Enabling and Accelerating Metallocatalysis with Hydrogen Bonding
Lead Research Organisation:
University of Liverpool
Department Name: Chemistry
Abstract
There are numerous important catalytic reactions that require the dissociation/displacement of a hydrogen bonding anion, e.g. halide and acetate anions, or a functional group, such as amines or carbonyls, from the catalytic centre. In many such reactions, the dissociation/displacement process impacts on the reaction rates and selectivities. Indeed, the presence of such a functionality coordinated to the catalyst can inhibit the catalysis entirely. We have recently discovered that the addition of simple, readily accessible hydrogen bond donors (HBD) can dramatically accelerate palladium-catalysed reactions such as the internal arylation of olefins by aryl bromides. The reaction rates we observed equal or exceed all previous catalytic systems for these reactions. We believe that the HBD functions by complexing the halide anion, aiding its removal from the metal coordination sphere without the need for, e.g., stoichiometric, toxic thallium salts as additives. It has recently been stated that The capacity to control anion-cation interactions is key to optimizing yield, chemoselectivity, regioselectivity, and stereoselectivity of chemical processes .... (Chem. Rev. 2005, 105, 2039). In this project, we wish to demonstrate that we can use hydrogen bonding to do this. In particular we will show that we can apply HBDs in order to: (i) accelerate, and direct, metallocatalysis; (ii) enable cascade metallo-organo catalytic reactions; and thus (iii) show that HBDs afford a new means of controlling catalytic activity and selectivity, and should always be considered for reactions in which hydrogen bonding anions/functionalities are involved. The capability to integrate homogeneous catalysis with organocatalysis to enable cascade metallo-organo catalysis would open up an exciting new area of catalysis, metallo-organo catalysis, given the promise being demonstrated by the emerging organocatalysis.
Publications
Colbon P
(2011)
Double arylation of allyl alcohol via a one-pot Heck arylation-isomerization-acylation cascade.
in Organic letters
Colbon P
(2010)
Direct acylation of aryl chlorides with aldehydes by palladium-pyrrolidine Co-catalysis.
in Organic letters
Colbon P
(2012)
Feeding the Heck Reaction with Alcohol: One-Pot Synthesis of Stilbenes from Aryl Alcohols and Bromides
in Advanced Synthesis & Catalysis
Hyder Z
(2008)
Hydrogen-bond-directed catalysis: faster, regioselective and cleaner Heck arylation of electron-rich olefins in alcohols.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Ruan J
(2011)
Direct synthesis of 1-indanones via Pd-catalyzed olefination and ethylene glycol-promoted aldol-type annulation cascade.
in Organic letters
Ruan J
(2010)
Hydrogen-bonding-promoted oxidative addition and regioselective arylation of olefins with aryl chlorides.
in Journal of the American Chemical Society
Ruan J
(2008)
Direct acylation of aryl bromides with aldehydes by palladium catalysis.
in Journal of the American Chemical Society
Ruan J
(2011)
From a-arylation of olefins to acylation with aldehydes: a journey in regiocontrol of the Heck reaction.
in Accounts of chemical research
Schenck G
(2022)
Efficient pKa Determination in a Nonaqueous Solvent Using Chemical Shift Imaging.
in Analytical chemistry
Description | Hydrogen bonding can be exploited to control the selectivity of the Heck reaction and accelerate one of the most fundamental reactions in organometallic chemistry and catalysis, i.e. oxidative addition. |
Exploitation Route | The chemistry developed has already been and is being exploited by other researchers. |
Sectors | Chemicals |
Description | The finding contributed to the founding of the spinout company Liverpool ChiroChem at Liverpool and Taizhou, China. |
First Year Of Impact | 2014 |
Sector | Chemicals |
Impact Types | Economic |
Description | Collaboration with AstraZeneca on acylation |
Organisation | AstraZeneca |
Country | United Kingdom |
Sector | Private |
PI Contribution | New acylation reaction was developed. |
Collaborator Contribution | Case award for a PhD studenship. |
Impact | A student was awarded the PhD degree. Peer-reviewed publications: 1. P. Colbon, J. H. Barnard, M. Purdie, K. Mulholland, I. Kozhevnikov, J. Xiao, Adv. Synth. Catal. 2012, 354, 1395-1400. 2. Colbon, P; Ruan, J; Purdie, M; Mulholland, K; Xiao, J. "Double Arylation of Allyl Alochol via a One-Pot Heck Arylation-Isomerization-Acylation Cascade", Org. Lett. 2011, 13, 5456-5459. 3. Colbon, P; Ruan, JW; Purdie, M; Xiao, JL, "Direct Acylation of Aryl Chlorides with Aldehydes by Palladium-Pyrrolidine Co-catalysis", Org. Lett. 2010, 12, 3670-3673. |
Start Year | 2008 |
Title | PARACYCLOPHANE-BASED LIGANDS, THEIR PREPARATION AND USE IN CATALYSIS |
Description | A substituted paracyclophane is described of formula (I) wherein X1 and X2 are linking groups comprising between 2 to 4 carbon atoms, Y1 and Y2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl, aryl or heteroaryl and Z is a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. Preferably X1 and X2 are -(C2H4)- and Z is a substituted aryl group. The substituted paracyclophane provides transition metal catalysts that are useful in C-C and C-N bond formation and asymmetric hydrogenation reactions. |
IP Reference | WO2009027729 |
Protection | Patent granted |
Year Protection Granted | 2009 |
Licensed | Yes |
Impact | The invention allows JOHNSON MATTHEY to prepare novel catalysts. |