Copper-Catalyzed Electrophilic Etherification of Arylboronic Esters with Isoxazolidines

Seiya Katahara; Tenga Takahashi; Kengo Nomura; Masanobu Uchiyama; Takaaki Sato; Noritaka Chida

doi:10.1002/asia.202000270

Copper-Catalyzed Electrophilic Etherification of Arylboronic Esters with Isoxazolidines

Seiya Katahara, Tenga Takahashi, Kengo Nomura, Masanobu Uchiyama, Takaaki Sato, Noritaka Chida

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

A copper-catalyzed electrophilic etherification of arylboronic esters is reported. Isoxazolidines are utilized as easily available and stable [RO]⁺ surrogates to give 1,3-amino aryl ethers. The O-selective arylation of isoxazolidines takes place without causing competitive N-arylation. In contrast to previously reported anionic conditions, our copper-catalyzed conditions are mild enough to achieve high functional group tolerance. Preliminary mechanistic studies and DFT calculations support that the reaction proceeds via a transmetalation/oxidative addition pathway, followed by a Lewis acid-promoted reductive elimination to induce the crucial O-selectivity.

Original language	English
Pages (from-to)	1869-1872
Number of pages	4
Journal	Chemistry - An Asian Journal
Volume	15
Issue number	12
DOIs	https://doi.org/10.1002/asia.202000270
Publication status	Published - 2020 Jun 17

Keywords

aryl ether
chemoselectivity
copper catalyst
electrophilic reaction
isoxazolidine

ASJC Scopus subject areas

Biochemistry
Organic Chemistry

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title = "Copper-Catalyzed Electrophilic Etherification of Arylboronic Esters with Isoxazolidines",

abstract = "A copper-catalyzed electrophilic etherification of arylboronic esters is reported. Isoxazolidines are utilized as easily available and stable [RO]+ surrogates to give 1,3-amino aryl ethers. The O-selective arylation of isoxazolidines takes place without causing competitive N-arylation. In contrast to previously reported anionic conditions, our copper-catalyzed conditions are mild enough to achieve high functional group tolerance. Preliminary mechanistic studies and DFT calculations support that the reaction proceeds via a transmetalation/oxidative addition pathway, followed by a Lewis acid-promoted reductive elimination to induce the crucial O-selectivity.",

keywords = "aryl ether, chemoselectivity, copper catalyst, electrophilic reaction, isoxazolidine",

author = "Seiya Katahara and Tenga Takahashi and Kengo Nomura and Masanobu Uchiyama and Takaaki Sato and Noritaka Chida",

note = "Funding Information: This research was supported by a Grant‐in‐Aid for Scientific Research (C) from MEXT (No. 18K05127), and a JSPS fellowship to S.K. (No. 19J10048), and Grants‐in‐Aid for Scientific Research (S) (No. 17H06173), and JST CREST (No. JPMJCR19R2) to M.U. Allotment of computational resources (Project G19012) from HOKUSAI BigWaterfall (RIKEN) is gratefully acknowledged. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = jun,

day = "17",

doi = "10.1002/asia.202000270",

language = "English",

volume = "15",

pages = "1869--1872",

journal = "Chemistry - An Asian Journal",

issn = "1861-4728",

publisher = "John Wiley and Sons Ltd",

number = "12",

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T1 - Copper-Catalyzed Electrophilic Etherification of Arylboronic Esters with Isoxazolidines

AU - Katahara, Seiya

AU - Takahashi, Tenga

AU - Nomura, Kengo

AU - Uchiyama, Masanobu

AU - Sato, Takaaki

AU - Chida, Noritaka

N1 - Funding Information: This research was supported by a Grant‐in‐Aid for Scientific Research (C) from MEXT (No. 18K05127), and a JSPS fellowship to S.K. (No. 19J10048), and Grants‐in‐Aid for Scientific Research (S) (No. 17H06173), and JST CREST (No. JPMJCR19R2) to M.U. Allotment of computational resources (Project G19012) from HOKUSAI BigWaterfall (RIKEN) is gratefully acknowledged. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/6/17

Y1 - 2020/6/17

N2 - A copper-catalyzed electrophilic etherification of arylboronic esters is reported. Isoxazolidines are utilized as easily available and stable [RO]+ surrogates to give 1,3-amino aryl ethers. The O-selective arylation of isoxazolidines takes place without causing competitive N-arylation. In contrast to previously reported anionic conditions, our copper-catalyzed conditions are mild enough to achieve high functional group tolerance. Preliminary mechanistic studies and DFT calculations support that the reaction proceeds via a transmetalation/oxidative addition pathway, followed by a Lewis acid-promoted reductive elimination to induce the crucial O-selectivity.

AB - A copper-catalyzed electrophilic etherification of arylboronic esters is reported. Isoxazolidines are utilized as easily available and stable [RO]+ surrogates to give 1,3-amino aryl ethers. The O-selective arylation of isoxazolidines takes place without causing competitive N-arylation. In contrast to previously reported anionic conditions, our copper-catalyzed conditions are mild enough to achieve high functional group tolerance. Preliminary mechanistic studies and DFT calculations support that the reaction proceeds via a transmetalation/oxidative addition pathway, followed by a Lewis acid-promoted reductive elimination to induce the crucial O-selectivity.

KW - aryl ether

KW - chemoselectivity

KW - copper catalyst

KW - electrophilic reaction

KW - isoxazolidine

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Copper-Catalyzed Electrophilic Etherification of Arylboronic Esters with Isoxazolidines

Abstract

Keywords

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