Synthesis of allenes by [2,3]-sigmatropic rearrangement of prop-2-yn-1-yl oxonium ylides formed in rhodium(II) carboxylate catalysed reactions of diazo compounds

1990 ◽  
pp. 46 ◽  
Author(s):  
Michael P. Doyle ◽  
Vahid Bagheri ◽  
E. Elizabeth Claxton
Keyword(s):  
Sigmatropic Rearrangement ◽  
Diazo Compounds ◽  
Oxonium Ylides

Enantioselective tandem formation and [2,3]-sigmatropic rearrangement of cyclic propargylic oxonium ylides catalyzed by dirhodium(II) tetrakis[N-phthaloyl-(S)-tert-leucinate]

2001 ◽  
Vol 41 (4) ◽  
pp. 283-296 ◽  
Author(s):  
Hideyuki Tsutsui ◽  
Maya Matsuura ◽  
Kazuishi Makino ◽  
Seiichi Nakamura ◽  
Makoto Nakajima ◽  
...  
Keyword(s):  
Sigmatropic Rearrangement ◽  
Oxonium Ylides

scholarly journals DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O

2010 ◽  
Vol 8 (1) ◽  
pp. 223-228 ◽  
Author(s):  
Zhenfeng Liu ◽  
Jianyong Liu
Keyword(s):  
Dft Calculations ◽  
Nucleophilic Addition ◽  
Diazo Compound ◽  
Experimental Results ◽  
Diazo Compounds ◽  
Reaction Pathways ◽  
Insertion Reaction ◽  
Oxonium Ylides ◽  
Oxonium Ylide ◽  
Very High

AbstractThe mechanism of the dirhodium tetracarboxylate-catalyzed O-H insertion reaction of diazomethane and methyl diazoacetate with H2O has been studied in detail using DFT calculations. The rhodium catalyst and a diazo compound couple to form a rhodiumcarbene complex. Of two reaction pathways of the Rh(II)-carbene complex with H2O, the stepwise pathway is more preferable than the concerted one. Formation of a Rh(II) complex-associated oxonium ylide is an exothermal process, and direct decomposition of the ylide gives a very high barrier. The high barriers for the 1,2-H shift of Rh(II) complex-associated oxonium ylides make the ylides become stable intermediates in both reactions, especially for the reactions in solution. Difficulty in formation of a free oxonium ylide supports experimental results, indicating that the Rh(II) complex-catalyzed nucleophilic addition of a diazo compound proceeds via a Rh(II) complex-associated oxonium ylide rather than via a free oxonium ylide.

Trapping of Oxonium Ylides with Michael Acceptors: Highly Diastereoselective Three-Component Reactions of Diazo Compounds with Alcohols and Benzylidene Meldrum’s Acids/4-Oxo-enoates

Synlett ◽  
2011 ◽  
Vol 2011 (12) ◽  
pp. 1717-1722 ◽  
Author(s):  
Liqing Jiang ◽  
Wenhao Hu ◽  
Xingchun Han ◽  
Minghua Gan ◽  
Huang Qiu ◽  
...  
Keyword(s):  
Diazo Compounds ◽  
Oxonium Ylides ◽  
Michael Acceptors ◽  
Meldrum's Acids
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