under Deoxyfluorination Conditions. Journal of Organic Chemistry, 82(24), 13141-13151. https://doi.org/10.1021/acs.joc.7b02208

@article{50be8c724b824f069b0e7452cc424d18,

title = "Regioselective Rearrangement of 4,4-Disubstituted 2-Hydroxycyclohexa-2,5-Dienones under Deoxyfluorination Conditions",

abstract = "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.",

author = "Keita Takubo and Ahmed Mohamed and Takafumi Ide and Kazuyuki Saito and Takashi Ikawa and Takehiko Yoshimitsu and Shuji Akai",

year = "2017",

month = dec,

day = "15",

doi = "10.1021/acs.joc.7b02208",

language = "English",

volume = "82",

pages = "13141--13151",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "24",

}

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

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.

UR - http://www.scopus.com/inward/record.url?scp=85038415134&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85038415134&partnerID=8YFLogxK

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 -