477565-36-9Relevant academic research and scientific papers
Highly trans-Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ-Deoxygenation and Heck-Matsuda Reaction: Asymmetric Total Synthesis of (-)-Musellarins A-C and Their Analogues
Li, Zhilong,Ip, Fanny C. F.,Ip, Nancy Y.,Tong, Rongbiao
, p. 11152 - 11157 (2015/11/10)
Fully functionalized pyranuloses derived from Achmatowicz rearrangement (AR) are versatile building blocks in organic synthesis. However, access to trans-2,6-dihydropyrans from pyranuloses remains underexplored. Herein, we report a new two-step trans arylation of AR products to access 2,6-trans-dihydropyranones. This new trans-arylation method built on numerous plausible, but unsuccessful, direct arylation reactions, including Ferrier-type and Tsuji-Trost-type reactions, was finally enabled by an unprecedented, highly regioselective γ-deoxygenation of AR products by using Zn/HOAc and a diastereoselective Heck-Matsuda coupling. The synthetic utility of the reaction was demonstrated in the first asymmetric total synthesis of (-)-musellarins A-C and 12 analogues in 11-12 steps. The brevity and efficiency of our synthetic route permitted preparation of enantiomerically pure musellarins and analogues (>20 mg) for preliminary cytotoxicity evaluation, which led us to identify two analogues with three-to-six times greater potency than the musellarins as promising new leads. O leaves, Ar comes: A highly regio- and diastereoselective trans-arylation of Achmatowicz rearrangement products by an unprecedented Zn-mediated reductive γ-deoxygenation and Heck-Matsuda reaction was developed for the efficient synthesis of trans-2-aryl-6-alkyl dihydropyranones (see scheme: L.A.=Lewis acid). The synthetic utility of this new method was further demonstrated in the first asymmetric total synthesis of (-)-musellarins A-C and 12 analogues in 11-12 steps.
Total syntheses of (±)-musellarins A-C
Li, Zhilong,Leung, Tsz-Fai,Tong, Rongbiao
supporting information, p. 10990 - 10993 (2014/10/15)
The first, diastereoselective total syntheses of musellarins A-C were achieved concisely with 7.8-9.8% yields in 15-16 steps. The key synthetic features include (i) an Achmatowicz rearrangement, Kishi reduction, and Friedel-Crafts cyclization to construct
