Base-Controlled Diastereodivergent Synthesis of (R)- and (S)-2-Substituted-4-alkylidenepiperidines by the Wadsworth−Emmons Reaction

Significant base and reaction time effects have been observed in the Wadsworth−Emmons reaction between a chiral 2-substituted-4-oxopiperidine and phosphonates. In the reactions carried out using a large excess of DBU as the base and prolonged reaction times, the initially formed 2R products epimeriz...

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Veröffentlicht in:	Journal of organic chemistry 2007-02, Vol.72 (3), p.1005-1008
Hauptverfasser:	Etayo, Pablo, Badorrey, Ramón, Díaz-de-Villegas, María D, Gálvez, José A
Format:	Artikel
Sprache:	eng
Schlagworte:	Alkadienes - chemical synthesis Chemistry Exact sciences and technology Ligands Models, Chemical Organic chemistry Organophosphonates - chemistry Piperidines - chemical synthesis Stereoisomerism Thermodynamics
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container_end_page	1008
container_issue	3
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container_title	Journal of organic chemistry
container_volume	72
creator	Etayo, Pablo Badorrey, Ramón Díaz-de-Villegas, María D Gálvez, José A
description	Significant base and reaction time effects have been observed in the Wadsworth−Emmons reaction between a chiral 2-substituted-4-oxopiperidine and phosphonates. In the reactions carried out using a large excess of DBU as the base and prolonged reaction times, the initially formed 2R products epimerized into thermodynamically more stable products through a retro-conjugate/conjugate addition sequence and 2-substituted-4-alkylidenepiperidines of 2S configuration were selectively synthesized. In contrast, when the reaction was carried out using LDA as the base, epimerization did not occur and 2-substituted-4-alkylidenepiperidines of 2R configuration were obtained with excellent yields.
doi_str_mv	10.1021/jo062075c
format	Article
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Org. Chem</addtitle><description>Significant base and reaction time effects have been observed in the Wadsworth−Emmons reaction between a chiral 2-substituted-4-oxopiperidine and phosphonates. In the reactions carried out using a large excess of DBU as the base and prolonged reaction times, the initially formed 2R products epimerized into thermodynamically more stable products through a retro-conjugate/conjugate addition sequence and 2-substituted-4-alkylidenepiperidines of 2S configuration were selectively synthesized. 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Org. Chem</addtitle><date>2007-02-02</date><risdate>2007</risdate><volume>72</volume><issue>3</issue><spage>1005</spage><epage>1008</epage><pages>1005-1008</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Significant base and reaction time effects have been observed in the Wadsworth−Emmons reaction between a chiral 2-substituted-4-oxopiperidine and phosphonates. In the reactions carried out using a large excess of DBU as the base and prolonged reaction times, the initially formed 2R products epimerized into thermodynamically more stable products through a retro-conjugate/conjugate addition sequence and 2-substituted-4-alkylidenepiperidines of 2S configuration were selectively synthesized. In contrast, when the reaction was carried out using LDA as the base, epimerization did not occur and 2-substituted-4-alkylidenepiperidines of 2R configuration were obtained with excellent yields.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>17253823</pmid><doi>10.1021/jo062075c</doi><tpages>4</tpages></addata></record>
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subjects	Alkadienes - chemical synthesis Chemistry Exact sciences and technology Ligands Models, Chemical Organic chemistry Organophosphonates - chemistry Piperidines - chemical synthesis Stereoisomerism Thermodynamics
title	Base-Controlled Diastereodivergent Synthesis of (R)- and (S)-2-Substituted-4-alkylidenepiperidines by the Wadsworth−Emmons Reaction
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