2,2′-(Ethane-1,2-diyl)bis(4-chlorophenol)

The X-ray structure of the title compound, obtained as a byproduct in a natural product synthesis, has been determined and shows an unusual pattern featuring chains of molecules with both intra- and intermolecular hydrogen bonding of the OH groups.

14 Electrochemistry in Natural Product Synthesis

The multistep synthesis of natural products has historically served as a useful and informative platform for showcasing the best, state-of-the-art synthetic methodologies and technologies. Over the last several decades, electrochemistry has proved itself to be a useful tool for conducting redox reactions. This is primarily due to its unique ability to selectively apply any oxidizing or reducing potential to a sufficiently conductive reaction solution. Electrochemical redox reactions are readily scaled and can be more sustainable than competing strategies based on conventional redox reagents. In this chapter, we summarize the examples where electrochemistry has been used in the synthesis of natural products. The chapter is organized by the reaction type of the electrochemical step and covers both oxidative and reductive reaction modes.

Recognition of Symmetry as a Powerful Tool in Natural Product Synthesis

The design of concise and efficient synthetic strategies to access naturally occurring, pharmaceutically active complex molecules is of utmost importance in current chemistry. It not only enables rapid access to these molecules and their analogues but also provides sufficient quantities for their biological evaluation. Identification of any symmetric or pseudosymmetric synthetic intermediates upon retrosynthetic bond disconnection of the target molecule holds the promise to significantly streamline the route towards the compound of interest. This review will highlight recent examples of successful natural product syntheses reported within the past five years that benefited from the recognition of symmetry elements during the retrosynthetic design.

Catalytic, contra-Thermodynamic Alkene Isomerization

The positional isomerization of C–C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here we report the discovery of a dual catalyst system that promotes contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing access to terminal alkene isomers directly from conjugated, internal alkene starting materials. The utility of the method is demonstrated in the deconjugation of diverse electron rich/poor alkenes and through strategic application to natural product synthesis. Mechanistic studies are consistent with a regiospecific bimolecular homolytic substitution (SH2') mechanism proceeding through an allyl-cobaloxime intermediate.

Group-Selective Approaches to Complex Natural Product Synthesis: Three Examples of Diastereotopos-Selective Reactions

This Account showcases three diastereotopos-selective reactions exploited in our complex natural syntheses.1 Introduction2 Malyngolide: Hydroalumination of Bisalkynyl tert-Alcohols3 Cavicularin: Acetal Cleavage4 Carthamin: Bromoacetoxylation5 Conclusions

Recent Advance of Domino Michael Reaction in Natural Product Synthesis

Recent advances in the total syntheses of cyclic natural products and related compounds from 2005 to 2021, which employ domino Michael reactions as key steps, have been reviewed, focusing mainly on the domino Michael reactions catalyzed by organocatalysts.

Synthesis of α-exo-Methylene-γ-butyrolactone: Recent Developments and Applications in Natural Product Synthesis

The α-exo-methylene-γ-butyrolactone moiety is present in a vast array of structurally diverse natural products and is often central to their biological activity. In this review, we summarize new approaches to α-exo-methylene-γ-butyrolactones developed over the past decade as well as their applications in total synthesis.