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Preparation of Substituted Enol Derivatives From Terminal Alkynes and Their Synthetic Utility
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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 α-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, α-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.
Citing Articles
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This article has been cited by 5 ACS Journal articles (5 most recent appear below).
Palladium-Catalyzed Coupling of Haloalkynes with Allyl Acetate: A Regio- and Stereoselective Synthesis of (Z)-β-Haloenol Acetates
Xiaoyi Chen, Dongxu Chen, Zenghui Lu, Lichun Kong, and Gangguo ZhuThe Journal of Organic Chemistry2011 Article ASAPPalladium-Catalyzed Coupling of Haloalkynes with Allyl Acetate: A Regio- and Stereoselective Synthesis of (Z)-β-Haloenol Acetates
Xiaoyi Chen, Dongxu Chen, Zenghui Lu, Lichun Kong, and Gangguo ZhuThe Journal of Organic Chemistry2011 Article ASAPA Pd-catalyzed coupling of haloalkynes with allyl acetate has been reported, providing a convenient method for the stereoselective synthesis of (Z)-β-haloenol acetates in good yields. The synthetic utility of this method is demonstrated by the formation ...
Enol Silyl Ethers via Copper(II)-Catalyzed C–O Bond Formation
Daniel G. Chan, David J. Winternheimer, and Craig A. MerlicOrganic Letters2011 Article ASAPEnol Silyl Ethers via Copper(II)-Catalyzed C–O Bond Formation
Daniel G. Chan, David J. Winternheimer, and Craig A. MerlicOrganic Letters2011 Article ASAPCopper(II) acetate catalyzes the coupling of pinacol vinylboronates with silanols producing enol silyl ethers. This represents a novel enol silyl ether synthesis via formation of the C–O bond instead of the conventional Si–O bond. This also constitutes ...
Ruthenium(IV)-Catalyzed Markovnikov Addition of Carboxylic Acids to Terminal Alkynes in Aqueous Medium
Victorio Cadierno, Javier Francos, and José GimenoOrganometallics2011 30 (4), 852-862Ruthenium(IV)-Catalyzed Markovnikov Addition of Carboxylic Acids to Terminal Alkynes in Aqueous Medium
Victorio Cadierno, Javier Francos, and José GimenoOrganometallics2011 30 (4), 852-862The dimeric bis(allyl)ruthenium(IV) complex [{RuCl(μ-Cl)(η3:η3-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) (5) and several mononuclear species trans-[RuCl2(η3:η3-C10H16)(L)] (L = two-electron-donor ligand) (6) derived from 5 have been ...
Silver-Catalyzed Difunctionalization of Terminal Alkynes: Highly Regio- and Stereoselective Synthesis of (Z)-β-Haloenol Acetates
Zhengwang Chen, Jinghao Li, Huanfeng Jiang, Shifa Zhu, Yibiao Li and Chaorong QiOrganic Letters2010 12 (14), 3262-3265Silver-Catalyzed Difunctionalization of Terminal Alkynes: Highly Regio- and Stereoselective Synthesis of (Z)-β-Haloenol Acetates
Zhengwang Chen, Jinghao Li, Huanfeng Jiang, Shifa Zhu, Yibiao Li and Chaorong QiOrganic Letters2010 12 (14), 3262-3265A new silver-catalyzed highly regio- and stereoselective difunctionalization reaction of simple terminal alkynes was reported in which the (Z)-β-haloenol acetate derivatives were formed efficiently. The resulting products were versatile intermediates in ...
Scope and Mechanistic Investigations on the Solvent-Controlled Regio- and Stereoselective Formation of Enol Esters from the Ruthenium-Catalyzed Coupling Reaction of Terminal Alkynes and Carboxylic Acids
Chae S. Yi and Ruili GaoOrganometallics2009 28 (22), 6585-6592Scope and Mechanistic Investigations on the Solvent-Controlled Regio- and Stereoselective Formation of Enol Esters from the Ruthenium-Catalyzed Coupling Reaction of Terminal Alkynes and Carboxylic Acids
Chae S. Yi and Ruili GaoOrganometallics2009 28 (22), 6585-6592The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the alkyne-to-carboxylic acid coupling reaction to give synthetically useful enol ester products. A strong solvent effect was observed for the ruthenium ...
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History
- Published In Issue June 25, 2008
- Article ASAPJune 03, 2008
- Received: May 09, 2008
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