0000000000178199
AUTHOR
Eva Molina
Total Syntheses of Four Stereoisomers of 4α-Hydroxy-1β,7β-peroxy- 10βH-guaia-5-ene
[reaction: see text]. The first total syntheses of four stereoisomers of 4alpha-hydroxy-1beta,7beta-peroxy-10betaH-guaia-5-ene are reported starting from the readily available (+)-dihydrocarvone. These compounds have been synthesized from dienes (-)-isoguaiene and (-)-10-epi-isoguaiene by tandem ene hydroperoxylation-[4 + 2] cycloaddition with O(2) followed by selective reduction. The structure of the natural 4alpha-hydroxy-1beta,7beta-peroxy-10betaH-guaia-5-ene isolated from Liabum floribundum has been confirmed.
Diastereoselective Michael addition of (S)-mandelic acid enolate to 2-arylidene-1,3-diketones: enantioselective diversity-oriented synthesis of densely substituted pyrazoles
[EN] A diversity-oriented approach to enantiomerically pure densely substituted pyrazoles, ¿-aryl-¿-pyrazolylatrolactic acid and ¿-aryl-¿-pyrazolylacetophenones has been developed. The approach utilises the conjugated addition of the lithium enolate of the (2S,5S)-cis-1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde to several 2-arylidene-1,3-diketones, which proceeds readily to give the corresponding Michael adducts in good yields and diastereoselectivities. The cyclocondensation of the 1,3-diketone moieties present in Michael adducts with several hydrazines leads to enantiomerically pure densely substituted pyrazoles. Subsequent basic hydrolysis of the …
A Bioinspired Approach to Tri-nor-guaianes. Synthesis of (−)-Clavukerin A
A bioinspired approach to tri-nor-guaianes by degradation of the C-7 side chain of related guaia-11-enes is described. In this approach (-)-clavukerin A (1) is obtained by selective ozonolysis-Criegge rearrangement of (+)-1alphaH,7alphaH,10alphaH-guaia-4,11-dien-3-one (4) to afford 7beta-hydroxy and 7beta-acetoxy tri-nor-guaiane derivatives 6 and 7, respectively, which after elimination and deoxygenation give the title compound. The starting guaiadienone is readily obtained from commercially available santonin or (+)-dihydrocarvone.
ChemInform Abstract: Synthesis of (+)-Pechueloic Acid and (+)-Aciphyllene. Revision of the Structure of (+)-Aciphyllene.
Abstract 1α H ,7α H ,10α H -Guaia-4,11-dien-3-one and its 1β H ,10β H diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1α H ,10α H isomer gave as main product its 13-hydroxy derivative and a small amount of (+)-7β-hydroxy-1α H ,10α H -guaia-4,11-dien-3-one, whereas the 1β H ,10β H diastereomer afforded selectively the (−)-7α-hydroxy-1β H ,10β H enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C 3 of the 1β H ,10β H guaiadienone afforded a guaiadiene with the reported structure for aciphylle…
Syntheses of (+)-alismoxide and (+)-4-epi-alismoxide.
The first total syntheses of (+)-alismoxide and (+)-4-epi-alismoxide are reported. Formal chemo-, regio-, and stereoselective addition of water to 10alpha-acetoxy-1alphaH,5betaH-guaia-3,6-diene afforded the target compounds after reduction. The absolute stereochemistry of (+)-alismoxide has been established. The low [alpha](D) +8.6 value indicates that significant amounts of alismoxide result from biosynthetic processes. Furthermore, the structure of the natural guaienediol isolated from Silphium perfoliatum has been corrected to (-)-alismoxide.
Synthesis of all 7αH-guaia-4,11-dien-3-one diastereomers from (+)-dihydrocarvone
Abstract All four 7α H -guaia-4,11-dien-3-one diastereomers have been synthesized from the common intermediate 1α H ,10α-acetoxy-7α H -guaia-4,11-dien-3-one obtained from (+)-dihydrocarvone. The spectral features of the four diasteromers have been correlated and the structure and absolute configuration of 1β H ,10β H ,7α H -guaia-4,11-dien-3-one isolated from Pleocarphus revolutus has been confirmed.
Synthesis of (+)-pechueloic acid and (+)-aciphyllene. Revision of the structure of (+)-aciphyllene
Abstract 1α H ,7α H ,10α H -Guaia-4,11-dien-3-one and its 1β H ,10β H diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1α H ,10α H isomer gave as main product its 13-hydroxy derivative and a small amount of (+)-7β-hydroxy-1α H ,10α H -guaia-4,11-dien-3-one, whereas the 1β H ,10β H diastereomer afforded selectively the (−)-7α-hydroxy-1β H ,10β H enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C 3 of the 1β H ,10β H guaiadienone afforded a guaiadiene with the reported structure for aciphylle…