Total synthesis of the Z-isomers of nonenolide and desmethyl nonenolide

RCM and Yamaguchi esterification reactions were used as the key steps for the stereoselective total synthesis of Z-isomers of nonenolide and desmethyl nonenolide.

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(3S)-3-{[1-(tert-Butyl)-1,1-dimethylsilyl]oxy}-4-pentenoic acidC11H22O3Si[α]D25=+1.2 (c 1.2, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S)

(2R)-5-(Benzyloxy)pentan-2-olC12H18O2[α]D25=+9.0 (c 1.25, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R)

(4R)-4-(Tetrahydro-2H-2-pyranyloxy)pentan-1-olC10H20O3[α]D25=+19.6 (c 0.65, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3R)

Ethyl (E,6R)-6-(tetrahydro-2H-2-pyranyloxy)-2-heptenoateC14H24O4[α]D25=+5.6 (c 1.45, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (E,6R)

(E,6R)-6-(Tetrahydro-2H-2-pyranyloxy)-2-hepten-1-olC12H22O3[α]D25=-1.4 (c 1.25, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (E,6R)

{(2R,3R)-3-[(3R)-3-(Tetrahydro-2H-2-pyranyloxy)butyl]oxirane-2-yl}methanolC12H22O4[α]D25=+15.1 (c 1.15, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3R) (3R)

tert-Butyl(dimethyl)({(1R)-1-[(3R)-3-(tetrahydro-2H-2-pyranyloxy)butyl]-2-propenyl}oxy)silaneC18H36O3Si[α]D25=-0.8 (c 0.75, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R) (3R)

(2R,5R)-5-{[1-(tert-Butyl)-1,1-dimethylsilyl]oxy}-6-hepten-2-olC13H28O2Si[α]D25=-0.8 (c 0.7, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,5R)

tert-Butyl[((1R,4R,8S)-8-{[1-(tert-butyl)-1,1-dimethylsilyl]oxy}-4-methyl-6-methylene-1-vinyl-9-decenyl)oxy]dimethylsilaneC24H48O4Si2[α]D25=-7.7 (c 0.4, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,4R,8S)

(3S,7R,10R)-3,10-Dihydroxy-7-methyl-1,11-dodecadiene-5-oneC12H20O4[α]D25=-6.6 (c 0.75, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S,7R,10R)

(4S,7R,10R)-4,7-Dihydroxy-10-methyl-3,4,7,8,9,10-hexahydro-2H-2-oxecinoneC10H16O4[α]D25=-29.2 (c 0.5, MeOH)Source of chirality: asymmetric synthesisAbsolute configuration: (4S,7R,10R)

{(2R,3R)-3-[3-(Tetrahydro-2H-2-pyranyloxy)propyl]oxiran-2-yl}methanolC11H20O4[α]D25=+17.5 (c 2.95, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3R)

2-{3-[(2R,3S)-3-(Iodomethyl)oxiran-2-yl]propoxy}tetrahydro-2H-2-pyranC11H19O3I[α]D25=-3.8 (c 2.4, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3S)

(3R)-6-(Tetrahydro-2H-2-pyranyloxy)-1-hexen-3-olC11H20O3[α]D25=-9.1 (c 0.45, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R)

tert-Butyl(dimethyl)({(1R)-1-[3-(tetrahydro-2H-2-pyranyloxy)propyl]-2-propenyl}oxy)silaneC17H34O3Si[α]D25=-7.1 (c 1.95, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R)

(4R)-4-{[1-(tert-Butyl)-1,1-dimethylsilyl]oxy}-5-hexen-1-olC12H26O2Si[α]D25=-5.3 (c 2.55, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (4R)

tert-Butyl[((1R,8S)-8-{[1-(tert-butyl)-1,1-dimethylsilyl]oxy}-6-methylene-1-vinyl-9-decenyl)oxy]dimethylsilaneC23H46O4Si2[α]D25=-2.8 (c 0.7, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,8S)

(4R)-4-Hydroxy-5-hexenyl(3S)-3-hydroxy-4-pentenoateC11H18O4[α]D25=-3.8 (c 0.55, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (4R) (3S)