Stereoselective synthesis and antitumor activity of macrodiolides containing 1Z,5Z-diene and 1,3-diyne moieties

New macrodiolides incorporating 1Z,5Z-diene and 1,3-diyne moieties were obtained in 55–79% yields and with >98% stereoselectivity by Hf(OTf)4-catalyzed intermolecular cyclocondesation of (5Z,9Z)-tetradeca-5,9-diene-1,14-dioic acid with a,ω-diols. Alternative route included intramolecular oxidative coupling of a,ω-diynes, esterification products of (5Z,9Z)-tetradeca-5,9-diene-1,14-dioic acid with alkynols. The macrodiolides synthesized exhibit in vitro cytotoxic activity toward Jurkat, K562, U937, HL-60, HeLa and Hek293 cell lines.