Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts

Zhenzhong Zhang, Taishin Hashiguchi, Tamao Ishida, Akiyuki Hamasaki, Tetsuo Honma, Hironori Ohashi, Takushi Yokoyama, Makoto Tokunaga

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Transformation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts using molecular oxygen as the sole oxidant is developed. Several metal oxide supported Pd catalysts were used to activate the C-H bond in cyclohexanones to produce cyclohexenones and phenols through oxidation. Although the selectivity of cyclohexenones was difficult to control, phenols were obtained in excellent yield with a broad substrate scope. A novel catalytic system, using ZrO2 supported Pd(OH)2, was proposed for the synthesis of aryl ethers, and the products were obtained in moderate to excellent yields. Orthoesters, such as trimethyl orthoformate (TMOF), triethyl orthoformate (TEOF), and triisopropyl orthoformate (TIPOF), enabled nucleophilic addition and elimination after activation of cyclohexanones over a Pd catalyst to produce the corresponding aryl ethers. TIPOF was also used as the dehydrating reagent to promote the reaction of cyclohexanones with alcohols for the preparation of versatile aryl ethers.

Original languageEnglish
Pages (from-to)654-660
Number of pages7
JournalOrganic Chemistry Frontiers
Volume2
Issue number6
DOIs
Publication statusPublished - Jun 1 2015

Fingerprint

Cyclohexanones
Ethers
Phenols
Catalyst supports
Oxidation
Molecular oxygen
Oxidants
Oxides
Metals
Chemical activation
Alcohols
Catalysts
Substrates

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts. / Zhang, Zhenzhong; Hashiguchi, Taishin; Ishida, Tamao; Hamasaki, Akiyuki; Honma, Tetsuo; Ohashi, Hironori; Yokoyama, Takushi; Tokunaga, Makoto.

In: Organic Chemistry Frontiers, Vol. 2, No. 6, 01.06.2015, p. 654-660.

Research output: Contribution to journalArticle

Zhang, Z, Hashiguchi, T, Ishida, T, Hamasaki, A, Honma, T, Ohashi, H, Yokoyama, T & Tokunaga, M 2015, 'Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts', Organic Chemistry Frontiers, vol. 2, no. 6, pp. 654-660. https://doi.org/10.1039/c4qo00354c
Zhang, Zhenzhong ; Hashiguchi, Taishin ; Ishida, Tamao ; Hamasaki, Akiyuki ; Honma, Tetsuo ; Ohashi, Hironori ; Yokoyama, Takushi ; Tokunaga, Makoto. / Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts. In: Organic Chemistry Frontiers. 2015 ; Vol. 2, No. 6. pp. 654-660.
@article{bc5d9170048b40869c72b1b8e24102fd,
title = "Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts",
abstract = "Transformation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts using molecular oxygen as the sole oxidant is developed. Several metal oxide supported Pd catalysts were used to activate the C-H bond in cyclohexanones to produce cyclohexenones and phenols through oxidation. Although the selectivity of cyclohexenones was difficult to control, phenols were obtained in excellent yield with a broad substrate scope. A novel catalytic system, using ZrO2 supported Pd(OH)2, was proposed for the synthesis of aryl ethers, and the products were obtained in moderate to excellent yields. Orthoesters, such as trimethyl orthoformate (TMOF), triethyl orthoformate (TEOF), and triisopropyl orthoformate (TIPOF), enabled nucleophilic addition and elimination after activation of cyclohexanones over a Pd catalyst to produce the corresponding aryl ethers. TIPOF was also used as the dehydrating reagent to promote the reaction of cyclohexanones with alcohols for the preparation of versatile aryl ethers.",
author = "Zhenzhong Zhang and Taishin Hashiguchi and Tamao Ishida and Akiyuki Hamasaki and Tetsuo Honma and Hironori Ohashi and Takushi Yokoyama and Makoto Tokunaga",
year = "2015",
month = "6",
day = "1",
doi = "10.1039/c4qo00354c",
language = "English",
volume = "2",
pages = "654--660",
journal = "Organic Chemistry Frontiers",
issn = "2052-4110",
publisher = "Royal Society of Chemistry",
number = "6",

}

TY - JOUR

T1 - Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts

AU - Zhang, Zhenzhong

AU - Hashiguchi, Taishin

AU - Ishida, Tamao

AU - Hamasaki, Akiyuki

AU - Honma, Tetsuo

AU - Ohashi, Hironori

AU - Yokoyama, Takushi

AU - Tokunaga, Makoto

PY - 2015/6/1

Y1 - 2015/6/1

N2 - Transformation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts using molecular oxygen as the sole oxidant is developed. Several metal oxide supported Pd catalysts were used to activate the C-H bond in cyclohexanones to produce cyclohexenones and phenols through oxidation. Although the selectivity of cyclohexenones was difficult to control, phenols were obtained in excellent yield with a broad substrate scope. A novel catalytic system, using ZrO2 supported Pd(OH)2, was proposed for the synthesis of aryl ethers, and the products were obtained in moderate to excellent yields. Orthoesters, such as trimethyl orthoformate (TMOF), triethyl orthoformate (TEOF), and triisopropyl orthoformate (TIPOF), enabled nucleophilic addition and elimination after activation of cyclohexanones over a Pd catalyst to produce the corresponding aryl ethers. TIPOF was also used as the dehydrating reagent to promote the reaction of cyclohexanones with alcohols for the preparation of versatile aryl ethers.

AB - Transformation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts using molecular oxygen as the sole oxidant is developed. Several metal oxide supported Pd catalysts were used to activate the C-H bond in cyclohexanones to produce cyclohexenones and phenols through oxidation. Although the selectivity of cyclohexenones was difficult to control, phenols were obtained in excellent yield with a broad substrate scope. A novel catalytic system, using ZrO2 supported Pd(OH)2, was proposed for the synthesis of aryl ethers, and the products were obtained in moderate to excellent yields. Orthoesters, such as trimethyl orthoformate (TMOF), triethyl orthoformate (TEOF), and triisopropyl orthoformate (TIPOF), enabled nucleophilic addition and elimination after activation of cyclohexanones over a Pd catalyst to produce the corresponding aryl ethers. TIPOF was also used as the dehydrating reagent to promote the reaction of cyclohexanones with alcohols for the preparation of versatile aryl ethers.

UR - http://www.scopus.com/inward/record.url?scp=84946707929&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84946707929&partnerID=8YFLogxK

U2 - 10.1039/c4qo00354c

DO - 10.1039/c4qo00354c

M3 - Article

AN - SCOPUS:84946707929

VL - 2

SP - 654

EP - 660

JO - Organic Chemistry Frontiers

JF - Organic Chemistry Frontiers

SN - 2052-4110

IS - 6

ER -