Triple-bond-containing hydroxy compounds

Scheme 41 Resolution of triple-bond-containing hydroxy compounds.

Addition of thiols in basic solution to the C=C—C=0 bond system in a,/3 imsaturated ketones, such as 4-benqrlidene-l-buQrl-pyrrolidine-2,3-dione, has been observed, forming with benzenethiol in piperidine, l-butyl-3-hydroxy-4(a-phenylthiobenzyl)-3-pyrrolin-2-one . Addition of thiols primarily to the C=C bond in C=C—C=0 systems in quinones and lactones has been observed . The reactions were studied in neutral or alkaline solution and probably involve attack by the thiolate anion. In compounds containing both carbonyl or carboxyl groups and acetylenic triple bonds, addition occurs primarily across the acetylene bond. Cyclization of the initial product so formed is also observed . ... 

The enantioselective esterification of unsaturated secondary alcohols has been extensively studied [182] and has found several successful additional applications with substrates containing double bonds [183-188]. The results have been collected in Table 2 and Scheme 40, whereas Scheme 41 shows interesting examples of the resolution of hydroxy compounds that contain a triple bond in the molecule [189,190]. 

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