First Total Synthesis of Mosin B

Abstract

[figure: see text] The first total synthesis of mosin B and a diastereomer was accomplished using asymmetric desymmetrization of the sigma-symmetric diol and the Nozaki-Hiyama-Kishi reaction as the key steps. The THF core segment was stereoselectively constructed employing a stereodivergent synthesis starting from a common intermediate, 4-cyclohexene-1,2-diol, based on a desymmetrization strategy. By virtue of these synthetic results, it is suggested that the absolute configuration is 1a.

The Chemistry of C2‐Symmetric Bis(sulfoxides): A New Approach in Asymmetric Synthesis

“…[38,113] Thus, diols 132a and 132b were acetalized with 131 in the presence of TMSOTf and 2,6-lutidine in good yields to provide 133a and 133b (Scheme 31). [117] Mechanistic insights of this reaction have been given and the authors have proposed the intermediate 138, displaying minimised steric interactions and leading to the major desymmetrized adduct 139. This strategy has proved quite useful for the total synthesis of several relevant natural compounds such as (Ϫ)-allosamizoline [114] (135 Ǟ 137), (Ϫ)-galaquercitol, [115] (ϩ)-aspicillin, [116] mosin B.…”

Systematic Synthesis of Diastereomeric THF Ring Cores and Total Synthesis of Anti-Tumor Annonaceous Acetogenins

“…35,36 Assembly of the THF-ring segment 40 and the g-lactone segment 42 was carried out by Sonogashira coupling 37 (Scheme 15) to give the coupling product 43 in 72% yield. Selective reduction of endiyne 43 by Wilkinson catalyst afforded the product in only moderate yield.…”

Selective Monoprotection of Symmetrical Diols in a Flow Reactor

“…Desymmetrization reactions have attracted much attention in organic synthesis because they provide a powerful tool to access complex molecules from readily available symmetrical compounds [1] [2]. For instance, the desymmetrization of diols [3] [4] [5] [6] [7], dicarbonyls [8] [9] [10] [11] [12], diamines [13], and alkenes [14] [15] [16] has been successfully applied to the synthesis of natural products such as (-)-spongidepsin [7] and merrilactone A [9] [10]. In particular, the monoprotection of diols with the tetrahydropyranyl (THP) group has been widely used in the synthesis of bioactive compounds [17] [18] [19] [20].…”