Synthesis of alkenes: claisen rearrangement of allyl vinyl ethers, part i; mechanistic views; the organic chemistry notebook series, a didactical approach, N2 9
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Spanish title: Síntesis de alquenos mediante transposición de Claisen de éteres alil-vinílicos, parte I; vistas mecanicísticas; de la serie: El cuaderno de notas de química orgánica, un enfoque didáctico, N"9. Llegamos al noveno ensayo teórico en la serie: "El cuaderno de química orgánica, un enfoque didáctico". El objetivo de esta serie de estudios es ayudar a los estudiantes a disponer de una visión gráfica de reacciones de síntesis orgánicas de diversa naturaleza. En el actual capítulo, abordamos el fascinante tema de la transposición de Claisen de éteres alil-vinílicos como un método de obtener alquenos. A partir de alcoholes alílicos y por transposición del correspondiente derivado, alil-vinil éter, es factible la obtención de compuestos carbonílicos insaturados en posición: y8; éstos incluyen aldehídos, cetonas, esteres y amidas. Hemos propuesto mecanismos teóricos para la conversión de alcohol alílico en éter alil-vinílico. La síntesis de la feromona de insectos: 3,7-dimetil-2,6-decadien-1,10-diol a partir de alcohol alílico y ortoacetato de metilo, es mecanicísticamente revisada. Se discute también por mecanismos, la formación de N,N-dimetil amidas j#insaturadas. Para terminar la parte I de esta serie de síntesis de alquenos por transposición de Claisen de éteres alil-vinílicos, hemos estudiado un mecanismo factible, alternativa sintética al proceso acídico y bajo calor involucrado en la síntesis de compuestos carbonílicos j^insaturados: la transposición de Claisen de enolatos de litio, ó trimetíl ó terbutil dimetilsilil enol éteres. Hemos tomado una serie de reacciones revisadas por W. Carruthers en: 'Some modern methods of organic synthesis', para las cuales hemos propuesto vistas mecanicísticas y didácticas. Este tema esta incluido en el capítulo "Formation of carbon-carbon double bonds" del mencionado texto
We present now the ninth theoretical assay in the series: "The Organic Chemistry Notebook Series, a Didactical Approach". The aim of this series of studies is to help students to have a graphical view of organic synthesis reactions of diverse nature. In the present chapter, we board the fascinating thematic on Claisen rearrangements of ally-vinyl ethers as a way to obtain alkenes. Starting from allyl alcohols by rearrangements of the corresponding derivative allyl vinyl ether it is feasible the obtaining of carbonyl compounds unsaturated at the positions: yS; these include aldehydes, ketones, esters and amides. We have assayed theoretical mechanisms for the conversion of allyl alcohol into allyl vinyl ether. The synthesis of the insect pheromone: 3,7-dimethyl-2,6-decadiene-1,10-diol from allyl alcohol and methyl orthoacetate is mechanistically reviewed. The formation of j^unsaturated N,N-dimethyl amides is mechanistically discussed. To end the part I of this series on synthesis of alkenes by Claisen rearrangement of allyl vinyl ethers, we study a feasible mechanism of an alternative to the acidic and heated process involved in the synthesis of the j#unsaturated carbonyl compounds: the Claisen rearrangement of lithium enolates, or the trimethyl or the t-butyl dimethylsilyl enol ethers. We have taken a series of reactions reviewed by W. Carruthers in 'Some modern methods of organic synthesis', and we have proposed didactical and mechanistic views for them. This theme is included in the chapter "Formation of carbon-carbon double bonds" in the mentioned text.
We present now the ninth theoretical assay in the series: "The Organic Chemistry Notebook Series, a Didactical Approach". The aim of this series of studies is to help students to have a graphical view of organic synthesis reactions of diverse nature. In the present chapter, we board the fascinating thematic on Claisen rearrangements of ally-vinyl ethers as a way to obtain alkenes. Starting from allyl alcohols by rearrangements of the corresponding derivative allyl vinyl ether it is feasible the obtaining of carbonyl compounds unsaturated at the positions: yS; these include aldehydes, ketones, esters and amides. We have assayed theoretical mechanisms for the conversion of allyl alcohol into allyl vinyl ether. The synthesis of the insect pheromone: 3,7-dimethyl-2,6-decadiene-1,10-diol from allyl alcohol and methyl orthoacetate is mechanistically reviewed. The formation of j^unsaturated N,N-dimethyl amides is mechanistically discussed. To end the part I of this series on synthesis of alkenes by Claisen rearrangement of allyl vinyl ethers, we study a feasible mechanism of an alternative to the acidic and heated process involved in the synthesis of the j#unsaturated carbonyl compounds: the Claisen rearrangement of lithium enolates, or the trimethyl or the t-butyl dimethylsilyl enol ethers. We have taken a series of reactions reviewed by W. Carruthers in 'Some modern methods of organic synthesis', and we have proposed didactical and mechanistic views for them. This theme is included in the chapter "Formation of carbon-carbon double bonds" in the mentioned text.
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Vol. 33, No. 1