Stereoselective Construction of the Methylcyclopentane Core of Peditithins B–H with Five Continuous Stereocenters

Abstract

A stereoselective construction of the methylcyclopentane core (3) of jatrophane diterpenoids peditithins B−H was achieved in 14 steps from commercially available D-(+)-ribono-1,4-lactone (9). The linear 5-ene-heptanal derived from 9 was cyclized to the five-membered ring by an intramolecular carbonyl ene reaction, and five continuous stereocenters on 3 were stereoselectively introduced via a successive substrate-controlled manner, involving diastereoselective 1,4-addition, MoOPH-induced hydroxylation, and stereospecific epoxidation.

Gilman reagent toward the synthesis of natural products

“…Ni et al in 2020 performed this challenging task and presented an efficient and facile route for the synthesis of methylcyclopentane 87 (containing five stereocenters) as a building block for the synthesis of peditithins H ( Scheme 9 ). 51 In their synthetic procedure with 14 steps, the easily available lactone 78 was transformed into α,β-unsaturated compound 79 under given conditions. Next, the installation of a methyl group with the desired stereochemistry was accomplished via 1,4-conjugate addition using a well-suited Gilman reagent.…”