C(1→4)-linked disaccharides through carbonylative Stille cross-coupling |
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| Institution: | 1. Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR China;2. The Experimental High School Attached to Beijing Normal University, Beijing 100032, PR China;3. School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK |
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| Abstract: | A tinglucal tributyl4,6-O-bis(t-butyl)silylidene-3-O-tris(isopropyl)silyl]tin 7 and a triflate derived from isolevoglucosenone (1R,4R,5R)-4-benzyloxy-6,8-dioxabicyclo3.2.1]oct-2-en-2-yl trifluoromethanesulfonate 10 undergo the carbonylative Stille condensation under special conditions requiring AsPh3, LiCl, and powdered charcoal as co-catalysts to give a cross-conjugated dienone 6 in which the bicyclic alkene moiety is more reactive than the glucal alkene moiety. This allows the regio- and stereoselective hydrogenation of the bicyclic alkene moiety giving an enone 21 that can be reduced stereoselectively to an allylic alcohol 22. Hydroboration of the glucal and bicyclic acetal opening generates a C(1→4) linked disaccharide 25 in which a protected form of β-d-glucopyranose is attached at position C(4) of a α-d-3-deoxy-ribo-hexopyranoside derivative via a (S)-hydroxymethano linker. |
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