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Title: Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides

Abstract

Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, {alpha}-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of {alpha}-phenoxy ethyl acetates. The use of EDA to form {alpha}-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethylmore » diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and to benzil; at the same time the epoxide was converted to an olefin. 75 refs., 1 fig., 7 tabs.« less

Authors:
;  [1]
  1. Ames Lab., IA (United States)
Publication Date:
OSTI Identifier:
420838
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 118; Journal Issue: 41; Other Information: PBD: 16 Oct 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; 66 PHYSICS; ORGANIC COMPOUNDS; CATALYSIS; CHEMICAL REACTIONS; ORGANIC NITROGEN COMPOUNDS; CYCLOALKANES; SYNTHESIS; AZO COMPOUNDS; ALKENES; ORGANOMETALLIC COMPOUNDS; NUMERICAL DATA; RHENIUM COMPLEXES; RHENIUM OXIDES; CATALYSTS; ACETATES

Citation Formats

Zhu, Z, Espenson, J H, and Iowa State Univ., Ames, IA. Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides. United States: N. p., 1996. Web. doi:10.1021/ja954039t.
Zhu, Z, Espenson, J H, & Iowa State Univ., Ames, IA. Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides. United States. https://doi.org/10.1021/ja954039t
Zhu, Z, Espenson, J H, and Iowa State Univ., Ames, IA. 1996. "Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides". United States. https://doi.org/10.1021/ja954039t.
@article{osti_420838,
title = {Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides},
author = {Zhu, Z and Espenson, J H and Iowa State Univ., Ames, IA},
abstractNote = {Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, {alpha}-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of {alpha}-phenoxy ethyl acetates. The use of EDA to form {alpha}-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and to benzil; at the same time the epoxide was converted to an olefin. 75 refs., 1 fig., 7 tabs.},
doi = {10.1021/ja954039t},
url = {https://www.osti.gov/biblio/420838}, journal = {Journal of the American Chemical Society},
number = 41,
volume = 118,
place = {United States},
year = {Wed Oct 16 00:00:00 EDT 1996},
month = {Wed Oct 16 00:00:00 EDT 1996}
}