Chiron approach for the formal synthesis of (+)-syributin 1

A chiron approach for the formal synthesis of (+)-syributin 1 from d-mannitol has been described. The key steps are a Wittig reaction and RCM.

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2-(tert-Butyldiphenylsilyloxy)-1-((4R,4′R,5S)-2,2,2′,2′-tetramethyl-4,4′-bi(1,3-dioxolan)-5-yl)ethanoneC28H38O6Si[α]D25=-3.7 (c 1.0, CHCl3)Source of chirality: d-mannitolAbsolute configuration: (4R,4′R,5S)

tert-Butyldiphenyl(2-((4S,4′R,5R)-2,2,2′,2′-tetramethyl-4,4′-bi(1,3-dioxolan)-5-yl)allyloxy)silaneC28H38O6Si[α]D25=+1.5 (c 1.19, CHCl3)Source of chirality: d-mannitolAbsolute configuration: (4S,4’R,5R)

2-((4S,4′R,5R)-2,2,2′,2′-Tetramethyl-4,4′-bi(1,3-dioxolan)-5-yl)prop-2-en-1-olC13H22O5[α]D25=-11.5 (c 1.21, CHCl3)Source of chirality: d-mannitolAbsolute configuration: (4S,4′R,5R)

2-((4S,4′R,5R)-2,2,2′,2′-Tetramethyl-4,4′-bi(1,3-dioxolan)-5-yl)allyl acrylateC16H24O6[α]D25=-16.5 (c 0.38, CHCl3)Source of chirality: d-mannitolAbsolute configuration: (4S,4′R,5R)

4-((4S,4′R,5R)-2,2,2′,2′-Tetramethyl-4,4′-bi(1,3-dioxolan)-5-yl)furan-2(5H)-oneC14H20O6[α]D34=-13.8 (c 1.05, CHCl3)Source of chirality: d-mannitolAbsolute configuration: (4S,4′R,5R).

4-((4R,5R)-5-((R)-1,2-Dihydroxyethyl)-2,2-dimethyl-1,3-dioxolan-4-yl)furan-2(5H)-oneC11H17O6[α]D25=+4.2 (c 0.8, MeOH)Source of chirality: d-mannitolAbsolute configuration: (4R,5R)-5-(R)

4-((4R,5R)-5-(Hydroxymethyl)-2,2-dimethyl-1,3-dioxolan-4-yl)furan-2(5H)-oneC10H14O5[α]D25=-5.8 (c 0.4, CHCl3)Source of chirality: d-mannitolAbsolute configuration: (4R,5R)

(1′R,2′R)-3-[3′-(Hexanoyloxy)-1′,2′-(isopropylidenedioxy)-2-buten-4-olideC16H24O6[α]D25=10.5 (c 1.22, CHCl3)Source of chirality: d-mannitolAbsolute configuration: (1′R,2′R)