Stereodivergent synthesis of both (2S)- and (2R)-1-monoricinolein derivatives by lipase-catalyzed hydrolysis or transesterification directed to new ferroelectric liquid crystals

The preparation of both (2S)- and (2R)-1-monoricinolein derivatives has been developed to synthesize ferroelectric liquid crystals. Lipase-catalyzed hydrolysis of 2-protected-1,3-diricinoleins provided (2S)-1-monoricinolein derivatives with high diastereoselectivities, while transesterification of 2-protected glycerols with vinyl recinoleate gave (2R)-1-monoricinolein counterparts in good yields with high diastereoselectivities.

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(9Z,2′S,12R)-3′-Hydroxy-2′-(methoxymethoxy)propyl 12-hydroxyoctadec-9-enoateC23H44O6De = 94%[α]D21=+8.2 (c 0.093, CHCl3)Source of chirality: enzymatic hydrolysisAbsolute configuration: (2′S,12R)

(9Z,2′R,12R)-3′-Benzoyloxy-2′-(methoxymethoxy)propyl 12-benzoyloxyoctadec-9-enoateC37H52O8De = 94%[α]D20=+14.6 (c 0.091, CHCl3)Source of chirality: enzymatic hydrolysisAbsolute configuration: (2′R,12R)

(9Z,2′R,12R)-2′-Benzyloxy-3′-hydroxypropyl 12-hydroxyoctadec-9-enoateC28H46O5De = 96%[α]D24=-8.5 (c 0.218, CHCl3)Source of chirality: enzymatic transesterificationAbsolute configuration: (2′R,12R)

(9Z,2′R,12R)-3′-4-(4-hexyloxyloxyphenyl)benzoyl-2′-(methoxymethoxy)propyl 12-hydroxyoctadec-9-enoateC42H64O8De = 94%[α]D26=+0.91 (c 0.29, CHCl3)Source of chirality: enzymatic hydrolysisAbsolute configuration: (2′R,12R)