Iterative methods are ideal in the synthesis of molecules bearing common repeat motifs as they not only simplify synthesis but also analysis (retrosynthesis), since they allow disconnections around the common repeating building blocks. Indeed, using a comprehensive knowledge base of individual reactions, iterative methods can also now be recognised by computer algorithms in the construction of complex molecules. We recently reported the iterative synthesis of 1,3-polyols through a sequence of asymmetric alkene diboration and selective homologation of the resulting primary boronic ester with a metalated butenyl TIB ester A (Figure , M = Li, MgCl, TIB = 2,4,6triisopropylbenzoyl). We reasoned that performing anti-Markovnikov hydroboration, instead of diboration, followed by homologation with the same metalated butenyl TIB ester A could provide an iterative strategy for the construction of 1,5-polyols in just 2 steps per iteration rather than 3 (Figure ). In this paper we describe the success of this approach and its application to the first total synthesis of bastimolide B (1, Scheme 1A), one of the most complex polyketides, featuring 10 hydroxylated stereocenters, six of which feature 1,5-relationships.