title: Preparation of both C5' epimers of 5'-C-methyladenosine: reagent control trumps substrate control.
abstract: Adenosine-derived ketone 5 was subjected to Noyori asymmetric transfer hydrogenation (ATH) using aqueous sodium formate as a stoichiometric reductant. Despite the well-known sensitivity of ATH to stereoelectronic effects from a contiguous stereogenic center, the 5' stereochemistry was overwhelmingly controlled by the chirality of the catalyst. Both the (5'S,4'R) and the (5'R,4'R) diastereomers could be prepared selectively in good yields. An efficient three-step route that provides ketone 5 in 75% overall yield was developed.
authors.affiliation: Vertex Pharmaceuticals, Inc. , 50 Northern Avenue, Boston, Massachusetts 02210, United States.
authors.forename: Cavan M
authors.initials: CM
authors.lastname: Bligh
authors.forename: Luigi
authors.initials: L
authors.lastname: Anzalone
authors.forename: Young Chun
authors.initials: YC
authors.lastname: Jung
authors.forename: Yuegang
authors.initials: Y
authors.lastname: Zhang
authors.forename: William A
authors.initials: WA
authors.lastname: Nugent
mesh_terms: D000241:Adenosine / Q000031:analogs & derivatives* / Q000737:chemistry*; D002384:Catalysis; D003849:Deoxyguanosine / Q000737:chemistry*; D007202:Indicators and Reagents / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D007202:Indicators and Reagents; D007659:Ketones; D003849:Deoxyguanosine; D000241:Adenosine