Palladium-Catalyzed Formation of Substituted Tetrahydropyrans: Mechanistic Insights and Structural Revision of Natural Products

Franco Della-Felice; Francisco F. de Assis; Ariel M. Sarotti; Ronaldo A. Pilli

doi:10.1055/s-0037-1611708

Synthesis, Table of Contents

Synthesis 2019; 51(07): 1545-1560
DOI: 10.1055/s-0037-1611708

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Palladium-Catalyzed Formation of Substituted Tetrahydropyrans: Mechanistic Insights and Structural Revision of Natural Products

Authors

Franco Della-Felice

^aUniversity of Campinas, Institute of Chemistry, 13084-971, Campinas, SP, Brazil Email: pilli@iqm.unicamp.br
Francisco F. de Assis

^aUniversity of Campinas, Institute of Chemistry, 13084-971, Campinas, SP, Brazil Email: pilli@iqm.unicamp.br
Ariel M. Sarotti

^bInstituto de Química Rosario, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario-CONICET, Suipacha 531, S2002 LRK, Rosario, Argentina
Ronaldo A. Pilli*

^aUniversity of Campinas, Institute of Chemistry, 13084-971, Campinas, SP, Brazil Email: pilli@iqm.unicamp.br

Abstract

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This work is dedicated to Professor Albert J. Kascheres for his guidance and positive example to one of us (R.A.P.).

Abstract

A comprehensive study on the stereochemical outcome of palladium-catalyzed formation of 2,4,6-trisubstituted tetrahydropyrans through cyclization of the corresponding allylic acetates using both Pd(0) and Pd(II) catalysts is presented. We have found that the stereochemical outcome of this cyclization is dependent not only on the stereochemistry of the acyclic precursor but also on the nature of the palladium catalyst. These results were applied to the total synthesis of the putative structure of cryptoconcatone H. Experimental and computational DP4+ NMR results were used to assess the structures proposed for cryptoconcatones K and L.

Key words

tetrahydropyran - palladium catalysis - DP4+ - structural revision - natural product synthesis

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References

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