Regio- and Stereoselectivity of β-Himachalene Epoxidation by <i>m</i>-CPBA. A Theoretical Study

Chekroun, Ahmed; Jarid, Abdellah; Benharref, A.; Boutalib, Abderrahim

doi:10.1021/jo991848c

Cited by 35 publications

(33 citation statements)

References 25 publications

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“…33 Performing the epoxidation of 7a but with 1 equiv of m-CPBA at ambient temperature yielded the same mixture of mono-epoxides (13a and 13b) in a 35:65 ratio, along with the bis-epoxides (14a− 14d) (Scheme 1). Addition of excess oxidant furnished the two pairs of bis-epoxides (14a/14b and 14c/14d) in a ratio of 36:64, consistent with that found for mono-epoxide formation and merely reflects that the more electron-rich bridged CC is epoxidized at a much faster rate than the external isopropylene unit (Scheme 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-epi-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol

et al. 2014

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The diastereomeric ratio of epoxidation of the internally bridged carbon-carbon double bond of guaiol (1a) is strongly influenced by the combined effects of the types of remote protecting groups on the hydroxyisopropyl side chain, choice of solvent, and epoxidizing reagent. This observation has allowed us to devise concise stereoselective syntheses of a range of guaiane-type sesquiterpenoids via an epoxidation, ring-opening/elimination, and functionality manipulation sequence. Natural products guaia-4(5)-en-11-ol (2a), guaia-5(6)-en-11-ol (3), and aciphyllene (4a) and epimers of the recently isolated natural products, 1-epi-guaia-4(5)-en-11-ol (2b), 1-epi-aciphyllene (4b), and 1-epi-melicodenones C (5a) and E (6a), were synthesized in good yields in relatively few steps.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-epi-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol

et al. 2014

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“…For the reactivity of this sesquiterpene, see: Lassaba et al (1997); Chekroun et al (2000); El ; Sbai et al (2002); Dakir et al (2004). For its biological activity, see: Daoubi et al (2004).…”

Section: Related Literaturementioning

confidence: 99%

(1S,3R,8R)-2,2-Dibromo-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-9-ene

Benharref¹,

Ammari²,

Lassaba³

et al. 2012

Acta Cryst E

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The title compound, C16H24Br2, was synthesized from β-himachalene (3,5,5,9-tetramethyl-2,4a,5,6,7,8-hexahydro-1H-benzocycloheptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The molecule is built up from two fused six- and seven-membered rings and an additional three-membered ring from the reaction of β-himachalene with dibromocarbene. The six-membered ring shows a screw-boat conformation, whereas the seven-membered ring displays a boat conformation; the dihedral angle between the mean planes through the rings is 57.9 (4)°. The absolute structure was established unambiguously from anomalous dispersion effects.

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“…For the reactivity of this sesquiterpene, see: Lassaba et al (1998); Chekroun et al (2000); El ; Sbai et al (2002); Dakir et al (2004). For its biological activity, see: Daoubi et al (2004).…”

Section: Related Literaturementioning

confidence: 99%

“…The reactivity of this sesquiterpene has been studied extensively by our team in order to prepare new products having biological proprieties (Lassaba et al, 1998;Chekroun et al, 2000;El Jamili et al, 2002;Sbai et al, 2002;Dakir et al, 2004). Indeed, these compounds were tested, using the food poisoning technique, for their potential antifungal activity against phytopathogen Botrytis cinerea (Daoubi et al, 2004).…”

Section: Commentmentioning

confidence: 99%

(1S,2R,8R)-2,2-Dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-10-en-9-one

Benharref¹,

Ammari²,

Berraho³

2010

Acta Cryst E

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The title compound, C16H22Cl2O, was synthesized from β-himachalene, which was isolated from essential oil of the Atlas cedar (cedrus atlantica). The asymmetric unit contains two independent molecules, in each of which the six-membered ring shows a half-chair conformation, whereas the seven-membered ring displays a boat conformation. The dihedral angle between the two rings is slightly different in the two molecules [63.22 (13) and 61.81 (14)°].

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Regio- and Stereoselectivity of β-Himachalene Epoxidation by m-CPBA. A Theoretical Study

Cited by 35 publications

References 25 publications

Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-epi-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol

Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-epi-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol

(1S,3R,8R)-2,2-Dibromo-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-9-ene

(1S,2R,8R)-2,2-Dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-10-en-9-one

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Regio- and Stereoselectivity of β-Himachalene Epoxidation by m-CPBA. A Theoretical Study

Cited by 35 publications

References 25 publications

Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-epi-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol

Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-epi-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol

(1S,3R,8R)-2,2-Dibromo-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodec-9-ene

(1S,2R,8R)-2,2-Dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodec-10-en-9-one

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(1S,3R,8R)-2,2-Dibromo-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-9-ene

(1S,2R,8R)-2,2-Dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.0^1,3]dodec-10-en-9-one