Simple Modular Synthetic Approaches to Asymmetric NN′N′′, NN′C, or NN′P-Type Amido Pincer Ligands: Synthesis, Characterisation, and Preliminary Ligation Studies

Khrystyna Herasymchuk; Jennifer Huynh; Alan J. Lough; Laura Roces Fernández; Robert A. Gossage

doi:10.1055/s-0035-1561953

Synthesis, Table of Contents

Synthesis 2016; 48(13): 2121-2129
DOI: 10.1055/s-0035-1561953

paper

Simple Modular Synthetic Approaches to Asymmetric NN′N′′, NN′C, or NN′P-Type Amido Pincer Ligands: Synthesis, Characterisation, and Preliminary Ligation Studies

Khrystyna Herasymchuk

^aDepartment of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, Canada Email: gossage@ryerson.ca

,

Jennifer Huynh

^aDepartment of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, Canada Email: gossage@ryerson.ca

,

Alan J. Lough

^bDepartment of Chemistry, University of Toronto, Toronto, ON M5H 3S6, Canada Email: alough@chem.utoronto.ca

,

Laura Roces Fernández

^cDepartamento de Química Orgánica e Inorgánica, Facultad de Química, c/ Julián Clavería, n° 8, Universidad de Oviedo, 33006 Oviedo, Spain Email: roceslaura@uniovi.es

,

Robert A. Gossage*

^aDepartment of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, Canada Email: gossage@ryerson.ca

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Abstract

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‡ Corresponding author for the crystallographic characterisation of compound 1.

§ Corresponding author for the crystallographic characterisation of compound 3m•oxide.

Abstract

A simple modular approach is presented which has been directed towards the synthesis of potentially monoanionic NN′N′′, NN′C, and NN′P pincer-type ligands. These pincers incorporate an amide functionality derived from the skeletal structure of readily available 2-(2-aminophenyl)-4,5-dioxooxazoles. All of the pincers are synthesized in moderate yields (up to 74%) and are characterised by nuclear magnetic spectroscopy (NMR), elemental analyses, and infrared (IR) spectroscopy. X-ray crystallography is also performed on the chiral and achiral alkyl halide precursors and on an oxide derivative of a pincer with a NN′P-atom donor set. A palladium derivative of one of the NN′N′′-pincers is shown to be an active catalyst for the addition of an allyl group to various benzaldehydes using n-Bu₃Sn(allyl) as allyl source.

Key words

pincer - oxazoline - ligands - palladium complex - allyl group transfer

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References

References
1 New address: K. Herasymchuk, Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby BC V5A 1S6 Canada.
2 Undergraduate research participant.

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