Cyrene™ is Circa’s trade name for (-)-dihydrolevoglucosenone (1S,5R)-6,8-Dioxabicyclo[3.2.1]octan-4-one; CAS Reg. No. 53716-82-8
General properties overview:
Stability in the Presence of Bases
Cyrene™ is a cyclic ketone containing two protons alpha to the carbonyl group and, like cyclohexanone, it will form initially dimers and then oligomers and insoluble polymers when treated with strong bases such as sodium hydroxide, potassium carbonate and many strongly basic organic amines. Cyrene is however unchanged by heating in chloroform in the presence of triethylamine at 60oC for 18 hours.
Stability in the Presence of Acids
Cyrene™ is relatively stable in the presence of weak acids and, for example, can be heated with trifluoracetic acid at 60oC for 18h without apparent change. Brief treatment with aqueous 2M HCl however rapidly converts Cyrene™ to a mixture of products that have not yet been characterised.
Stability to Oxidizing Agents
Cyrene™ reacts violently with 30% aqueous hydrogen peroxide at room temperature. It will react selectively with hydrogen peroxide and peracids, such as peracetic and m-chloroperbenzoic acid under carefully controlled conditions to afford a mixture of (5S)-dihydro-5-(hydroxymethyl)-2(3H)-furanone and its formyl ester. Reactivity with other strong oxidants has not been tested and caution should be exercised whenever doing so in view of the violence of the reaction with 30% hydrogen peroxide.
Other Reactions of Cyrene™
Because dihydrolevoglucosenone has only been available in useful quantities quite recently, its chemistry remains relatively unexplored. Some useful recent investigations of the reactivity and solvent properties of Cyrene™ have been published by Clark et al and by Greatrex and co-workers.
Romero et al, Ind. Eng. Chem. Res., (2013), 52, 2257
Allais, F. et al, Green Chem., (2015), 17, 404
Clark, J. H. et al, Chem Commun., (2014), 50, 9650
Greatrex, B. W. et al, Eur. J. Org. Chem., (2015), 6999
Cyrene (dihydrolevoglucosenone) properties as a bioactive compound, and effect observed over Salmonella enterica (S. typhimurium)
Cyrene as a bio-based alternative for dipolar aprotic solvents
James Sherwood, Mario De Bruyn, Andri Constantinou, Laurianne Moity, C. Rob McElroy, Thomas J. Farmer, Tony Duncan, Warwick Raverty, Andrew J. Hunt and James H. Clark, 2014
Dihydrolevoglucosenone (Cyrene) is a bio-based molecule, derived in two simple steps from cellulose, which demonstrates significant promise as a dipolar aprotic solvent.
USING CYRENE AS A REPLACEMENT FOR DMF IN SONOGASHIRA CROSS-COUPLING AND CACCHI- TYPE ANNULATIONS
Kirst L. Wilson, Alan R. Kennedy, Jane Murray, Ben Greatrex, Craig Jamieson and Allan J. B. Watson
Green and Sustainable Solvents in Chemical Processes
Coby J. Clarke, Wei-Chien Tu, Oliver Levers, Andreas Bröhl, and Jason P. Hallett
Department of Chemical Engineering, Imperial College, London SW7 2AZ, United Kingdom
Cyrene as a bio-based solvent for HATU mediated amide coupling
Kirsty L Wilson, Jane Murray, Craig Jamieson and Allan J. B. Watson
Synthesis of Bioacrylic Polymers from Dihydro-5-hydroxyl furan-2-one (2H-HBO) by Free and Controlled Radical Polymerization
Parijat Ray, Timothy Hughes, Craig Smith, George P. Simon and Kei Saito,
Department of Materials Science and Engineering and New Horizons Research Centre and ‡ School of Chemistry, Monash University, Clayton, Victoria, Australia
Synthesis of Triazole Derivatives of Levoglucosenone As Promising Anticancer Agents: Effective Exploration of the Chemical Space through retro-aza-Michael//aza-Michael Isomerizations
Tsai YH, Borini Etichetti CM, Di Benedetto C, Girardini JE, Martins FT, Spanevello RA, Suárez AG, Sarotti AM
Method for synthesizing a precursor
of a single Dairy-Lactone Isomer
Florent Allais, Aurélien Peru, Ben Greatrex, Douglas Warwick, Anthony Duncan
Bio‐based Chiral Amines via Aza‐Michael Additions to (‐)‐Levoglucosenone Under Aqueous Conditions
John Sperry, Ben Greatrex, Shinji Kudo, Shi-Wei Kim, Ed Ledingham
Institut des Science et Industries du Vivant et de L'environnement-Agroparis Tech, University of New England, Circa Group PTY LTD
Siddarth H. Krishna, Kefeng Huang, Kevin J. Barnett, Jiayue He, Christos T. Maravelias, James A. Dumesic, George W. Huber, Mario De bruyn, Bert M. Weckhuysen