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Total Synthesis of Penicibilaenes via C-C Activation-Enabled Skeleton Deconstruction and Desaturation Relay-Mediated C-H Functionalization.

ABSTRACT: Herein, we describe the first total synthesis of sesquiterpene penicibilaenes A and B through a "C-C/C-H" approach. In the "C-C" stage, the Rh-catalyzed "cut-and-sew" transformation between trisubstituted alkene and cyclobutanone has been employed to construct the unique tricyclo[6.3.1.0^1,5]dodecane skeleton and the all-carbon quaternary center. Critical linker and Lewis acid effects have been identified for the C-C activation process. In the "C-H" stage, a desaturation relay-based strategy involving consecutive ketone α,β-dehydrogenation and β-functionalization has been adopted to introduce the 1,3,5-triad stereocenters to the core. The synthesis of penicibilaenes A and B has been completed in 13 and 14 steps, respectively, in the longest linear sequence.

SUBMITTER: Xue Y

PROVIDER: S-EPMC9112325 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Total Synthesis of Penicibilaenes via C-C Activation-Enabled Skeleton Deconstruction and Desaturation Relay-Mediated C-H Functionalization.

Xue Yibin Y Dong Guangbin G

Journal of the American Chemical Society 20210526 22

Herein, we describe the first total synthesis of sesquiterpene penicibilaenes A and B through a "C-C/C-H" approach. In the "C-C" stage, the Rh-catalyzed "cut-and-sew" transformation between trisubstituted alkene and cyclobutanone has been employed to construct the unique tricyclo[6.3.1.0<sup>1,5</sup>]dodecane skeleton and the all-carbon quaternary center. Critical linker and Lewis acid effects have been identified for the C-C activation process. In the "C-H" stage, a desaturation relay-based st ...[more]

PMID: 34038107

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