Total Synthesis of (+)-Aberrarone

Abstract

The structurally intriguing diterpene (+)-aberrarone has been assembled in only 12 steps from the commercially available (S,S)-carveol without protecting group manipulations. This concise synthesis features a Cu-catalyzed asymmetric hydroboration to generate the chiral methyl group, a Ni-catalyzed reductive coupling to link two fragments, and a Mn-mediated radical cascade cyclization to construct the triquinane system.

Total Synthesis with Gram-Scale Radical Process: An Inspiration for Pharmaceutical Industry

“…To date, the total syntheses of aberrarone (92) have been described by Carreira 49 and Jia. 50 In 2022, Carreira et al reported the first total synthesis of (+)-aberrarone (92) in 15 steps using a creative Au-catalyzed Nazarov cascade reaction. 49 In 2023, Jia et al disclosed a 12step protocol to (+)-aberrarone (92) via a radical cascade reaction 50 which will be discussed herein (Scheme 10).…”

“…50 In 2022, Carreira et al reported the first total synthesis of (+)-aberrarone (92) in 15 steps using a creative Au-catalyzed Nazarov cascade reaction. 49 In 2023, Jia et al disclosed a 12step protocol to (+)-aberrarone (92) via a radical cascade reaction 50 which will be discussed herein (Scheme 10). Their synthesis began with the preparation of alkyl iodide (93) and vinyl iodide (94).…”

“…This material was reported to exhibit in vitro activity against the malaria parasite. To date, the total syntheses of aberrarone ( 92 ) have been described by Carreira and Jia . In 2022, Carreira et al reported the first total synthesis of (+)-aberrarone ( 92 ) in 15 steps using a creative Au-catalyzed Nazarov cascade reaction .…”

Natural Product Synthesis: The Endless Quest for Unreachable Perfection

“…A few months later, the group of Jia reported a different synthesis of the same natural product . Jia’s approach involved intermediates 101 and 102 , synthesized in 2 steps from commercial compounds.…”

Divergent Synthesis of Scabrolide A and Havellockate via an exo-exo-endo Radical Cascade

“…Among these creative solutions, two-electron transformations play a dominate role in the construction of the central ring system and the polycyclic structures. Here we report our work on the concise and divergent synthesis of scabrolide A ( 1 ) and havellockate ( 2 ) through a rare exo - exo - endo radical cascade, which is notably different from all previous works.…”