Themed collection Synthesis III

This Highlight provides a brief overview of covalent, asymmetric modes of organocatalysis and applications of scalable versions of these methods applied to the total synthesis of natural products.

This Highlight article provides an overview of recent total syntheses that are characterized by high efficiency and enabled through a neat application of transition metal-catalyzed insertions of carbenes and nitrenes into C–H bonds.

This Highlight describes factors that contribute to an ideal synthesis, including economies (step, time, atom, solvent, energy) and orientations (target, diversity, safety, function), and the role of synthesis-informed design directed at function in advancing synthesis and its impact on science.

This Highlight covers the current status of relatively unexplored sp³–sp³ cross-coupling reactions with particular focus on natural product and related syntheses.

In this Highlight, we discuss recent examples of natural product synthesis from our laboratory and others, where the preparation of gram-scale quantities of a target compound or a key intermediate allowed for a deeper understanding of biological activities or enabled further investigational collaborations. (Picture courtesy of Frank Fang of Eisai Inc.)

The structurally unique calyciphylline A-type Daphniphyllum alkaloids have recently attracted the interest of natural product synthesis groups, due to the challenge posed by the complex structural framework. Recently, several noteworthy core syntheses were reported using a variety of novel synthetic strategies, which include intramolecular Michael addition, Pd-catalysis, cycloaddition and Mannich-type reactions.

This review will provide an overview on the recent developments of polyketide synthesis using the vinylogous Mukaiyama aldol reaction for the construction of advanced intermediates. In general, four different motifs can be constructed efficiently using the recent developments of asymmetric variants of this strategy.

The crux in multistep natural product synthesis is the exponential decrease of the yield with the number of steps. In this article various strategies are explained on how to circumvent this problem and to achieve efficient approaches nevertheless.

This review covers the synthetic assembly of peptide natural products in which a Cu-mediated C(sp²)–N bond formation is the key transformation, and particularly focuses on the total syntheses of cyclopeptide alkaloids, pacidamycin D, and yaku'amide A.

This review highlights the isolation and the structural determination of amphidinol 3 (AM3) with an emphasis on the different synthetic approaches.

Direct alcohol C–H bond functionalization bypasses the use of chiral auxiliaries, premetallated C-nucleophiles, and discrete alcohol-to-aldehyde redox reactions. This technology has enabled syntheses of 6-deoxyerythronolide B, bryostatin 7, trienomycins A and F, cyanolide A, roxaticin.

Important biomimetic steps in natural product synthesis have been promoted by transition metals, as exemplified by this beautiful ruthenium-catalyzed rearrangement of an endoperoxide into elysiapyrone A. Such reactions are supposed to occur during the biosynthesis, yet under different catalysis conditions.

This review has been organized from the perspective of synthetic target families, with emphasis on the use of gold-catalyzed transformations and cascade reactions that significantly increase molecular complexity.

This review presents selected recent advances in sequential catalytic methods developed in our group for the rapid and stereoselective synthesis of key structural features of complex polyketides and their successful application in complex target synthesis.

A personal selection of 32 recent papers is presented covering various aspects of current developments in bioorganic chemistry and novel natural products such as thelepamide from Thelepus crispus.