title: 6-Deoxyhexoses from l-Rhamnose in the Search for Inducers of the Rhamnose Operon: Synergy of Chemistry and Biotechnology.
abstract: In the search for alternative non-metabolizable inducers in the l-rhamnose promoter system, the synthesis of fifteen 6-deoxyhexoses from l-rhamnose demonstrates the value of synergy between biotechnology and chemistry. The readily available 2,3-acetonide of rhamnonolactone allows inversion of configuration at C4 and/or C5 of rhamnose to give 6-deoxy-d-allose, 6-deoxy-d-gulose and 6-deoxy-l-talose. Highly crystalline 3,5-benzylidene rhamnonolactone gives easy access to l-quinovose (6-deoxy-l-glucose), l-olivose and rhamnose analogue with C2 azido, amino and acetamido substituents. Electrophilic fluorination of rhamnal gives a mixture of 2-deoxy-2-fluoro-l-rhamnose and 2-deoxy-2-fluoro-l-quinovose. Biotechnology provides access to 6-deoxy-l-altrose and 1-deoxy-l-fructose.
authors.affiliation: Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.|Glycobiology Institute, Department of Biochemistry, University of Oxford, Oxford, OX1 3QU, UK.
authors.forename: Zilei
authors.identifier: http://orcid.org/0000-0002-8749-7595
authors.initials: Z
authors.lastname: Liu
authors.affiliation: International Institute of Rare Sugar Research and Education, Kagawa University, Miki, Kagawa, 761-0795, Japan. yoshihara@ag.kagawa-u.ac.jp.
authors.forename: Akihide
authors.initials: A
authors.lastname: Yoshihara
authors.affiliation: Centre for Synthetic Biology and Innovation, Department of Life Sciences, Imperial College, London, SW7 2AZ, UK.
authors.forename: Ciarán
authors.initials: C
authors.lastname: Kelly
authors.affiliation: Centre for Synthetic Biology and Innovation, Department of Life Sciences, Imperial College, London, SW7 2AZ, UK.
authors.forename: John T
authors.identifier: http://orcid.org/0000-0001-9991-5160
authors.initials: JT
authors.lastname: Heap
authors.affiliation: Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.
authors.forename: Mikkel H S
authors.initials: MH
authors.lastname: Marqvorsen
authors.affiliation: Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.
authors.forename: Sarah F
authors.initials: SF
authors.lastname: Jenkinson
authors.affiliation: Glycobiology Institute, Department of Biochemistry, University of Oxford, Oxford, OX1 3QU, UK.
authors.forename: Mark R
authors.initials: MR
authors.lastname: Wormald
authors.affiliation: Departamento de Química Orgánica and Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain.
authors.forename: José M
authors.identifier: http://orcid.org/0000-0001-5543-4859
authors.initials: JM
authors.lastname: Otero
authors.affiliation: Departamento de Química Orgánica and Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain.
authors.forename: Amalia
authors.identifier: http://orcid.org/0000-0001-9981-1337
authors.initials: A
authors.lastname: Estévez
authors.affiliation: Department of Hospital Pharmacy, University of Toyama, Toyama, 930-0194, Japan.
authors.forename: Atsushi
authors.initials: A
authors.lastname: Kato
authors.affiliation: Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK. george.fleet@chem.ox.ac.uk.
authors.forename: George W J
authors.identifier: http://orcid.org/0000-0003-1903-270X
authors.initials: GW
authors.lastname: Fleet
authors.affiliation: Departamento de Química Orgánica and Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain. ramon.estevez@usc.es.
authors.forename: Ramón J
authors.identifier: http://orcid.org/0000-0002-3764-0832
authors.initials: RJ
authors.lastname: Estévez
authors.affiliation: International Institute of Rare Sugar Research and Education, Kagawa University, Miki, Kagawa, 761-0795, Japan.
authors.forename: Ken
authors.initials: K
authors.lastname: Izumori
mesh_terms: D001709:Biotechnology; D003837:Deoxy Sugars / Q000737:chemistry*; D003847:Deoxyglucose / Q000031:analogs & derivatives* / Q000737:chemistry; D005632:Fructose / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry*; D006601:Hexoses / Q000737:chemistry*; D009876:Operon; D012210:Rhamnose / Q000737:chemistry*
chemical_list: D003837:Deoxy Sugars; D006601:Hexoses; C057406:gulose; D005632:Fructose; C002055:allose; C407877:olivose; C011754:6-deoxytalose; D003847:Deoxyglucose; D005947:Glucose; C037904:6-deoxyglucose; D012210:Rhamnose
keywords: 6-deoxyhexoses; carbohydrates; gene expression; rhamnonolactone; rhamnose operon