A convergent strategy for the synthesis of dideoxysalarin C (3) as a potential intermediate for the total synthesis of the marine macrolide salarin C (1) is described. The macrolactone core of 3 was assembled by Suzuki coupling between alkyl iodide 9 and vinyl iodide 8 and Shiina macrolactonization as key transformations. All macrocyclic intermediates were found to be of low stability.Letter pubs.acs.org/OrgLett

Furan‐ and indole‐derived boronate complexes react with alkyl iodides under radical (photoredox) or polar (SN2) conditions to generate three‐component alkylation products with high efficiency and complete stereospecificity. The methodology allows the incorporation of versatile functional groups such as nitriles, ketones, esters, sulfones, and amides, providing rapid access to complex chiral heteroaromatic molecules in enantioenriched form. Interestingly, while indolyl boronate complexes react directly with alkyl halides in a polar pathway, furyl boronates require photoredox catalysis. Careful mechanistic analysis revealed that the boronate complex not only serves as a substrate in the reaction but also acts as a reductive quencher for the excited state of the photocatalyst.

Several synthetic routes toward triazole building block 2-(3-methyl-1H-1,2,4-triazol-1-yl)acetic acid are described. The main problems of the initial synthetic route via alkylation of 3-Me-1H-1,2,4-triazole, such as poor regioselectivity, low yield, and purification by column chromatography, could be significantly improved or completely avoided in the second-generation approaches. Key concepts for the design of the alternative synthesis approaches to solve the problem of regioselectivity were the desymmetrization of 3,5-dibromo-1H-1,2,4-triazole and the de novo synthesis of the triazole core. The scalability of all routes was demonstrated on >100 g scale.