A versatile Cu-catalyzed cross-coupling reaction to various unsymmetrical disulfanes has been presented, from phthalimide-carried disulfur transfer reagents and commercially available boronic acids under mild and practical conditions. The method features the unprecedented use of phthalimide-carried disulfurating reagents (Harpp reagent) in cross-coupling chemistry and is highlighted by the broad substrate scopes, even applicable for the transfer of aryldisulfur moieties (ArSS−). Notably, the robustness of this methodology is shown by the late-stage modification of bioactive scaffolds of coumarin, estrone, and captopril.

The first asymmetric total syntheses of tuberostemoamide, sessilifoliamide A, and their epimers have been accomplished via the common intermediate ethylstemoamide. The stereochemistry control relationship at C8/C9/C10 of ethylstemoamide is clearly revealed for the first time, and a subtle difference of substituent at the C10 position between stemoamide and ethylstemoamide (Me vs Et) drastically changes the stereoselectivity, which is significantly valuable for syntheses of ethylstemoamide structurally related Stemona alkaloids. Biological studies reveal that the activities of each epimer show a significant difference. 11,13-Bis-epi-sessilifoliamide A is expected to be a selective and reversible BChE inhibitor for the treatment of neurodegenerative diseases, and sessilifoliamide A may be a part of the antiinflammatory substances in Stemonaceae plants.

Total synthesis and structure revision of chrysamide B are described, the strategy features a convergent assembly of the chiral piperazine core and epoxy-acid.