| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1345765 | Tetrahedron: Asymmetry | 2014 | 9 Pages |
A ring closing metathesis (RCM) reaction of dienes and an intramolecular Pauson–Khand (PKR) reaction of enynes derived from tertiary allyl, homoallyl, and homopropargyl alcohol backbones to afford the corresponding spirocyclic dihydrofuran and dihydropyrans and spirocyclic cyclopentenone pyrans, respectively, are described. Cyclopent-2-ene anchored tertiary allyl, homoallyl, and homopropargyl alcohols 1a–c have been efficiently resolved via enzymatic resolution with high ee (up to 90%) with 44%, 40%, and 43% chemical yields, respectively. Moreover, the cyclohex-2-ene anchored tertiary allyl, homoallyl, and homopropargyl alcohols 3a–c have also been resolved in the same manner with high ee (up to 97%) and in 42%, 45%, and 49% chemical yields. Enantiomerically enriched dienes derived from tertiary homoallyl alcohols yield the corresponding enantiomerically enriched spirocyclic dihydropyran derivatives via RCM with 74% and 78% chemical yields and with 90% and 97% ee, respectively. Moreover, enantiomerically enriched enynes derived from tertiary homoallyl alcohols afford the corresponding enantiomerically enriched cyclopentenone pyrans with spirocyclic motifs via PKR with 80% and 81% chemical yields, respectively, and as single diastereomers.
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(−)-1-Vinylcyclopent-2-enolC7H10OEe = 45%[α]D26=-7.50 (c 0.70, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(−)-1-Allylcyclopent-2-enolC8H12OEe = 90%[α]D26=-4.7 (c 1.10, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(+)-1-(Prop-2-ynyl)cyclopent-2-enolC8H10OEe = 60%[α]D26=+3.9 (c 1.40, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(+)-1-Vinylcyclopent-2-enyl acetateC9H12O2Ee = 52%[α]D26=+7.1 (c 1.0, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(+)-1-Allylcyclopent-2-enyl acetateC10H14O2Ee = 85%[α]D26=+5.7 (c 1.20, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(−)-1-(Prop-2-ynyl)cyclopent-2-enyl acetateC10H12O2Ee = 84%[α]D26=-6.6 (c 0.50, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(+)-1-Vinylcyclohex-2-enolC8H12OEe = 55%[α]D26=+5.9 (c 1.0, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(−)-1-Allylcyclohex-2-enolC9H14OEe = 65%[α]D26=-8.65 (c 1.0, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(−)-1-(Prop-2-ynyl)cyclohex-2-enolC9H12OEe = 25%[α]D26=-5.7 (c 1.0, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(−)-1-Vinylcyclohex-2-enyl acetateC10H14O2Ee = 58%[α]D26=-5.2 (c 0.70, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(+)-1-Allylcyclohex-2-enyl acetateC11H16O2Ee = 97%[α]D26=+8.2 (c 1.0, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(+)-1-(Prop-2-ynyl)cyclohex-2-enyl acetateC11H14O2Ee = 72%[α]D26=+9.58 (c 0.5, CHCl3)Source of chirality: Enzymatic resolutionAbsolute configuration: not determined
(−)-3-Allyl-3-(allyloxy)cyclopent-1-eneC11H16O[α]D26=-5.3 (c 1.0, CHCl3)Source of chirality: (−)-1-Allylcyclopent-2enolAbsolute configuration: not determined
(+)-3-Allyl-3-(allyloxy)cyclohex-1-eneC12H18O[α]D26=+2.7 (c 1.0, CHCl3)Source of chirality: (+)-1-Allylcyclohex-2-enolAbsolute configuration: not determined
(+)-6-Oxaspiro[4,5]deca-1,8-dieneC9H12O[α]D26=+4.1 (c 2.20, CHCl3)Source of chirality: (−)-3-Allyl-3-(allyloxy)cyclopent-1-eneAbsolute configuration: not determined
(−)-1-Oxaspiro[5,5]undeca-3,7-dieneC10H14O[α]D26=-1.9 (c 1.0, CHCl3)Source of chirality: (+)-3-Allyl-3-(allyloxy)cyclohex-1-eneAbsolute configuration: not determined
(+)-3-Allyl-3-(prop-2ynyloxy)cyclopent-1-eneC11H14O[α]D26=+2.9 (c 1.6, CHCl3)Source of chirality: (−)-1-Allylcyclopent-2-enolAbsolute configuration: not determined
(−)-3-Allyl-3-(prop-2ynyloxy)cyclohex-1-eneC12H16O[α]D26=-3.9 (c 0.65, CHCl3)Source of chirality: (+)-1-Allylcyclohex-2-enolAbsolute configuration: not determined
(−)-4a,5-Dihydro-1H-spiro[cyclopent[2]ene-1,3-cyclopenta[c]pyran]-6 (4H)-oneC12H14O2[α]D26=-1.7 (c 0.5, CHCl3)Source of chirality: (+)-3-Allyl-3-(prop-2-ynyloxy)cyclopent-1-eneAbsolute configuration: not determined
(−)-4a,5-Dihydro-1H-spiro[cyclohex[2]ene-1,3-cyclopenta[c]pyran]-6 (4H)-oneC13H16O2[α]D26=-1.6 (c 0.25, CHCl3)Source of chirality: (−)-3-Allyl-3-(prop-2-ynyloxy)cyclohex-1-eneAbsolute configuration: not determined
