A total synthesis of the styryllactone (+)-goniodiol from naphthalene.
Author(s)
Banwell, MG
Coster, MJ
Edwards, AJ
Karunaratne, OP
Smith, JA
Welling, LL
Willis, AC
Griffith University Author(s)
Year published
2003
Metadata
Show full item recordAbstract
The cytotoxic natural product (+)-goniodiol was prepd. in twelve steps from enantiomerically pure cis-dihydrocatechol, which is readily obtained by microbial oxidn. of naphthalene. Elaboration of the cis-dihydrocatechol involves an initial oxidative cleavage to dialdehyde followed by redn. to give a diol. Conversion of the diol into an acetal required, inter alia, selective oxidn. of the benzylic alc. moiety followed by a metal-catalyzed decarbonylation of the resulting aldehyde. Allylation of I with allyltributylstannane in the presence of lithium perchlorate gave a ca. 2.7:1 mixt. of alcs., each of which was converted ...
View more >The cytotoxic natural product (+)-goniodiol was prepd. in twelve steps from enantiomerically pure cis-dihydrocatechol, which is readily obtained by microbial oxidn. of naphthalene. Elaboration of the cis-dihydrocatechol involves an initial oxidative cleavage to dialdehyde followed by redn. to give a diol. Conversion of the diol into an acetal required, inter alia, selective oxidn. of the benzylic alc. moiety followed by a metal-catalyzed decarbonylation of the resulting aldehyde. Allylation of I with allyltributylstannane in the presence of lithium perchlorate gave a ca. 2.7:1 mixt. of alcs., each of which was converted into the corresponding acrylate under std. conditions. Subjection of these ester derivs. to a ring-closing metathesis (RCM) reaction with Grubbs' first-generation catalyst gave the anticipated lactone II and its diastereomer. Acid-catalyzed removal of the acetonide protecting group within II then afforded (+)-goniodiol, while analogous deprotection of the congener afforded 6-epi-(+)-goniodiol.
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View more >The cytotoxic natural product (+)-goniodiol was prepd. in twelve steps from enantiomerically pure cis-dihydrocatechol, which is readily obtained by microbial oxidn. of naphthalene. Elaboration of the cis-dihydrocatechol involves an initial oxidative cleavage to dialdehyde followed by redn. to give a diol. Conversion of the diol into an acetal required, inter alia, selective oxidn. of the benzylic alc. moiety followed by a metal-catalyzed decarbonylation of the resulting aldehyde. Allylation of I with allyltributylstannane in the presence of lithium perchlorate gave a ca. 2.7:1 mixt. of alcs., each of which was converted into the corresponding acrylate under std. conditions. Subjection of these ester derivs. to a ring-closing metathesis (RCM) reaction with Grubbs' first-generation catalyst gave the anticipated lactone II and its diastereomer. Acid-catalyzed removal of the acetonide protecting group within II then afforded (+)-goniodiol, while analogous deprotection of the congener afforded 6-epi-(+)-goniodiol.
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Journal Title
Australian Journal of Chemistry
Volume
56
Issue
6
Subject
Chemical sciences