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Development and Elucidation of a Pd-Based Cyclization-Oxygenation Sequence for Natural Product Synthesis.

ABSTRACT: Pd-catalyzed sequences involving oxidative addition, cyclization, and termination through intermolecular nucleophile capture have tremendous utility. Indeed, they can generate a plethora of different polycyclic structures possessing a diverse range of functionality. However, one area of deficiency for Pd⁰ /Pd^II variants is the ability to conclude them with oxygen-based species. Inspired by the recent discovery of one such reaction in the course of a total synthesis program, we delineate herein that it has significant strength, both in terms of substrate scope as well as the terminating oxygen nucleophile. As a result, the reaction proved critical in achieving total syntheses of two oxygenated natural products, one of which was prone to over-oxidation. Finally, a mechanistic proposal that accounts for its success is provided.

SUBMITTER: Yi H

PROVIDER: S-EPMC7199387 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Development and Elucidation of a Pd-Based Cyclization-Oxygenation Sequence for Natural Product Synthesis.

Yi Heng H Hu Pengfei P Snyder Scott A SA

Angewandte Chemie (International ed. in English) 20200108 7

Pd-catalyzed sequences involving oxidative addition, cyclization, and termination through intermolecular nucleophile capture have tremendous utility. Indeed, they can generate a plethora of different polycyclic structures possessing a diverse range of functionality. However, one area of deficiency for Pd<sup>0</sup> /Pd<sup>II</sup> variants is the ability to conclude them with oxygen-based species. Inspired by the recent discovery of one such reaction in the course of a total synthesis program, ...[more]

PMID: 31742828

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Dataset Information

Development and Elucidation of a Pd-Based Cyclization-Oxygenation Sequence for Natural Product Synthesis.

Publications

Development and Elucidation of a Pd-Based Cyclization-Oxygenation Sequence for Natural Product Synthesis.

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