Unified Divergent Total Synthesis of Discorhabdin B, H, K, and Aleutianamine via the Late-Stage Oxidative N,S-Acetal Formation.

This study achieved the total syntheses of (+)-discorhabdin B, (-)-discorhabdin H, (+)-discorhabdin K, and (-)-aleutianamine. A phenethylamine fragment bearing a o-pivaloylthio group, corresponding to the D/E/G ring moiety, was prepared from benzothiophen-2-carboxylic acid methyl ester and condensed with a known pyrroloiminoquinone derivative. The adduct was subjected to [bis(trifluoroacetoxy)iodo]benzene (PIFA)-promoted oxidative spirocyclization to furnish the A/B/C/D/E spirocyclohexadienone fused with pyrroloiminoquinone. The total synthesis of (±)-discorhabdin B was completed via the key construction of the highly strained G ring with the N,S-acetal moiety featuring a newly developed CuBr2-mediated oxidative cascade cyclization. The stereocontrolled total synthesis of (+)-discorhabdin B was accomplished by a diastereoselective PIFA-promoted oxidative spirocyclization using a chiral thioester. (-)-Disocrhabdin H and (+)-discorhabdin K were synthesized by the site- and face-selective thia-Michael addition of l-ovothiol A to (+)-N-Ts-discorhabdin B with the concomitant formation of the F ring by forming the C2-N18 bond. The total synthesis of (-)-aleutianamine was achieved via a skeletal rearrangement initiated by the Luche reduction of the dienone moiety of (+)-N-Ts-discorhabdin B.

Cyclic Sulfamidite as Simultaneous Protecting Group for Amino Alcohols: Development of a Mild Deprotection Protocol Using Thiophenol.

This study describes the novel utility of cyclic sulfamidite as a simultaneous protecting group for 1,2- or 1,3-amino alcohols. An exceptionally mild and neutral condition for the removal of the cyclic sulfamidite was developed. The deprotection condition demonstrated a broad range of functional-group compatibility, including a substrate bearing a Z-enyne structure without any loss of double-bond stereochemistry.

Total Synthesis of (-)-Lepadiformine A via Radical Translocation-Cyclization Reaction.

Total synthesis of (-)-lepadiformine A featuring construction of the 1-azaspiro[4.5]decane skeleton by a highly diastereoselective radical translocation-cyclization reaction of a γ-lactam derivative bearing a chiral butenolide moiety is described. The enantioselective construction of butenolide is conducted via Krische's catalytic asymmetric allylation protocol. After the radical translocation-cyclization reaction, a hydroxymethyl group at the C-13 position was stereoselectively introduced by a one-pot partial reduction-allylation protocol of the unprotected lactam derivative. Finally, the total synthesis is completed by formation of a C ring.