Preparation of chiral cyclopropanecarboxylic acids and 3-oxabicyclo[3.1.0]hexane-2-ones from levoglucosenone

Levoglucosenone (a chiral α,β-unsaturated ketone derivative of cellulose) serves as a starting compound in 2 and 3 step syntheses of chiral cyclopropanecarboxylic acids and 3-oxabicyclo[3.1.0]hexane-2-ones, respectively.

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(1S,2S,3S)-2-Benzoyl-3-((S)-2-formyloxy-1-hydroxyethyl)cyclopropanecarboxylic acidC14H14O6Ee = 100%[α]D20=+112.4 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,2S,3S,1′S)

(1S,2S,3S)-2-(4-Chlorobenzoyl)-3-((S)-2-formyloxy-1-hydroxyethyl)cyclopropanecarboxylic acidC14H13ClO6Ee = 100%[α]D20=+98.0 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,2S,3S,1′S)

(1S,2S,3S)-2-(4-Bromobenzoyl)-3-((S)-2-formyloxy-1-hydroxyethyl)cyclopropanecarboxylic acidC14H13BrO6Ee = 100%[α]D20=+89.6 (c 0.5, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,2S,3S,1′S)

(1S,2S,3S)-2-((S)-2-Formyloxy-1-hydroxyethyl)-3-(2-thienoyl)cyclopropanecarboxylic acidC12H12O6SEe = 100%[α]D20=+140.0 (c 0.8, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,2S,3S,1′S)

(1S,4S,5S,6S)-6-Benzoyl-4-hydroxymethyl-3-oxabicyclo[3.1.0]hexane-2-oneC13H12O4Ee = 100%[α]D20=+112.8 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,4S,5S,6S)

(1S,4S,5S,6S)-6-(4-Chlorobenzoyl)-4-hydroxymethyl-3-oxabicyclo[3.1.0]hexane-2-oneC13H11ClO4Ee = 100%[α]D20=+88.1 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,4S,5S,6S)

(1S,4S,5S,6S)-6-(4-Bromobenzoyl)-4-hydroxymethyl-3-oxabicyclo[3.1.0]hexane-2-oneC13H11BrO4Ee = 100%[α]D20=+79.7 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,4S,5S,6S)

(1S,4S,5S,6S)-4-Hydroxymethyl-6-(2-thienoyl)-3-oxabicyclo[3.1.0]hexane-2-oneC12H12O6SEe = 100%[α]D20=+112.4 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,4S,5S,6S)

(1S,4S,5S,6S)-4-Hydroxymethyl-6-(4-methylfurazane-3-yl)carbonyl-3-oxabicyclo[3.1.0]hexane-2-oneC10H10N2O5Ee = 100%[α]D24=+97.2 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,4S,5S,6S)

(1S,4S,5S,6S)-6-(1-Adamantoyl)-4-hydroxymethyl-3-oxabicyclo[3.1.0]hexane-2-oneC17H22O4Ee = 100%[α]D20=+84.1 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,4S,5S,6S)

(1S,4S,5S,6S)-Methyl 4-hydroxymethyl-2-oxo-3-oxabicyclo[3.1.0]hexane-6-carboxylateC8H10O5Ee = 100%[α]D20=+98.8 (c 1.0, DMSO)Source of chirality: levoglucosenoneAbsolute configuration: (1S,4S,5S,6S)