In organic chemistry, alkynylation is an addition reaction in which a terminal alkyne () is added to a carbonyl group () to form an α-alkynyl alcohol ().
When the acetylide is formed from acetylene (), the reaction gives an α-ethynyl alcohol. This process is often referred to as ethynylation. Such processes often involve metal acetylide intermediates.
The principal reaction of interest involves the addition of the acetylene () to a ketone () or aldehyde ():
RR'C=O + HC#CR'' -> RR'C(OH)C#CR''
The reaction proceeds with retention of the triple bond. For aldehydes and unsymmetrical ketones, the product is chiral, hence there is interest in asymmetric variants. These reactions invariably involve metal-acetylide intermediates.
This reaction was discovered by chemist John Ulric Nef in 1899 while experimenting with reactions of elemental sodium, phenylacetylene, and acetophenone. For this reason, the reaction is sometimes referred to as Nef synthesis. Sometimes this reaction is erroneously called the Nef reaction, a name more often used to describe a different reaction (see Nef reaction). Chemist Walter Reppe coined the term ethynylation during his work with acetylene and carbonyl compounds.
In the following reaction (scheme 1), the alkyne proton of ethyl propiolate is deprotonated by n-butyllithium at -78 °C to form lithium ethyl propiolate to which cyclopentanone is added forming a lithium alkoxide. Acetic acid is added to remove lithium and liberate the free alcohol.
Several modifications of alkynylation reactions are known:
In the Arens–van Dorp synthesis the compound ethoxyacetylene is converted to a Grignard reagent and reacted with a ketone, the reaction product is a propargyl alcohol.
The Isler modification is a modification of Arens–Van Dorp Synthesis where ethoxyacetylene is replaced by β-chlorovinyl ether and lithium amide.
Alkynylations, including the asymmetric variety, have been developed as metal-catalyzed reactions. Various catalytic additions of alkynes to electrophiles in water have also been developed.
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L'acétylure ou acétylénure ou éthynure ou encore dicarbure est un anion divalent de formule C22− ou (C≡C)2−. C'est la base conjuguée de l'éthyne, C2H2 ou H-C≡C-H, le prototype des alcynes qui se comporte comme un acide faible, c'est-à-dire qui peut perdre ses deux protons. Ce terme est aussi utilisé pour tout anion monovalent de la forme R-C≡C−, où R peut être tout substituant organique monovalent comme hydrogénoacétylure, H-C≡C− ou méthylacétylure, H3C-C≡C−.
Ethisterone, also known as ethinyltestosterone, pregneninolone, and anhydrohydroxyprogesterone and formerly sold under the brand names Proluton C and Pranone among others, is a progestin medication which was used in the treatment of gynecological disorders but is now no longer available. It was used alone and was not formulated in combination with an estrogen. The medication is taken by mouth. Side effects of ethisterone include masculinization among others.
vignette|Schéma d'une addition nucléophile sur un carbonyle En chimie organique, une réaction nucléophile s'effectue entre un substrat quelconque et un réactif nucléophile. Une addition, en chimie, consiste en l'ajout d'un atome ou groupe d'atomes sur un substrat possédant une liaison insaturée. Un nucléophile est un atome ou une molécule qui présente une forte affinité pour les substances électrophiles.
Le cours se focalisera sur les composés carbonyles: leur structures, réactivités, et leurs transformations; la réactivité des énols/énolates et leurs réactions fondamentales. L'importance de la compré
The alkyne motif is a versatile functional group often encountered in organic chemistry. It can be involved in various transformations such as the alkyne-azide cycloaddition and has found widespread application in medicinal chemistry, chemical biology and ...
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Although alkynes are one of the smallest functional groups, they are among the most versatile building blocks for organic chemistry, with applications ranging from biochemistry to material sciences. Alkynylation reactions have traditionally relied on the u ...
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