No abstract

A versatile process for the construction of 1,3-polyols, a key structural element of polyketide-type natural products, is presented. The modular synthesis strategy involves the iterative chain elongation with novel four-carbon building blocks to access all possible stereoisomers of a growing 1,3-polyol chain. These chiral building blocks are designed to install four carbon atoms with two stereogenic centres by performing only four experimentally simple steps per elongation cycle, thus making these building blocks attractive for the realization of a universal platform from which to access a diverse range of polyketidic molecules.

A new chiral building block for the direct installation of the 1,3‐diol motif is presented. Aldehyde olefination followed by directed reduction allows for the synthesis of both the syn‐ and the anti‐configured diol in a fully stereocontrolled way. The building block was used for the total synthesis of naturally occurring 1,2,4‐trihydroxynonadecanes starting from pentadecanal.

New enantiopure building blocks (I) and (II) for direct installation of the 1,3‐diol motif are presented.

The cover picture shows a newly developed building block, which gives a simple and flexible access to 1,3‐diols as demonstrated in the Communication by S. F. Kirsch et al. on p. . This building block is chiral, and the stereogenic center that is part of the building block is unambiguously fixed. Attaching the building block to an aldehyde through olefination followed by substrate‐directed reduction then allows for the stereocontrolled creation of a 1,3‐diol unit. For example, both diastereomers of the naturally occurring 1,2,4‐trihydroxynonadecane, isolated from the unripe avocado fruit, can be synthesized in a stereocontrolled way by using this building block: One compound to create them all ...