An Efficient Protocol for Selective Silylation of Hydroxy Group Using N,O-Bis(tert-butyldimethylsilyl)acetamide and N,N-Dimethyl-4-aminopyridine N-Oxide

Hiroki Mandai; Yuichiro Matsuura; Fatin Mahfuzah Binti Johari; Koichi Mitsudo; Seiji Suga

doi:10.1246/cl.220281

An Efficient Protocol for Selective Silylation of Hydroxy Group Using N,O-Bis(tert-butyldimethylsilyl)acetamide and N,N-Dimethyl-4-aminopyridine N-Oxide

Hiroki Mandai, Yuichiro Matsuura, Fatin Mahfuzah Binti Johari, Koichi Mitsudo, Seiji Suga

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

Abstract

An efficient method for the silylation of alcohols was developed using N,O-bis(tert-butyldimethylsilyl)acetamide (BTBSA) and 3mol% of N,N-dimethyl-4-aminopyridine Noxide (DMAPO). Monosilylation of 1,2-diols was successfully achieved with high chemoselectivity. In addition, several control experiments revealed that a phenolic hydroxy group was silylated much faster than a primary alcohol in both an inter- and intramolecular manner. The reactivity toward silylation under these systems might stem from the pKa of the hydroxy group.

Original language	English
Pages (from-to)	953-956
Number of pages	4
Journal	Chemistry Letters
Volume	51
Issue number	9
DOIs	https://doi.org/10.1246/cl.220281
Publication status	Published - Sept 2022

Keywords

Chemoselective silylation
DMAPO
Organocatalyst

ASJC Scopus subject areas

Chemistry(all)

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10.1246/cl.220281

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title = "An Efficient Protocol for Selective Silylation of Hydroxy Group Using N,O-Bis(tert-butyldimethylsilyl)acetamide and N,N-Dimethyl-4-aminopyridine N-Oxide",

abstract = "An efficient method for the silylation of alcohols was developed using N,O-bis(tert-butyldimethylsilyl)acetamide (BTBSA) and 3mol% of N,N-dimethyl-4-aminopyridine Noxide (DMAPO). Monosilylation of 1,2-diols was successfully achieved with high chemoselectivity. In addition, several control experiments revealed that a phenolic hydroxy group was silylated much faster than a primary alcohol in both an inter- and intramolecular manner. The reactivity toward silylation under these systems might stem from the pKa of the hydroxy group.",

keywords = "Chemoselective silylation, DMAPO, Organocatalyst",

author = "Hiroki Mandai and Yuichiro Matsuura and Johari, {Fatin Mahfuzah Binti} and Koichi Mitsudo and Seiji Suga",

note = "Funding Information: This research was partially supported by JSPS Kakenhi Grant Number JP19K05456. The authors also thank DAICEL corporation for analyzing an enantiomeric ratio of 5f. Publisher Copyright: {\textcopyright} 2022 The Chemical Society of Japan.",

year = "2022",

month = sep,

doi = "10.1246/cl.220281",

language = "English",

volume = "51",

pages = "953--956",

journal = "Chemistry Letters",

issn = "0366-7022",

publisher = "Chemical Society of Japan",

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T1 - An Efficient Protocol for Selective Silylation of Hydroxy Group Using N,O-Bis(tert-butyldimethylsilyl)acetamide and N,N-Dimethyl-4-aminopyridine N-Oxide

AU - Mandai, Hiroki

AU - Matsuura, Yuichiro

AU - Johari, Fatin Mahfuzah Binti

AU - Mitsudo, Koichi

AU - Suga, Seiji

N1 - Funding Information: This research was partially supported by JSPS Kakenhi Grant Number JP19K05456. The authors also thank DAICEL corporation for analyzing an enantiomeric ratio of 5f. Publisher Copyright: © 2022 The Chemical Society of Japan.

PY - 2022/9

Y1 - 2022/9

N2 - An efficient method for the silylation of alcohols was developed using N,O-bis(tert-butyldimethylsilyl)acetamide (BTBSA) and 3mol% of N,N-dimethyl-4-aminopyridine Noxide (DMAPO). Monosilylation of 1,2-diols was successfully achieved with high chemoselectivity. In addition, several control experiments revealed that a phenolic hydroxy group was silylated much faster than a primary alcohol in both an inter- and intramolecular manner. The reactivity toward silylation under these systems might stem from the pKa of the hydroxy group.

AB - An efficient method for the silylation of alcohols was developed using N,O-bis(tert-butyldimethylsilyl)acetamide (BTBSA) and 3mol% of N,N-dimethyl-4-aminopyridine Noxide (DMAPO). Monosilylation of 1,2-diols was successfully achieved with high chemoselectivity. In addition, several control experiments revealed that a phenolic hydroxy group was silylated much faster than a primary alcohol in both an inter- and intramolecular manner. The reactivity toward silylation under these systems might stem from the pKa of the hydroxy group.

KW - Chemoselective silylation

KW - DMAPO

KW - Organocatalyst

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JO - Chemistry Letters

JF - Chemistry Letters

IS - 9

ER -

An Efficient Protocol for Selective Silylation of Hydroxy Group Using N,O-Bis(tert-butyldimethylsilyl)acetamide and N,N-Dimethyl-4-aminopyridine N-Oxide

Abstract

Keywords

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