| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1349370 | Tetrahedron: Asymmetry | 2009 | 9 Pages |
A convenient method for the synthesis of optically active trans-hydroxyselenides and trans-hydroxydiselenides from the bicyclic terpene group based on the reactions of sodium selenide or sodium diselenide with cis- and trans-(+)-3-carane, trans-(+)-2-carane and (−)-β-pinane epoxides is described. The corresponding cis-hydroxy and cis-methoxydiselenides were obtained in the reaction of sodium diselenide with β-hydroxy- and β-methoxytosylates. The influence of a hydroxy group at the β-position on the diastereomeric ratio of the products of the asymmetric methoxyselenenylation of styrene has been established by composition of the products, crystal structure analyses, and theoretical calculations using a DFT method on the B3LYP level (6-311G(d)).
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(1S,3S,1′S,3′S)-(+)-Bis(3-hydroxy-4-caranyl) selenideC20H34O2SeEe >99%[α]D20=+117.3 (c 5.00, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3S,4S,6R,1′S,3′S,4′S,6′R)
(1S,3R,1′S,3′R)-(−)-Bis(3-hydroxy-4-isocaranyl) diselenideC20H34O2SeEe >99%[α]D20=-129.4 (c 4.80, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3R,4R,6R 1′S,3′R,4′R,6′R)
(1R,2S,1′R,2′S)-(−)-Bis(2-hydroxymyrtanyl) diselenideC20H34O2SeEe >96%[α]D22=-70.0 (c 5.20, CHCl3)Source of chirality: (−)-β-pineneAbsolute configuration: (1R,2S,5S,1′R,2′S,5′S)
(1S,3S,1′S,3′S)-(+)-Bis(3-hydroxy-4-caranyl) diselenideC20H34O2Se2Ee >99%[α]D20=+230.7 (c 5.50, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3S,4S,6R,1′S,3′S,4′S,6′R)
(1S,3R,1′S,3′R)-(−)-Bis(3-hydroxy-4-isocaranyl)C20H34O2Se2Ee >99%[α]D20=-219.5 (c 5.10, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3R,4R,6R,1′S,3′R,4′R,6′R)
(1S,3R,1′S,3′R)-(−)-Bis(3-hydroxy-2-caranyl)C20H34O2Se2Ee >98%[α]D20=-174.9 (c 4.86, CHCl3)Source of chirality: (+)-2-caraneAbsolute configuration: (1S,2R,3R,6R,1′S,2′R,3′R,6′R)
(1R,3S,1′R,3′S)-(−)-Bis(2-hydroxymyrtanyl) diselenideC20H34O2Se2Ee >96%[α]D20=-99.7 (c 5.40, CHCl3)Source of chirality: (−)-β-pineneAbsolute configuration: (1R,2S,5S,1′R,2′S,5′S)
(1S,3R,1′S,3′R)-(+)-Bis(3-hydroxy-4-caranyl) diselenideC20H34O2Se2Ee >99%[α]D20=+190.0 (c 10.70, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3R,4S,6R 1′S,3′R,4′S,6′R)
(1S,3R)-(−)-3-Methoxy-4-isocaranolC11H20O2Ee >99%[α]D20=-9.5 (c 4.44, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3R,4R,6R 1′S,3′R,4′R,6′R)
(1S,3R)-(−)-3-methoxy-4-isocaranyl tosylateC20H34O2Se2Ee >99%[α]D20=-21.6 (c 7.63, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3R,4R,6R 1′S,3′R,4′R,6′R)
(1S,3R,1′S,3′R)-(+)-Bis(3-methoxy-4-caranyl) diselenideC22H38O2Se2Ee >99%[α]D20=+257.9 (c 4.28, CHCl3)Source of chirality: (+)-3-caraneAbsolute configuration: (1S,3R,4S,6R 1′S,3′R,4′S,6′R)
