Regioselective Syntheses of Fluorinated Cyclopentanone Derivatives: Ring Construction Strategy Using Transition-Metal–Difluorocarbene Complexes and Free Difluorocarbene

Kohei Fuchibe; Ryo Takayama; Tatsuya Aono; Ji Hu; Tomohiro Hidano; Hisashi Sasagawa; Masaki Fujiwara; Shinji Miyazaki; Ryo Nadano; Junji Ichikawa

doi:10.1055/s-0036-1591728

Synthesis, Table of Contents

Synthesis 2018; 50(03): 514-528
DOI: 10.1055/s-0036-1591728

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Regioselective Syntheses of Fluorinated Cyclopentanone Derivatives: Ring Construction Strategy Using Transition-Metal–Difluorocarbene Complexes and Free Difluorocarbene

Kohei Fuchibe

^aDivision of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305–8571, Japan Email: junji@chem.tsukuba.ac.jp

,

Ryo Takayama

^aDivision of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305–8571, Japan Email: junji@chem.tsukuba.ac.jp

,

Tatsuya Aono

^aDivision of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305–8571, Japan Email: junji@chem.tsukuba.ac.jp

,

Ji Hu

^aDivision of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305–8571, Japan Email: junji@chem.tsukuba.ac.jp

,

Tomohiro Hidano

^aDivision of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305–8571, Japan Email: junji@chem.tsukuba.ac.jp

,

Hisashi Sasagawa

^aDivision of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305–8571, Japan Email: junji@chem.tsukuba.ac.jp

,

Masaki Fujiwara

^bDepartment of Applied Chemistry, Kyushu Institute of Technology, Kitakyushu, Fukuoka 804–8550, Japan

,

Shinji Miyazaki

^bDepartment of Applied Chemistry, Kyushu Institute of Technology, Kitakyushu, Fukuoka 804–8550, Japan

,

Ryo Nadano

^cDepartment of Chemistry, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113–0033, Japan

,

Junji Ichikawa *

^aDivision of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305–8571, Japan Email: junji@chem.tsukuba.ac.jp

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Abstract

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Abstract

The syntheses of fluorinated cyclopentanone derivatives, which have pharmaceutical and agrochemical importance are reported. The catalytic reaction of copper(I) and nickel(II) difluorocarbenes with silyl dienol ethers afforded 4,4-difluoro- and 5,5-difluorocyclopent-1-en-1-yl silyl ethers, respectively. The fluorine-directed and -activated Nazarov cyclization of 1-fluorovinyl vinyl ketones, which were prepared from silyl dienol ethers and free difluorocarbene, proceeded efficiently to afford 2-fluorocyclopent-2-en-1-ones. Moreover, fluorine-directed Nazarov cyclizations of 2,2-difluorovinyl vinyl ketones and 1-(trifluoromethyl)vinyl vinyl ketones afforded 3-fluorocyclopent-2-en-1-ones and 5-(trifluoromethyl)cyclopent-2-en-1-ones, respectively. In addition, derivatization of ring-difluorinated products also provided 3-fluorocyclopent-2-en-1-ones.

Key words

fluorine - carbene complexes - carbocation - difluorocarbene - Nazarov cyclization - cyclopentanones - organocatalysts

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