Inspirations from tetrafibricin and related polyketides: new methods and strategies for 1,5-polyol synthesis

Abstract

Selective synthesis with control of remote stereogenic centers has long been a challenge in organic chemistry.

Microbiological Aspects of Unique, Rare, and Unusual Fatty Acids Derived from Natural Amides and Their Pharmacological Profile

“…are producers of zwitterionic polyketides with FA (163) and their biosynthesis is well described [180]. Three polyene antibiotics, mediomycins A (164), B (165), and clethramycin (163), were detected in extracts of Streptomyces mediocidicus ATCC23936 [181,182]. Actinomycete Amycolatopsis orientalis (see Figure 26), deposited as a vancomycin producer, produced, a glycosidic polyketide ECO-0501, which contained fatty acid (160) [174].…”

“…are producers of zwitterionic polyketides with FA (163) and their biosynthesis is well described [180]. Three polyene antibiotics, mediomycins A (164), B (165), and clethramycin (163), were detected in extracts of Streptomyces mediocidicus ATCC23936 [181,182].…”

Stereocontrolled Total Synthesis of Bastimolide B Using Iterative Homologation of Boronic Esters

“…Indeed, the stereoselective synthesis of polypropionates/polyacetates represents one of the crowning achievements of synthesis in the 20th century. − Despite the advances in polyketide synthesis, several challenges still remain, such as the stereoselective construction of 1,5-stereogenic centers . Of particular interest is the construction of 1,5-polyols, as they occur in many polyketides . The current state-of-the-art technology to access 1,5-diols is through a three-step sequence comprising stereoselective aldehyde allylation, cross-metathesis with acrolein, and alcohol protection (Figure A) .…”

An Iterative Phosphate Tether Mediated Approach for the Synthesis of Complex Polyol Subunits

“…The development of atom-, step-, , redox-, and pot-economical − methods to generate important subunits within biologically relevant natural products is an important component of modern-day synthesis and drug discovery. Among many synthetic approaches that aspire toward these goals are domino/cascade/multicomponent reactions, pot-efficient telescoped strategies, and iterative methods, − to name a few. Polyketide natural products are constructed in nature in an iterative and modular manner using enzymatic assembly with simple building blocks, which has inspired the development of synthetic methods to access polyketides and other natural products, allowing SAR studies and biological evaluation. − …”

“…In 2018, Burke and co-workers provided the field with a comprehensive review toward the generalized iterative synthesis of small molecules using a building block approach . In 2020, Friestad reviewed developments in 1,5-polyol synthesis, several methods which were iterative and dedicated to remote stereocontrol . Collectively, these reviews highlight a number of elegant iterative methods to various skipped polyols, and representative examples are contained in Scheme …”