ChemInform Abstract: Synthesis of 4-Oxo Aldehydes by the Ceric Ammonium Nitrate Promoted Oxidative Addition of Trimethylsilyl Enol Ethers to Ethyl Vinyl Ether.

ChemInform ◽  
2010 ◽  
Vol 22 (13) ◽  
pp. no-no
Author(s):  
E. BACIOCCHI ◽  
A. CASU ◽  
R. RUZZICONI
Keyword(s):  
Ammonium Nitrate ◽  
Vinyl Ether ◽  
Oxidative Addition ◽  
Ceric Ammonium Nitrate ◽  
Ethyl Vinyl Ether ◽  
Ethyl Vinyl ◽  
Enol Ethers

scholarly journals Dihydrofurans from α-diazoketones due to facile ring opening – cyclization of donor–acceptor cyclopropane intermediates

1996 ◽  
Vol 74 (12) ◽  
pp. 2401-2412 ◽  
Author(s):  
Elizabeth A. Lund ◽  
Isaac A. Kennedy ◽  
Alex G. Fallis
Keyword(s):  
Vinyl Ether ◽  
Ring Opening ◽  
Ethyl Vinyl Ether ◽  
Reaction Conditions ◽  
Substitution Pattern ◽  
Initial Product ◽  
Ethyl Vinyl ◽  
Enol Ethers ◽  
Donor Acceptor ◽  
Rhodium Acetate

A series of α-diazoketones, 8, 25, 28, 31, and 34, have been synthesized and their reaction with ethyl vinyl ether examined under various reaction conditions. In the presence of metal salts (Rh2(OAc)4, Pd(OAc)2, CuCl) the ethoxy-dihydrofurans 12, 37, 39, 41, and 43 are produced. Sensitized irradiation of the α-diazoketone 8 afforded the dihydrofuran 12 plus cyclobutanone 7, while direct photolysis of α-diazoketones 8, 25, 28, 31, and 34 gave the cyclobutanones 7, 38,40,42, and 44, respectively. A sample of the cyclopropylketone 45 was isolated from the rhodium(II) acetate mediated reaction of 34 and its facile rearrangement to dihydrofuran 43 demonstrated. Collectively, these results indicate that the initial product from the reaction of an α-diazoketone with an electron-rich alkene such as ethyl vinyl ether is a cyclopropylketone. The donnor–acceptor substitution pattern of this intermediate results in spontaneous rearrangement to a dihydrofuran. Thus a direct dipolar cycloaddition mechanism is not involved when α-diazoketones react with enol ethers under metal-mediated conditions. Instead, these reactions follow a cyclopropanation rearrangement or, more accurately, cyclopropanation – ring opening – cyciization pathway. Key words: diazoketone, rhodium acetate, dihydrofuran, cyclopropylketone, vinyl ether.

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