The β-selective phenylation of benzyl and boronate protected 1,6-anhydroglucose and the direct phenylation of unprotected 1,6-anhydroglucose (10), pretreated with i-Bu2AlH, i-Bu3Al, Et3Al, Me3Al, or n-octyl3Al, with triphenylalane or aryl(chloro)alanes is reported. The utility of the unprotected version of the method is demonstrated by the synthesis of the SGLT2 inhibitor, canagliflozin (1a), from commercially available 10 in one C-C bond-forming step. This approach circumvents the need for conventional protecting groups, and therefore no formal protection and deprotection steps are required.

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The skeletal rearrangement of bicyclo[2.2.2]lactones, involving a mild and chemoselective palladium-catalysed translocation key-step, provides an efficient and diastereoselective access to synthetically useful bicyclo[3.3.0]lactones.

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Structure. -The skeletal rearrangement of bicyclo[2.2.2]lactones involves a mild Pd-catalyzed translocation to afford a variety of fused bicyclo[3.3.0]lactones. The method can be applied to the diastereoselective synthesis of oxa-triquinane (IX). -(LIAO, J.-H.; MAULIDE, N.; AUGUSTYNS, B.; MARKO*, I. E.; Org.