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

Author(s)

Della-Felice, Franco ^[1] ; de Assis, Francisco F. ^[1] ; Sarotti, Ariel M. ^[2] ; Pilli, Ronaldo A. ^[1]

Affiliation

^[1] Univ Estadual Campinas, Inst Chem, BR-13084971 Campinas, SP - Brazil

^[2] Univ Nacl Rosario CONICET, Fac Ciencias Bioquim & Farmaceut, Inst Quim Rosario, Suipacha 531, S2002 LRK, Rosario, Santa Fe - Argentina

• Document type: Journal article
• Source: SYNTHESIS-STUTTGART; v. 51, n. 7, p. 1545-1560, APR 2019.
• Web of Science Citations: 0

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. (AU)

• FAPESP's process: 13/07607-8 - OCRC - Obesity and Comorbidities Research Center
• Grantee: Licio Augusto Velloso
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 16/12541-4 - A biomimetic approach to the total synthesis of Stemona alkaloids
• Grantee: Ronaldo Aloise Pilli
• Support Opportunities: Regular Research Grants
• FAPESP's process: 14/25474-8 - Synthesis and biological evualuation of Brevipolide A, Cryptomoskatone F1 and related compounds
• Grantee: Franco Della Felice
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)