Olefin cross-metathesis based approach for the first total synthesis of phomopsolidone B and total synthesis of phomopsolidone A

The first total synthesis of phomopsolidone B and the total synthesis of phomopsolidone A have been achieved based on an olefin cross-metathesis approach starting from l-(+)-diethyl tartrate.

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(S)-5-((S)-1-Hydroxyallyl)dihydrofuran-2(3H)-oneC7H10O3[α]D25 = +20.0 (c 0.25, CHCl3)Absolute configuration: (S,S)Source of chirality: l-(+)-DET

(S)-1-((S)-5-Oxotetrahydrofuran-2-yl)allyl (E)-2-methylbut-2-enoateC12H16O4[α]D25 = −5.4 (c 0.28, CHCl3)Absolute configuration: (S,S,E)Source of chirality: l-(+)-DET

((1S,4S,5S,E)-4,5-Dihydroxy-1-((S)-5-oxotetrahydrofuran-2-yl)hex-2-en-1-yl(E)-2-methylbut-2-enoateC15H22O6[α]D25 = −10.5 (c 0.32, MeOH)Absolute configuration: (1S,4S,5S,E,S,E)Source of chirality: l-(+)-DET

Methyl (Z)-3-((4S,5S)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)acrylateC11H16O4[α]D25 = +15.4 (c 0.24, CHCl3)Absolute configuration: (Z,4S,5S)Source of chirality: l-(+)-DET

(S)-5-((S)-1-Hydroxyallyl)furan-2(5H)-oneC7H8O3[α]D25 = −20.3 (c 0.24, CHCl3)Absolute configuration: (S,S)Source of chirality: l-(+)-DET

(S)-1-((S)-5-Oxo-2,5-dihydrofuran-2-yl)allyl (E)-2-methylbut-2-enoateC12H14O4[α]D25 = −11.9 (c 0.20, CHCl3)Absolute configuration: (S,S,E)Source of chirality: l-(+)-DET

(1S,4S,5S,E)-4,5-Dihydroxy-1-((S)-5-oxo-2,5-dihydrofuran-2-yl)hex-2-en-1-yl(E)-2-methylbut-2-enoate)C15H20O6[α]D25 = −16.2 (c 0.16, CHCl3)Absolute configuration: (1S,4S,5S,E,S,E)Source of chirality: l-(+)-DET