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Palladium-Cleavable Linkers: Solid-Phase Synthesis of 4-Methylene Pyrrolidines and Allylic Amines

Palladium-Cleavable Linkers: Solid-Phase Synthesis of 4-Methylene Pyrrolidines and Allylic Amines
Palladium-Cleavable Linkers: Solid-Phase Synthesis of 4-Methylene Pyrrolidines and Allylic Amines

The solid-phase synthesis of several 4-methylene pyrrolidines has been used to demonstrate the viability of a cyclisation-cleavage reaction. The treatment of a reversed allylic linker with catalytic palladium (0) generates a π-allyl palladium species, which is released into solution and subsequently trapped by an intramolecular nucleophile. An imino-Sakurai reaction is the key step in the construction of the cyclisation-cleavage substrates. A carboxyethylated polystyrene resin, prepared from Merrifield resin, was used as the solid support in this study.

A reversed allylic linker based on a phenyl ether template was used in the preparation of allylic amines on the solid-phase. In this case the π-allyl palladium species, which is released into solution, is trapped primary and secondary amines. The substrates were prepared by coupling secondary allylic alcohols to hydroxypolystyrene resin under Mitsunobu conditions.

University of Southampton
Fisher, Martyn Lewis
Fisher, Martyn Lewis

Fisher, Martyn Lewis (2002) Palladium-Cleavable Linkers: Solid-Phase Synthesis of 4-Methylene Pyrrolidines and Allylic Amines. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The solid-phase synthesis of several 4-methylene pyrrolidines has been used to demonstrate the viability of a cyclisation-cleavage reaction. The treatment of a reversed allylic linker with catalytic palladium (0) generates a π-allyl palladium species, which is released into solution and subsequently trapped by an intramolecular nucleophile. An imino-Sakurai reaction is the key step in the construction of the cyclisation-cleavage substrates. A carboxyethylated polystyrene resin, prepared from Merrifield resin, was used as the solid support in this study.

A reversed allylic linker based on a phenyl ether template was used in the preparation of allylic amines on the solid-phase. In this case the π-allyl palladium species, which is released into solution, is trapped primary and secondary amines. The substrates were prepared by coupling secondary allylic alcohols to hydroxypolystyrene resin under Mitsunobu conditions.

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Published date: 2002

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Local EPrints ID: 464613
URI: http://eprints.soton.ac.uk/id/eprint/464613
PURE UUID: d5973ada-ce50-4519-b212-7dedfbe53937

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Date deposited: 04 Jul 2022 23:50
Last modified: 05 Jul 2022 02:36

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Author: Martyn Lewis Fisher

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