摘要：

The total synthesis of 16-membered macrolides, macraosphelides I and G, has been achieved starting from ethyl-()-lactate and ()-malic acid. A combination of Jacobsen's hydrolytic kinetic resolution and Sharpless epoxidation is used for the creation of two stereogenic centres, while Yamaguchi esterification and ring-closing metathesis strategies were used for the construction of the lactone ring.Graphical abstractRCM mediated synthesis of macrosphelides I and G from ()-lactic acid, ()-malic acid and propylene oxide is reported.(4,5)-5-(Benzyloxy)-4-[1-(-butyl)-1,1-dimethylsilyl]oxyhexanoic acid19324[]=+22.0 ( 0.2, CHCl)Source of chirality: asymmetric synthesisAbsolute configuration: (4,5)(2,3)-3-[1-(-Butyl)-1,1-dimethylsilyl]oxy-4-penten-2-ol11242[]=+51.7 ( 0.25, CHCl)Source of chirality: asymmetric synthesisAbsolute configuration: (2,3)(3)-3-Acryloyloxybutanoic acid7104[]=+10.3 ( 0.2, CHCl)Source of chirality: ()-malic acidAbsolute configuration: (3)E)-5-[(4-Methoxybenzyl)oxy]-2-hexenoic acid14184[]=+58.1 ( 0.25, CHCl)Source of chirality: asymmetric synthesisAbsolute configuration: (5)(1)-3-[((1,2)-2-Hydroxy-5-[(1,2)-2-hydroxy-1-methyl-3-butenyl]oxy-1-methyl-5-oxopentyl)oxy]-1-methyl-3-oxopropyl acrylate18288[]=+1.3 ( 0.5, CHCl)Source of chirality: asymmetric synthesisAbsolute configuration: (1,1a,2a,1b,2b)(1,2)-2-Hydroxy-1-methyl-3-butenyl (,5)-5-[(3)-3-(acryloyloxy)butanoyl]oxy-2-hexenoate18267[]=23.7 ( 0.1, CHCl)Source of chirality: asymmetric synthesisAbsolute configuration: (1,2,5a,3b)Macrosphelide I ()16248[]=+9.6( 0.15, CHCl)Source of chirality: asymmetric synthesisAbsolute configuration: (3,8,9,14,15)Macrosphelide G ()16227[]=+54.3 ( 0.1, CHCl)Source of chirality: asymmetric synthesisAbsolute configuration: (3,8,9,15)

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