1,4-Enynes acetylene derivs., synthesi

Cuprous chloride sodium chloride Synthesis of 1,4-enynes from acetylene derivatives... 

General Synthesis.—Terminal acetylenes can be transformed into carboxylic acids by conversion into the trimethylsilyl derivatives followed by addition of a dialkyl-borane and oxidative hydrolysis (Scheme 1). Conjugated enynes can undergo a similar conversion, and yields throughout are high. 

The Conia-ene reaction of P-ketoesters bearing a pendant triple bond involves the cycloisomerization of an enyne formed by enolization. This transformation is efficiently catalyzed by cationic gold(I) complexes and afforded cyclopentane derivatives with excellent yields and moderate to good diastereoselectivities (Scheme 4-40). Acetylenic silyl enol ethers or imines react in an analogous manner. By this method, iodoalkynes were converted into iodocyclopentenes, which are highly useful in natural product synthesis. 

Further work from Vollhardt s group on cobalt-catalysed cycloadditions of olefins and acetylenes has led to a synthesis of cyclohexadiene derivatives (188 n = 0—2) by addition of trimethyl silylacetylenes the reactions can also be carried out in an intramolecular sense, leading to tricyclic compounds. The novel tricyclic compound (189) has been obtained from naphthoquinone by a [2 + 2]addition of l,l-bis(silylmethyl)ethylene followed by treatment with a Lewis acid. A key step in the first total synthesis of a decipiene diterpene is the formation of tricyclic ketone (190) by an intramolecular aldol condensation, which required the use of methanolic barium oxide. ... 

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