Chemical Synthesis of Aspidosperma Alkaloids Inspired by the Reverse of the Biosynthesis of the Rhazinilam Family of Natural Products

Total Synthesis of Rhazinilam through Gold-Catalyzed Cycloisomerization–Sulfonyl Migration and Palladium-Catalyzed Suzuki–Miyaura Coupling of Pyrrolyl Sulfonates

“…The known conditions, some already used in the synthesis of rhazinilam and related natural products, 16 only led to degradation. Eventually, a combination of solvents similar to those reported by Trauner, 17 and with dioxygen as the oxidant at room temperature as in Gaunt's conditions, 18 allowed formation of the cyclized products 4a-b. However, careful analysis of the product structures revealed that the cyclization occurred at the less nucleophilic carbon 5 of the pyrrole instead of carbon 2, 19 suggesting a C-H activation mechanism.…”

A Longitudinal Study of Alkaloid Synthesis Reveals Functional Group Interconversions as Bad Actors

“…Gaunt and his team at Cambridge University published the eighth total synthesis of rhazinilam ( 386 ) in 2012 . This team’s route targeted several members of the Aspidosperma alkaloids, such as aspidospermidine and kopsiyunnanine C3, in addition to rhazinilam.…”

“…Gaunt and his team at Cambridge University published the eighth total synthesis of rhazinilam (386) in 2012. 229 This team's route targeted several members of the Aspidosperma alkaloids, such as aspidospermidine and kopsiyunnanine C3, in addition to rhazinilam. [Aspidospermidine possesses a pyrrolidine core that could be obtained in three steps directly from the pyrrole core of rhazinilam (386).…”

Royal Society of Chemistry Prize Winners 2013

“…Gaunt was honored for his work on enantioselective catalysis, CH functionalization, and copper catalysis. He has reported in Angewandte Chemie on the synthesis of aspidosperma alkaloids,5a and on the copper‐catalyzed arylative Meyer–Schuster Rearrangement 5b. Gaunt is on the Academic Advisory Board of Advanced Synthesis & Catalysis…”