Stereocontrolled Synthesis of the Quinaldic Acid Macrocyclic System of Thiostrepton We thank Drs. D. H. Huang and G. Suizdak for NMR spectroscopic and mass spectrometric assistance, respectively, as well as Mike Sertic (University of California, San Diego) for experimental assistance. Financial support for this work was provided by The Skaggs Institute for Chemical Biology, the National Institutes of Health (USA), fellowships from The Skaggs Institute for Research (to M.Z. and F.Z.), and grants from Abbott

Abstract

Ein wesentliches Strukturelement des Antibiotikums Thiostrepton ist ein Chinaldinsäure‐Makrocyclus (siehe Bild), der neben einer Chinaldinsäureeinheit mit drei Chiralitätszentren einen Thiazolring und eine Dehydroalanineinheit enthält. Schlüsselschritte für den konvergenten Aufbau waren: a) eine Amidverknüpfung, b) eine Veresterung und c) der Ringschluss zum Makrolactam.

Synthetic Studies on Thiostrepton: Construction of Thiostrepton Analogues with the Thiazoline‐Containing Macrocycle

“…Thiostrepton ( 1 , Scheme )1 is a highly complex thiopeptide antibiotic endowed with an unusual molecular architecture and a mode of action that involves RNA binding. As part of our program directed towards the total synthesis of this unique natural product, we have already reported synthetic approaches to both its dehydropiperidine domain2 and its segment corresponding to the quinaldic acid macrocycle 3. Herein we disclose further advances that pave the way for an eventual total synthesis of 1 and its analogues by addressing the remaining challenges posed by the imposing and sensitive structure of the molecule.…”

A Biomimetically Inspired Synthesis of the Dehydropiperidine Domain of Thiostrepton We thank Drs. D. H. Huang and L. Pasternack, G. Suizdak, and R. Chadja for NMR spectroscopic, mass spectrometric, and X-ray crystallographic assistance, respectively. Financial support for this work was provided by The Skaggs Institute for Chemical Biology, the National Institutes of Health (USA), fellowships from The Academy of Finland (M.N.), The Skaggs Institute for Research (M.Z.), and Bayer AG (S.B.), and grants from A

“…In the preceding communication,1 we described a stereoselective construction of the macrocycle of thiostrepton ( 1 )2 which incorporates the quinaldic acid moiety of the molecule 3a. Herein we report an expedient synthesis of the dehydropiperidine domain 2 (Scheme )3b of this complex antibiotic based on a biomimetic strategy involving a cascade reaction, which features a striking dimerization of a designed azadiene 3 , through a hetero‐Diels–Alder reaction,4 followed by hydrolytic excision of the superfluous thiazole moiety.…”

Catalytic Asymmetric Baeyer–Villiger Oxidation in Water by Using PtII Catalysts and Hydrogen Peroxide: Supramolecular Control of Enantioselectivity

“…The synthesis of such a quinoline has been addressed by two research groups, both electing to use ring opening of a chiral epoxide formed by Jacobson‐style asymmetric epoxidation as the key step (Scheme ) 87. 96–98 Since both strategies are essentially the same, only the route developed by Nicolaou et al. is shown in Scheme .…”