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.
Subject(s)
Polymers/chemistry , StereoisomerismABSTRACT
An operationally simple, direct azidation of 1,3-dicarbonyl compounds has been developed. The reaction proceeds readily under ambient conditions using sodium azide and an iodine-based oxidant such as I(2) or 2-iodoxybenzoic acid (IBX)-SO(3)K/NaI. In particular, the latter method, as a new and well-balanced oxidizing agent, shows excellent functional group tolerance and substrate scope and thus allows access to a variety of tertiary 2-azido and 2,2-bisazido 1,3-dicarbonyl compounds that would be more difficult to access by using traditional methods. Because the azide-containing products easily undergo 1,3-dipolar cycloaddition with alkynes, our report represents a novel route to analogues of sensitive complex molecules.
Subject(s)
Azides/chemistry , Carbon/chemistry , Iodine/chemistry , Oxygen/chemistry , Click Chemistry , Dimethyl Sulfoxide/chemistry , Molecular Structure , Oxidation-ReductionABSTRACT
Gold catalysis has emerged as one of the most dynamic fields in organic synthesis. Only recently, more and more domino processes, for which gold pre-catalysts were found to be outstandingly effective, were paralleled by employing iodine electrophiles in place of gold compounds. This review highlights how, in certain cases, iodonium activation can match gold-catalyzed reactions to construct identical product scaffolds. Likewise, processes are discussed where mostly identical starting materials are transformed into diverse frameworks depending on whether gold or iodonium activation was used to trigger the reaction.
