Mechanistic studies on nitrosation-deaminocyclization of mono-carbamoylated vicinal amino alcohols and diols

A new preparative in situ formation of ethanediazo hydroxide for the ethylation of carboxylates under mild conditions

Masumi Suzuki, Takeshi Sugai

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

While the cyclization of N-carbamoylamino alcohols into oxazolidinones via the activation with NO+ underwent smoothly, we found that similar reactions of vicinal diol monocarbamates were very slow. Mechanistic studies by means of time-resolved IR measurements of the former reaction suggested that the initial O-nitrosation was the rate-determining step. Indeed, the introduction of an ethyl group on the nitrogen terminus of diol monocarbamate promoted the desired cyclic carbonate formation. The concomitantly formed ethanediazo hydroxide, the precursor of the protonated form of diazoethane, was evidenced by trapping with p-nitrobenzoic acid as an ethyl ester. The formation of ethyl ester accelerates the reaction in an irreversible manner. Based on an elaboration of the substrates and reaction conditions, 2,3-dimethyl-2,3- butanediol mono-N-ethyl-N-nitrosocarbamate, which is easily prepared in situ from the corresponding ethylcarbamate and t-butyl nitrite, was developed as a new ethylation reagent of various carboxylic acids under mild conditions.

Original languageEnglish
Pages (from-to)1217-1227
Number of pages11
JournalBulletin of the Chemical Society of Japan
Volume77
Issue number6
DOIs
Publication statusPublished - 2004

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Amino Alcohols
4-nitrobenzoic acid
Esters
Oxazolidinones
Carbonates
Cyclization
Carboxylic Acids
Nitrogen
Chemical activation
Alcohols
Substrates
Nitrosation
hydroxide ion
n-butyl nitrite
nitrosocarbamic acid
2,3-butylene glycol

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Mechanistic studies on nitrosation-deaminocyclization of mono-carbamoylated vicinal amino alcohols and diols: A new preparative in situ formation of ethanediazo hydroxide for the ethylation of carboxylates under mild conditions",
abstract = "While the cyclization of N-carbamoylamino alcohols into oxazolidinones via the activation with NO+ underwent smoothly, we found that similar reactions of vicinal diol monocarbamates were very slow. Mechanistic studies by means of time-resolved IR measurements of the former reaction suggested that the initial O-nitrosation was the rate-determining step. Indeed, the introduction of an ethyl group on the nitrogen terminus of diol monocarbamate promoted the desired cyclic carbonate formation. The concomitantly formed ethanediazo hydroxide, the precursor of the protonated form of diazoethane, was evidenced by trapping with p-nitrobenzoic acid as an ethyl ester. The formation of ethyl ester accelerates the reaction in an irreversible manner. Based on an elaboration of the substrates and reaction conditions, 2,3-dimethyl-2,3- butanediol mono-N-ethyl-N-nitrosocarbamate, which is easily prepared in situ from the corresponding ethylcarbamate and t-butyl nitrite, was developed as a new ethylation reagent of various carboxylic acids under mild conditions.",
author = "Masumi Suzuki and Takeshi Sugai",
year = "2004",
doi = "10.1246/bcsj.77.1217",
language = "English",
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pages = "1217--1227",
journal = "Bulletin of the Chemical Society of Japan",
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T1 - Mechanistic studies on nitrosation-deaminocyclization of mono-carbamoylated vicinal amino alcohols and diols

T2 - A new preparative in situ formation of ethanediazo hydroxide for the ethylation of carboxylates under mild conditions

AU - Suzuki, Masumi

AU - Sugai, Takeshi

PY - 2004

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N2 - While the cyclization of N-carbamoylamino alcohols into oxazolidinones via the activation with NO+ underwent smoothly, we found that similar reactions of vicinal diol monocarbamates were very slow. Mechanistic studies by means of time-resolved IR measurements of the former reaction suggested that the initial O-nitrosation was the rate-determining step. Indeed, the introduction of an ethyl group on the nitrogen terminus of diol monocarbamate promoted the desired cyclic carbonate formation. The concomitantly formed ethanediazo hydroxide, the precursor of the protonated form of diazoethane, was evidenced by trapping with p-nitrobenzoic acid as an ethyl ester. The formation of ethyl ester accelerates the reaction in an irreversible manner. Based on an elaboration of the substrates and reaction conditions, 2,3-dimethyl-2,3- butanediol mono-N-ethyl-N-nitrosocarbamate, which is easily prepared in situ from the corresponding ethylcarbamate and t-butyl nitrite, was developed as a new ethylation reagent of various carboxylic acids under mild conditions.

AB - While the cyclization of N-carbamoylamino alcohols into oxazolidinones via the activation with NO+ underwent smoothly, we found that similar reactions of vicinal diol monocarbamates were very slow. Mechanistic studies by means of time-resolved IR measurements of the former reaction suggested that the initial O-nitrosation was the rate-determining step. Indeed, the introduction of an ethyl group on the nitrogen terminus of diol monocarbamate promoted the desired cyclic carbonate formation. The concomitantly formed ethanediazo hydroxide, the precursor of the protonated form of diazoethane, was evidenced by trapping with p-nitrobenzoic acid as an ethyl ester. The formation of ethyl ester accelerates the reaction in an irreversible manner. Based on an elaboration of the substrates and reaction conditions, 2,3-dimethyl-2,3- butanediol mono-N-ethyl-N-nitrosocarbamate, which is easily prepared in situ from the corresponding ethylcarbamate and t-butyl nitrite, was developed as a new ethylation reagent of various carboxylic acids under mild conditions.

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