| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1348112 | Tetrahedron: Asymmetry | 2012 | 6 Pages |
The enantiospecific total synthesis of silphiperfol-6-ene has been accomplished starting from the readily available monoterpene (R)-limonene, employing a rhodium carbenoid insertion into the CH bond of a tertiary methyl group. A substrate dependent competitive insertion of the rhodium carbenoid in the γ- and β-CH bonds to form cyclopentanone and cyclobutanones, respectively, has been described.
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(1S,3R,6S,9S)-9-Isopropenyl-3,6-dimethyltricyclo[4.3.0.01,3]nonan-4-oneC14H20O[α]D24=-53.4 (c 6.4, CHCl3)Source of chirality: (R)-limoneneAbsolute configuration: (1S,3R,6S,9S)
2-[(1R,2R,5S)-1,5,7,8-Tetramethylbicyclo[3.3.0]oct-7-en-2-yl]ethanoneC14H22O[α]D25=-110.8 (c 4.3, CHCl3)Source of chirality: (R)-limoneneAbsolute configuration: (1′R,2′R,5′S)
(1R,5R,8S)-8,10,11-Trimethyltricyclo[6.3.0.01,5]undec-10-en-4-oneC14H20O[α]D24=-142.4 (c 1.6, CHCl3)Source of chirality: (R)-limoneneAbsolute configuration: (1R,5R,8S)
(1R,2R,5S,7R)-1,7,9,10-Tetramethyltricyclo[5.3.0.02,5]dec-9-en-3-oneC14H20O[α]D24=+214.9 (c 0.7, CHCl3)Source of chirality: (R)-limoneneAbsolute configuration: (1R,2R,5S,7R)
(1R,5S,8S)-9-Methylene-2,3,5-trimethyltricyclo[6.3.0.01,5]undec-2-eneC15H22[α]D23=-141.4 (c 1.0, CHCl3)Source of chirality: (R)-limoneneAbsolute configuration: (1R,5S,8S)
