Stereoselective synthesis of (+)-pericosine B and (+)-pericosine C using ring closing metathesis approach

Stereoselective synthesis of (+)-pericosine B and (+)-pericosine C were achieved from d-ribose using RCM and RCEYM as key steps.

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(1R,2R)-1-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)-1-(methoxymethoxy)-3-((tetrahydro-2H-pyran-2-yloxy)methyl)but-3-en-2-olC19H32O7[α]D24=+122.3 (c 0.3, CHCl3)Source of chirality: d-riboseAbsolute configuration: (1R,2R,4S,5S)

(3aS,4R,5R,7aS)-4-(Methoxymethoxy)-2,2-dimethyl-6-((tetrahydro-2H-pyran-2-yloxy) methyl)-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxol-5-olC17H28O7[α]D24=-64.1 (c 2.1, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3S,4R,5R,7S)

(3aS,4R,5R,7aS)-5-Methoxy-4-(methoxymethoxy)-2,2-dimethyl-6-((tetrahydro-2H-pyran-2-yloxy)methyl)-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxoleC18H30O7[α]D24=+31.9 (c 0.6, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4R,5R,7S)

((3aS,6R,7R,7aS)-6-Methoxy-7-(methoxymethoxy)-2,2-dimethyl-3a,6,7,7a-tetrahydrobenzo[d][1,3]dioxol-5-yl)methanolC13H22O6[α]D24=+62.9 (c 0.5, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3S,6R,7R,7S)

(3aS,6R,7R,7aS)-6-Methoxy-7-(methoxymethoxy)-2,2-dimethyl-3a,6,7,7a-tetrahydrobenzo[d][1,3]dioxole-5-carbaldehydeC13H20O6[α]D24=-52.1 (c 0.7, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3S,6R,7R,7S)

(3aS,6R,7R,7aS)-Methyl 6-methoxy-7-(methoxymethoxy)-2,2-dimethyl-3a,6,7,7a-tetrahydrobenzo[d][1,3]dioxole-5-carboxylateC14H22O7[α]D24=-39.8 (c 0.8, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3S,6S,7R,7R)

(3S,4S,5S,6R)-Methyl 3,4,5-trihydroxy-6-methoxycyclohex-1-enecarboxylateC9H14O8[α]D24=+29 (c 0.12, EtOH)Source of chirality: d-riboseAbsolute configuration: (3S,4S,5S,6R)

(1R,2S)-1-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)-1-(methoxymethoxy)-4-(trimethylsilyl)but-3-yn-2-olC16H28O5Si[α]D25=-16.5 (c 1.4, CHCl3)Source of chirality: d-riboseAbsolute configuration: (R,2S,4S,5S)

(1R,2R)-1-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)-1-(methoxymethoxy)-4-(trimethylsilyl)but-3-yn-2-olC16H28O5Si[α]D25=+29.3 (c 2.2, CHCl3)Source of chirality: d-riboseAbsolute configuration: (R,2R,4S,5S)

(1R,2S)-1-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)-1-(methoxymethoxy)but-3-yn-2-olC13H20O5[α]D25=+11.0 (c 2.2, CHCl3)Source of chirality: d-riboseAbsolute configuration: (1R,2S,4S,5S)

(4S,5S)-4-((1R,2S)-2-Methoxy-1-(methoxymethoxy)but-3-ynyl)-2,2-dimethyl-5-vinyl-1,3-dioxolaneC19H22O5[α]D25=-8.9 (c 1.1, CHCl3)Source of chirality: d-riboseAbsolute configuration: (4S,5R,1S,2S)

(3aS,4R,5S,7aS)-5-Methoxy-4-(methoxymethoxy)-2,2-dimethyl-6-vinyl-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxoleC14H22O5[α]D25=+2.1 (c 0.9, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,4R,5S,7aS)

(3aS,6S,7R,7aS)-6-Methoxy-7-(methoxymethoxy)-2,2-dimethyl-3a,6,7,7a-tetrahydrobenzo[d][1,3]dioxole-5-carbaldehydeC13H20O6[α]D25=+78.2 (c 1.5, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,6S,7R,7aS)

(3aS,6S,7R,7aS)-Methyl 6-methoxy-7-(methoxymethoxy)-2,2-dimethyl-3a,6,7,7a-tetrahydrobenzo[d][1,3] dioxole-5-carboxylateC14H22O7[α]D25=+45.6 (c 0.8, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,6S,7R,7aS)

(3S,4S,5S,6S)-Methyl 3,4,5-trihydroxy-6-methoxycyclohex-1-enecarboxylateC9H14O8[α]D25=+72.1 (c 0.9, EtOH)Source of chirality: d-riboseAbsolute configuration: (3S,4S,5S,6S)

(1R,2S)-1-((4S,5S)-2,2-Dimethyl-5-vinyl-1,3-dioxolan-4-yl)-1-(methoxymethoxy)-3-((tetrahydro-2H-pyran-2-yloxy)methyl)but-3-en-2-olC19H32O7[α]D25=-14.3 (c 2.1, CHCl3)Source of chirality: d-riboseAbsolute configuration: (1R,2S,4S,5S)

(3aS,4R,5S,7aS)-4-(Methoxymethoxy)-2,2-dimethyl-6-((tetrahydro-2H-pyran-2-yloxy)methyl)-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxol-5-olC17H28O7[α]D25=+76.3 (c 0.56, CHCl3)Source of chirality: d-riboseAbsolute configuration: (1S,2R,3S,4S)

(3aS,4R,5S,7aS)-4-(Methoxymethoxy)-2,2-dimethyl-6-((tetrahydro-2H-pyran-2-yloxy)methyl)-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxol-5-olC18H30O7[α]D25=-7.3 (c 1.17, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,4R,5S,7aS)

((3aS,6S,7R,7aS)-6-Methoxy-7-(methoxymethoxy)-2,2-dimethyl-3a,6,7,7a-tetrahydrobenzo[d][1,3]dioxol-5-yl)methanolC13H22O6[α]D25=+22.5 (c 0 .17, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,6S,7R,7aS)