A facile chiral pool synthesis of 9-epi-decarestrictine-D, decarestrictine-D and O

A facile chiral pool total synthesis of 9-epi-decarestrictine-D, decarestrictine-D and O has been achieved from l-(+)-diethyl tartrate. The strategy utilized is conventional and flexible. Wittig homologation and Grubbs ring closing metathesis are the key reactions employed for the synthesis of the title molecules.

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((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)dimethanolC7H14O4[α]D25=+10.8 (c 0.5, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S)

((4S,5S)-5-((Benzyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)methanolC14H20O4[α]D25=+8.3 (c 1.0, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S)

2-((4S,5S)-5-((Benzyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)ethanolC15H22O4[α]D25=-7.9 (c 1.7, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S)

(2-((4S,5S)-5-((Benzyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)ethoxy)(tert-butyl)dimethylsilaneC21H36O4Si[α]D25=-16.5 (c 1.0, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S)

((4S,5S)-5-(2-((tert-Butyldimethylsilyl)oxy)ethyl)-2,2-dimethyl-1,3-dioxolan-4-yl)methanolC14H30O4Si[α]D25=-19.5 (c 2.3, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S)

tert-Butyl(2-((4S,5S)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)ethoxy)dimethylsilaneC15H30O3Si[α]D25-10.0 (c 1.05, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S)

2-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)ethanolC9H16O3[α]D25=-7.2 (c 0.8, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S)

2-((5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)acetic acidC9H14O4[α]D25=-29.2 (c 1.8, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (5S)

tert-Butyl(2-((4S,5R)-5-(iodomethyl)-2,2-dimethyl-1,3-dioxolan-4-yl)ethoxy)dimethylsilaneC14H29IO3Si[α]D25=-28.3 (c 0.6, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5R)

(S)-5-((tert-Butyldimethylsilyl)oxy)pent-1-en-3-olC11H24O2Si[α]D25=+11.8 (c 0.34, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (3S)

(S)-9,9,10,10-Tetramethyl-5-vinyl-2,4,8-trioxa-9-silaundecaneC13H28O3Si[α]D25=-51.6 (c 0.53, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (3S)

(S)-3-(Methoxymethoxy)pent-4-en-1-olC10H16O5[α]D25=-92.0 (c 0.4, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (3S)

(2R,4S)-4-(Methoxymethoxy)hex-5-en-2-yl 2-((4S,5S)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)acetateC17H28O6[α]D25=-55.9 (c 1.1, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (2R,4S) (4S,5S)

(2S,4S)-4-(Methoxymethoxy)hex-5-en-2-yl 2-((4S,5S)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)acetateC17H28O6[α]D25=-28.1 (c 1.6, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (2S,4S,4S,5S)

(3aS,7R,9S,11aS,E)-9-(Methoxymethoxy)-2,2,7-trimethyl-7,8,9,11a-tetrahydro-3aH-[1,3]dioxolo[4,5-d]oxecin-5(4H)-oneC15H24O6[α]D25=-8.3 (c 0.6, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (3aS,7R,9S,11aS,E)

(3aS,7S,9S,11aS,E)-9-(Methoxymethoxy)-2,2,7-trimethyl-7,8,9,11a-tetrahydro-3aH-[1,3]dioxolo[4,5-d]oxecin-5(4H)-oneC15H24O6[α]D25=+24.4 (c 0.9, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (3aS,7S,9S,11aS,E)

(4S,5S,8S,10R,E)-4,5,8-Trihydroxy-10-methyl-3,4,5,8,9,10-hexahydro-2H-oxecin-2-oneC10H16O5[α]D25=-47.85 (c 0.7, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S,8S,10R,E)

(4S,5S,8S,10S,E)-4,5,8-Trihydroxy-10-methyl-3,4,5,8,9,10-hexahydro-2H-oxecin-2-oneC10H16O5[α]D25=-4.2 (c 0.7, MeOH)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,5S,8S,10S,E)

(R)-1-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)propan-2-olC10H18O3[α]D25=-5.9 (c 1.7, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (2R,5S)

(S)-3-(Methoxymethoxy)pent-4-enoic acidC10H18O3[α]D25=-77.3 (c 0.75, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (3S)

(S)-(R)-1-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)propan-2-yl 3-(methoxymethoxy)pent-4-enoateC17H28O6[α]D25=-45.8 (c 0.9, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (S)-(R)-1-((4S,5S)

(3aS,5R,9S,11aS,E)-9-(Methoxymethoxy)-2,2,5-trimethyl-4,5,8,9-tetrahydro-3aH-[1,3]dioxolo[4,5-d]oxecin-7(11aH)-oneC15H24O6[α]D25=-58.5 (c 0.85, CHCl3)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (3aS,5R,9S,11aS,E)

(4S,7S,8S,10R,E)-4,7,8-Trihydroxy-10-methyl-3,4,7,8,9,10-hexahydro-2H-oxecin-2-oneC10H16O5[α]D25=-22.5 (c 0.2, MeOH)Source of chirality: (+)-DiethyltartrateAbsolute configuration: (4S,7S,8S,10R,E)