Alkyne zipper reaction
Encyclopedia
The alkyne zipper reaction is an organic reaction
which isomerizes an organic compound containing an internal alkyne
into a terminal alkyne. This was first reported by Charles Allen Brown and Ayako Yamashita in 1975. The isomerization reaction proceeds for straight-chain alkynes and acetylinic alcohols and provides a useful approach for remote functionalization in long-chain hydrocarbons.
The reaction requires a strong base. The base used by Brown and Yamashita was potassium 1,3-diaminopropanide, generated in situ by adding potassium hydride
to the solvent
1,3-diaminopropane
. Alternative approaches have been investigated due to the expensive and hazardous nature of potassium hydride; ethylenediamine has been found to be an unsuitable replacement for 1,3-diaminopropane. As an example, for the synthesis of 9-decyn-1-ol from 2-decyn-1-ol, the lithium salt of 1,3-diaminopropane in the presence of potassium tert-butoxide
affords yields of approximately 85%.
Organic reaction
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, photochemical reactions and redox reactions. In organic synthesis,...
which isomerizes an organic compound containing an internal alkyne
Alkyne
Alkynes are hydrocarbons that have a triple bond between two carbon atoms, with the formula CnH2n-2. Alkynes are traditionally known as acetylenes, although the name acetylene also refers specifically to C2H2, known formally as ethyne using IUPAC nomenclature...
into a terminal alkyne. This was first reported by Charles Allen Brown and Ayako Yamashita in 1975. The isomerization reaction proceeds for straight-chain alkynes and acetylinic alcohols and provides a useful approach for remote functionalization in long-chain hydrocarbons.
The reaction requires a strong base. The base used by Brown and Yamashita was potassium 1,3-diaminopropanide, generated in situ by adding potassium hydride
Potassium hydride
Potassium hydride, KH, is a chemical compound of potassium and hydrogen. It is a hydride of potassium. It reacts with water according to the reaction:...
to the solvent
Solvent
A solvent is a liquid, solid, or gas that dissolves another solid, liquid, or gaseous solute, resulting in a solution that is soluble in a certain volume of solvent at a specified temperature...
1,3-diaminopropane
1,3-Diaminopropane
1,3-Diaminopropane is a simple amine. The potassium salt is used in the alkyne zipper reaction, first reported by Charles Allen Brown and Ayako Yamashita in 1975....
. Alternative approaches have been investigated due to the expensive and hazardous nature of potassium hydride; ethylenediamine has been found to be an unsuitable replacement for 1,3-diaminopropane. As an example, for the synthesis of 9-decyn-1-ol from 2-decyn-1-ol, the lithium salt of 1,3-diaminopropane in the presence of potassium tert-butoxide
Potassium tert-butoxide
Potassium tert-butoxide is the chemical compound with the formula 3COK. This colourless solid is a strong base useful in organic synthesis. It exists as a tetrameric cubane-like cluster...
affords yields of approximately 85%.
- HO–CH2C≡C–(CH2)6CH3 → HO(CH2)8–C≡CH