Preparation of Substituted Enol Derivatives From Terminal Alkynes and Their Synthetic Utility
Year: 2008
Type: article
Abstract: Stereodefined enol derivatives of aldehydes are prepared from terminal alkynes. Specifically, terminal alkynes are known to undergo Cp2ZrCl2-catalyzed methylalumination. Here, we show that the resultant vinylalanes can be oxygenated with peroxyzinc species to generate trisubstituted enolates. Electrophilic trapping with carboxylic anydrides or silyl triflates yields trisubstituted enol esters or silanes, respectively. The tandem carbometalation/oxygenation tolerates free and protected alcohols, heterocycles, olefins, and nitriles. Stereodefined enol esters can undergo asymmetric dihydroxylation to yield optically active alpha-hydroxy aldehydes. Reduction with NaBH4 provides the diols of 1,1-disubstituted olefins in excellent ee. An application of this methodology to the enantioselective synthesis of the insect pheromone frontalin is presented. Finally, alpha-hydroxy aldehydes are shown to undergo homologation to a terminal alkyne, reductive amination, oxidation and olefination. Preliminary results indicate that tandem carbometalation/amination can be accomplished with azodicarboxylates. In this way, ene-hydrazines are formed in excellent yield.
DOI: 10.1021/ja803480b
Authors: John R. DeBergh, Kathleen M. Spivey, Joseph M. Ready
Institution: The University of Texas Southwestern Medical Center
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2018720744