∂. ∂ Efficient Catalytic Syntheses of Organoboronate Esters Ubiquitous building blocks for the...
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Transcript of ∂. ∂ Efficient Catalytic Syntheses of Organoboronate Esters Ubiquitous building blocks for the...
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Efficient Catalytic Syntheses of Organoboronate Esters Ubiquitous building blocks for the fine chemical and pharmaceutical industries
NORSC Sustainable Chemistry InitiativeRamside Hall, Durham
24th April 2012
Patrick SteelDepartment of Chemistry, Durham University, UK
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Why make aryl boronates?
Hall, Boronic Acids, Wiley-VCH, 2nd Ed 2011
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Why make aryl boronates?
Hall, Boronic Acids, Wiley-VCH, 2nd Ed 2011
• Non-toxic
• Tolerant to air and water
• Stable in the absence of a catalyst
• React under mild conditions
• Reaction by-product is inert and benign to humans
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Classical Aryl Boronate Synthesis a Sustainable Chemistry Challenge?
Asher et al., Tetrahedron Lett., 2003, 44, 7719
Snieckus et al., J. Org. Chem., 2009, 74, 4094
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Functional Group Tolerant Aryl Boronate Synthesis
Ishiyama, Miyaura et al., J. Org. Chem., 1995, 60, 7508
Kleeberg, Marder et al., Angew. Chem. Int. Ed., 2009, 48, 5350
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Iridium Catalysed Arene C-H Borylation
Mkhalid, Barnard, Marder, Murphy, Hartwig, Chem. Rev., 2010, 110, 890
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Iridium Catalysed Arene C-H Borylation
Mkhalid, Barnard, Marder, Murphy, Hartwig, Chem. Rev., 2010, 110, 890
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Iridium Catalysed Borylation – An Atom Economical Process
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Iridium Catalysed Borylation – An Atom Economical Process
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Iridium Catalysed Borylation – An Atom Economical Process
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‘One-pot’ Transformations from Arenes
Maleczka, Smith et al., Tetrahedron, 2008, 64, 6103
Ishiyama, Miyaura et al., Tetrahedron, 2008, 64, 4967
∂Solvent Temp ( ˚C) Time (h) GC-MS Conversion (%)
DMF 80 6 0
1,4-dioxane 80 6 25
MeCN 80 6 37
2-MeTHF 80 6 85
MTBE 80 6 100
One-pot C-H Borylation/Suzuki-Miyaura Cross-Coupling
Peter Harrisson
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Peter Harrisson
One-pot C-H Borylation/Suzuki-Miyaura Cross-Coupling
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Peter Harrisson
One-pot C-H Borylation/Suzuki-Miyaura Cross-Coupling
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Peter Harrisson
One-pot C-H Borylation/Suzuki-Miyaura Cross-Coupling
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Peter Harrisson
One-pot C-H Borylation/Suzuki-Miyaura Cross-Coupling
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Peter Harrisson
Microwave Accelerated “One-Pot” Biaryl Synthesis
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Challenges for Ir-Catalysed Arene C-H BorylationRegiocontrol
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Challenges for Ir-Catalysed Arene C-H BorylationHeterocyclic Organoboronic Acids
Data – Courtesy David Blakemore Pfizer - Neusentis
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Challenges for the Synthesis of Heterocyclic Boronate Esters
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Challenges for the Synthesis of Heterocyclic Boronate Esters
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Peter Harrisson
Quinoline Boronate Esters
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Where Now for ‘Cleaner Greener’ Aromatic C-H Borylation?
Other sequential chemistries
Faster more effective Catalysts.
Better ligand sets to control regiochemistry.
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Where Now for ‘Cleaner Greener’ Aromatic C-H Borylation?
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Where Now for ‘Cleaner Greener’ Aromatic C-H Borylation?
Other sequential chemistries
Faster more effective Catalysts.
Better ligand sets to control regiochemistry.
Cheaper metals than “Ir” – Cu????
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Hazmi Tajuddin
Alkyl Boronate Esters via Cu-Catalysed C-X Activation
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2012 Durham Lectures
Monday 14th MayTuesday 15th May
Wednesday 16th May
Department of Chemistry, Durham UniversityAll Lectures Commence at 4pm – Visitors Welcome
For Further Details [email protected]
Prof John HartwigUniversity of California, Berkeley
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Understanding and Optimising Chemical Processes
This two-day programme provides delegates with an opportunity to augment their process knowledge using Principal Components Analysis (PCA) and Design of Experiments (DoE) methodologies to expand process understanding, establish and develop capability, ensure robust and in-control processes, improve quality and reduce operational and environmental costs.
Further Information & RegistrationContact: Matthew Linsley, ISRU, Newcastle University
2nd & 3rd July 2012 Department of Chemistry
Durham University
Keynote SpeakerMartin Owen
Product Development, GlaxoSmithKline, Stevenage
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Acknowledgements
Peter HarrissonHazmi TajuddinBianca Bitterlich
Prof Lei Liu (Tsinghua University, Beijing)
Prof Todd Marder
James Morris (Syngenta)Aoife Maxwell (GSK)Lena Shukla (GSK)
Alan Kenwright (NMR)Jackie Mosely (MS)Andrei Batsanov (X-ray)
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Understanding and Optimising Chemical Processes
This two-day programme provides delegates with an opportunity to augment their process knowledge using Principal Components Analysis (PCA) and Design of Experiments (DoE) methodologies to expand process understanding, establish and develop capability, ensure robust and in-control processes, improve quality and reduce operational and environmental costs.
Further Information & RegistrationContact: Matthew Linsley, ISRU, Newcastle University
2nd & 3rd July 2012 Department of Chemistry
Durham University
Keynote SpeakerMartin Owen
Product Development, GlaxoSmithKline, Stevenage
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