Linked Life Data

10866628

Source:http://linkedlifedata.com/resource/pubmed/id/10866628

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
13
pubmed:dateCreated
2000-8-31
pubmed:abstractText
The treatment of 4-[(5E)-6-methoxycarbonyl-5-hexenyl]-3, 4-dimethyl-2-cyclopenten-1-one (5) with LHMDS, TMSI-HMDS, Bu(2)OTf-HMDS, or TMSCl-NEt(3)-ZnCl(2) caused the intramolecular double Michael addition to afford tricyclo[6.3.0.0(3, 9)]undecan-10-one 12 in high yields with perfect stereoselectivity. The methodology was further elaborated to achieve efficient total syntheses of (+/-)-culmorin (1) and (+/-)-longiborneol (2). The common precursor 13 of them was obtained from 14 in 94% yield as a single isomer by the treatment with LHMDS. After the conversion of 13 into the corresponding acid 24 by hydrolysis, oxidative decarboxylation using S-(1-oxido-2-pyridinyl)-1,1,3, 3-tetramethylthiouronium hexafluorophosphate (HOTT, 27), followed by the Birch reduction, stereoselectively afforded (+/-)-culmorin (1). (+/-)-Longiborneol (2) was synthesized from 24 by the standard transformation. Additionally, the treatment of 24 with Pb(OAc)(4) led to 28 via uncommon migration. Its structure was determined by X-ray analysis after the transformation into the diketone 29.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Jun
pubmed:issn
0022-3263
pubmed:author
pubmed:issnType
Print
pubmed:day
30
pubmed:volume
65
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
4112-9
pubmed:dateRevised
2006-11-15
pubmed:meshHeading
pubmed:year
2000
pubmed:articleTitle
Total synthesis of (+/-)-culmorin and (+/-)-longiborneol: an efficient construction of Tricyclo[6.3.0.0(3,9)]undecan-10-one by intramolecular double Michael addition.
pubmed:affiliation
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, Sendai 980-8578, Japan.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't