An Efficient Synthesis of the Fully Elaborated Isoindolinone Unit of Muironolide A

An efficient stereocontrolled construction of the fully substituted isoindolone subunit of muironolide A is described. The approach is centered on the intramolecular Diels–Alder reaction between the enol form of the <b>β</b>-keto amide and an <b>α</b>,<b>β</b>,<b>γ</b>,<b>δ</b>-unsaturated ester, followed by the installation of the cyclohexene double bond

An Efficient Synthesis of the Fully Elaborated Isoindolinone Unit of Muironolide A

An efficient stereocontrolled construction of the fully substituted isoindolone subunit of muironolide A is described. The approach is centered on the intramolecular Diels–Alder reaction between the enol form of the <b>β</b>-keto amide and an <b>α</b>,<b>β</b>,<b>γ</b>,<b>δ</b>-unsaturated ester, followed by the installation of the cyclohexene double bond

Total Synthesis of Maoecrystal V: Early-Stage C–H Functionalization and Lactone Assembly by Radical Cyclization

A total synthesis of the unusual <i>ent</i>-kaurane maoecrystal V is described. The synthesis strategy features a counterintuitive early disconnection of the lactone subunit to a polycyclic enol ether intermediate in order to preserve the central tetrahydrofuran ring until the beginning stages of the synthesis. This strategy enables an application of C–H functionalization at the early phase of the synthesis during the construction of a dihydrobenzofuran intermediate

Toward the Synthesis of <i>Nuphar</i> Sesquiterpene Thioalkaloids: Stereodivergent Rhodium-Catalyzed Synthesis of the Thiolane Subunit

A stereodivergent approach to the central thiolane subunit of <i>Nuphar</i> sesquiterpene thioalkaloids has been developed. This approach features a rhodium-catalyzed Stevens-type rearrangement in conjunction with an enzyme resolution reaction. Further elaboration into a polycyclic ring system via alcohol oxidation and ring-closing metathesis is also described

Total Synthesis and Structural Revision of (+)-Muironolide A

Muironolide A is a fascinating tetrachlorinated marine polyketide isolated from the sponge of <i>Phorbas</i> sp. Only 90 μg had been isolated, and the structure was established by nanoscale NMR techniques. Herein we report the total synthesis of the substance with the assigned structure of muironolide A, propose a revised structure based on NMR data, and complete the enantioselective total synthesis of muironolide A

Stereoselective α‑Fluorination of <i>N</i>‑Acyloxazolidinones at Room Temperature within 1 h

A direct α-fluorination of <i>N</i>-acyloxazolidinones based on the unique reactivity of group IVa metal enolates has been developed. The reaction is an experimentally simple, low-cost, quick, and energy-efficient alternative for asymmetric α-fluorination of <i>N</i>-acyloxazolidinones. Preliminary studies have shown compatibility with alkyl, alkenyl, and alkynyl, aromatic, and several heteroaromatic substituents. High diastereoselectivities have been achieved with most substrates tested, and the reaction is typically complete within 1 h at ambient temperature

Synthesis of 2‑Aminoazoles from Thioesters via α‑Heterosubstituted Ketones by Copper-Mediated Cross-Coupling

Facile synthesis of a variety of α-heterosubstituted ketones under mild conditions was achieved by copper-mediated cross-coupling of thioesters with functionalized organostannanes. Application of this coupling methodology provided a concise pathway for the conversion of carboxylic acids to 2-aminoimidazoles, 2-aminothiazoles, and 2-aminooxazoles via thioesters in practical yields

A Simple Method for Asymmetric Trifluoromethylation of <i>N</i>-Acyl Oxazolidinones via Ru-Catalyzed Radical Addition to Zirconium Enolates

A Ru-catalyzed direct thermal trifluoromethylation and perfluoroalkylation of <i>N</i>-acyloxazolidinones has been developed. The reaction is experimentally simple and requires inexpensive reagents while providing good yields of products with good levels of stereocontrol. Preliminary studies have shown notable compatibility with functional groups, aromatics, and certain heteroaromatic substituents. The described method provides a useful alternative for the synthesis of fluorinated materials in an experimentally convenient manner

Total Synthesis of (+)-Guadinomic Acid via Hydroxyl-Directed Guanidylation

Protecting-group-free total synthesis of (+)-guadinomic acid is reported using δ-valerolactone as a readily available starting material. The protocol utilizes the recent hydroxyl-directed guanidylation of unactivated alkenes as an approach for direct stereoselective incorporation of the guanidine unit furnishing the natural product in 7 steps

A Simple Method for Asymmetric Trifluoromethylation of <i>N</i>-Acyl Oxazolidinones via Ru-Catalyzed Radical Addition to Zirconium Enolates

A Ru-catalyzed direct thermal trifluoromethylation and perfluoroalkylation of <i>N</i>-acyloxazolidinones has been developed. The reaction is experimentally simple and requires inexpensive reagents while providing good yields of products with good levels of stereocontrol. Preliminary studies have shown notable compatibility with functional groups, aromatics, and certain heteroaromatic substituents. The described method provides a useful alternative for the synthesis of fluorinated materials in an experimentally convenient manner