A stereoselective synthesis of the C9-C19 subunit of (+)-peloruside AElectronic supplementary information (ESI) available: Experimental procedures for the preparation of known compounds 11, 9, 8, anti-1,3-acetonide of compounds 15, 23, 24, 25, 26, 33 and epi-33. Copies of 1H and 13C NMR spectra for the compounds. See DOI: 10.1039/c3ob27508f

The stereoselective synthesis of a C9-C19 fragment of the potent antitumor agent peloruside A is disclosed. The C11 stereogenic centre was created by a vinylogous Mukaiyama aldol reaction following Carreira's protocol, with excellent stereocontrol. The C13 stereogenic centre was introduced by a substrate controlled reduction. The C15 stereocentre was fashioned using Noyori's asymmetric transfer hydrogenation while the Z -trisubstituted double bond was formed by a regioselective hydrostannation of an alkyne followed by methylation of the resultant vinyl stannane using Lipshutz's protocol. The C18 chiral centre was introduced by a chemoenzymatic route. A stereoselective synthesis of the C9-C19 subunit of peloruside A is disclosed utilizing metal catalyzed catalytic asymmetric transformations, substrate controlled induction and enzymatic resolution.