Some alkali metal alkyl amides as alkyne isomerization reagents: selective isomerization of one triple bond of a diynol

Abstract

61, 1073 (1983).The lithium and sodium salts of 1.2-diaminocthanc. l,3-diarninopropane. n-butylamine, and the lithium salt of isobutylaminc were studied as potential rcapcnts for isomcrization of triple bonds in alkyn-I-01s. The sodium salts of the diamincs afforded high yields of the o-alkyn-1-01. Somewhat surprisingly. the sodium salt of n-butylamine also effects isomerization to the terminal position. The lithium salt of 1,3-diaminopropanc gave the highest conversion of 2-to 3-alkyn-1-01, A novel, selective rearrangement of one triple bond of a diynol. a 2.0-to 3.w-diyn-1-01 isomcrization, was incorporated into a synthesis of the insect sex pheromone 3.13-octadccadienol acetate. On a 6valuC I'utilisd des sels de sodium et dc lithium du diarnino-1.2 Cthane. du diamino-1.3 propane, de la n-butylaminc et du sel de lithium dc I'isobutylamine en tant qu'apents potentiels d'isomdrisation des triples liaisons des alcynols-I. Les scls dc sodium des dialnines donnent des rendemcnts dlevds en o-alcynols-I. Par opposition le sel de sodium de la n-butylamine affcctc aussi I'isornCrisarion vers la position terminale. LC sel dc lithium du diamino-1.3 propane donne le plus fort pourcentage dc transformation des alcync-l 01s-I en alcyne-3 01s-I. Dans le cadre dc la synthkse de la phCromone scxuclle des insectes, I 'acetate d'octadecadienc-3.13 ol, on a introduit une nouvelle transposition sdlcctive d'une triple liaison d'un diynol ii savoir I'isomdrisation d'un 2.0-diync 01-1 en un 3,o-diyne ol-I.[Traduit par le journal]

Synthesis of triphenylphosphonium vitamin E derivatives as mitochondria-targeted antioxidants

“…MitoE 10 ( 4 ) was synthesised starting from 1-hydroxy-11-dodecyne, obtained by the addition of 1-bromononane to lithiated propargyl THP ether followed by triple bond migration using NaH and ethylenediamine. 39 In both cases the final step involved reaction of triphenylphosphine with the mesyloxy phenol ( S7, S11, Supplementary data ) and the adverse effects of extended exposure of the unprotected phenol moiety to these reaction conditions was evident.…”

Synthesis and isomerization of enyne-group containing compounds in NaEDA/EDA media

“…The multipositional migration of the triple bond along the carbon chain in hydrocarbons and alcohols by potassium 3-aminopropanamide was introduced by Brown 1 . Later other superbasic systems based on different alkali metal amides of 1,2-diaminoethane and 1,3-diaminopropane for such processes were developed [2][3][4][5] . The triple bond usually migrates to the terminal position of carbon chain but in branched chain compounds 6 and carboxylic acids 7,8 , several other compounds have been obtained.…”

Isomerization and Following Alkylation of (Z,e)-2-Octen-4-Yn-1-Ol as a One Pot Procedure in Super Basic Media

“…[s], alkynols [6,7], tertiary alkynyl amines [B], conjugated alkadiynes, and hydroxyalkadiynes [9] to the terminal position in super bases…”