eCite Digital Repository

Supported Palladium Catalysis Using a Heteroleptic 2-Methylthiomethylpyridine -N,S- Donor Motif for Mizoroki-Heck and Suzuki-Miyaura Coupling, Including Continuous Organic Monolith in Capillary Microscale Flow-Through Mode

Citation

Jones, RC and Canty, AJ and Deverell, JA and Gardiner, MG and Guijt, RM and Rodemann, T and Smith, JA and Tolhurst, V, Supported Palladium Catalysis Using a Heteroleptic 2-Methylthiomethylpyridine -N,S- Donor Motif for Mizoroki-Heck and Suzuki-Miyaura Coupling, Including Continuous Organic Monolith in Capillary Microscale Flow-Through Mode, Tetrahedron, 65, (36) pp. 7474-7481. ISSN 0040-4020 (2009) [Refereed Article]


Preview
PDF
Restricted - Request a copy
479Kb
  

Copyright Statement

The definitive version is available at http://www.sciencedirect.com

Official URL: http://www.sciencedirect.com

DOI: doi:10.1016/j.tet.2009.07.013

Abstract

Flow-through catalysis utilising (2-methylthiomethylpyridine)palladium(II) chloride species covalently attached to a macroporous continuous organic polymer monolith synthesised within fused silica capillaries of internal diameter 250 mm is described, together with related studies of ground bulk monolith compared with supported catalysis on Merrifield and Wang beads and homogeneous catalysis under identical conditions to bulk supported catalysis. The monolith substrate, poly(chloromethylstyrene-co-divinylbenzene), has a backbone directly related to Merrifield and Wang resins. The homogeneous precatalyst PdCl2(L2) (L2¼4-(4-benzyloxyphenyl)-2-methylthiomethylpyridine) contains the benzyloxyphenyl group on its periphery as a model for the spacer between the ‘PdCl2(NwS)’ centre and the polymer substituent of the resins and monolith. Suzuki–Miyaura and Mizoroki–Heck catalysis exhibit anticipated trends in reactivity with variation of aryl halide reagents for each system, and show that supported catalysis on beads and monolith gives higher yields than for homogeneous catalysis. The synthesis of 2-methylthiomethylpyridines is presented, together with crystal structures of 4-bromo-2-bromomethylpyridine hydrobromide, 4-(4- hydroxyphenyl)-2-methylthiomethylpyridine (L1), PdCl2(L1) and PdCl2(L2). Hydrogen bonding occurs in 4-bromo-2-bromomethylpyridine hydrobromide as N–H/Br interactions, in 4-(4-hydroxyphenyl)-2- methylthiomethylpyridine as O–H/N to form chains, and in PdCl2(L1) as O–H/Cl interactions leading to adjacent p-stacked chains oriented in an antiparallel fashion.

Item Details

Item Type:Refereed Article
Keywords:Catalysis; Supported catalysis; Monolith; Flow-through microreactor; Pyridine; Methylthiomethylpyridine
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Jones, RC (Dr Roderick Jones)
Author:Canty, AJ (Professor Allan Canty)
Author:Deverell, JA (Dr Jeremy Deverell)
Author:Gardiner, MG (Associate Professor Michael Gardiner)
Author:Guijt, RM (Dr Rosanne Guijt)
Author:Rodemann, T (Dr Thomas Rodemann)
Author:Smith, JA (Associate Professor Jason Smith)
Author:Tolhurst, V (Dr Vicki-Anne Gardiner)
ID Code:57302
Year Published:2009
Web of Science® Times Cited:33
Deposited By:Chemistry
Deposited On:2009-07-05
Last Modified:2010-04-08
Downloads:0

Repository Staff Only: item control page