The full details of a synthesis of the hetidine framework of the C20-diterpenoid alkaloids and its conversion to the atisine core structure are reported. The application of the hetidine framework to the synthesis of dihydronavirine, which is the formal reduction product of the natural product navirine, is also described. Key to the success of these studies is the use of a Ga(III)-catalyzed cycloisomerization reaction of alkynylindenes to prepare a [6-7-6] framework that was advanced to the hetidine skeleton. Furthermore, a Michael/aldol sequence was developed for the construction of the bicyclo[2.2.2] framework that is characteristic of the hetidines and atisines.
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A Case for Bond-Network Analysis in the Synthesis of Bridged Polycyclic Complex Molecules: Hetidine and Hetisine Diterpenoid Alkaloids.
Angew Chem Int Ed Engl
June 2020
Fachbereich Chemie der Philipps Universität Marburg, 35032, Marburg, Germany.
A key challenge in the synthesis of diterpenoid alkaloids lies in identifying strategies that rapidly construct their multiply bridged polycyclic skeletons. Existing approaches to these structurally intricate secondary metabolites are discussed in the context of a "bond-network analysis" of molecular frameworks, which was originally devised by Corey some 40 years ago. The retrosynthesis plans that emerge from a topological analysis of the highly bridged frameworks of the diterpenoid alkaloids are discussed in the context of eight recent syntheses of hetidine and hetisine natural products and their derivatives.
View Article and Find Full Text PDFStudies on C20-diterpenoid alkaloids: synthesis of the hetidine framework and its application to the synthesis of dihydronavirine and the atisine skeleton.
J Org Chem
August 2014
Department of Chemistry, University of California, Berkeley, California 94720, United States.
The full details of a synthesis of the hetidine framework of the C20-diterpenoid alkaloids and its conversion to the atisine core structure are reported. The application of the hetidine framework to the synthesis of dihydronavirine, which is the formal reduction product of the natural product navirine, is also described. Key to the success of these studies is the use of a Ga(III)-catalyzed cycloisomerization reaction of alkynylindenes to prepare a [6-7-6] framework that was advanced to the hetidine skeleton.
View Article and Find Full Text PDFGallium(III)-catalyzed cycloisomerization approach to the diterpenoid alkaloids: construction of the core structure for the hetidines and hetisines.
Angew Chem Int Ed Engl
April 2013
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA.
A versatile core structure has been prepared that should provide a foundation for the syntheses of the hetidine and hetisine type of diterpenoid alkaloids. The synthesis of the caged polycyclic core structure, which features nine contiguous stereocenters, utilizes a Ga(III)-catalyzed cycloisomerization of alkynyl indenes as well as a Michael/aldol sequence to build the bicyclo-[2.2.
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