A synthetic sequence is described for construction of the tricyclic portion (35) of kempane diterpenes. The central stereochemistry was established by a Diels-Alder addition of 2,6-dimethyl-para-benzoquinone to a 5-membered, dithiane-protected diene, and the addition of acetylide, with very high chemoselectivity, provided a suitably functionalized handle that will be incorporated into the final seven-membered ring. The remaining stereogenic centres about the decalin moiety were established by a series of equilibration and reduction steps.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/b509777k | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Enantioselective Total Synthesis of 3β-Hydroxy-7β-kemp-8(9)-en-6-one, a Diterpene Isolated from Higher Termites.
Angew Chem Int Ed Engl
December 2017
Fachrichtung Chemie und Lebensmittelchemie, Organische Chemie I, Technische Universität Dresden, Bergstrasse 66, 01069, Dresden, Germany.
The first total synthesis of the title diterpene was accomplished starting from the Wieland-Miescher ketone. A diastereoselective sulfa-Michael addition enabled the generation of the delicate β,γ-unsaturated ketone moiety, while the tetracyclic kempane skeleton was readily constructed through domino metathesis.
View Article and Find Full Text PDFInvestigations into an anionic oxy-cope/transannular conjugate addition approach to 7,20-diisocyanoadociane.
Org Lett
September 2014
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697-2025, United States.
An anionic oxy-Cope/transannular conjugate addition approach to the potent antimalarial 7,20-diisocyanoadociane is presented. The unexpected formation of undesired diastereomers in the key reaction led to the structural reassignment of previous products of this type of cascade and a reevaluation of the reversibility of the transannular ring closure. During efforts to coax the reaction toward the desired product, a transannular ene reaction provided tricyclic compounds relevant to the kempane diterpenoids.
View Article and Find Full Text PDFSynthetic approach toward the total synthesis of kempane diterpenes via transannular Diels-Alder strategy.
J Org Chem
September 2006
Laboratoire de Synthèse Organique, Département de Chimie, Institut de Pharmacologie, Université de Sherbrooke, Sherbrooke, Québec J1H 5N4, Canada.
Total syntheses of two new (+/-)-kempane derivatives 30 and 47 were achieved with transannular Diels-Alder reaction (TADA) serving as the key step for the stereoselective formation of tricyclic [6.6.5] system 3.
View Article and Find Full Text PDFSynthesis of the tetracyclic core of the kempanes by a ring-closing metathesis strategy.
Org Lett
January 2006
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada.
[reaction: see text] The synthesis of the tetracyclic ring system of the kempane diterpenes was achieved through the highly regio- and stereoselective Diels-Alder reaction of an isopropenyl-diene with 2,6-dimethyl-p-benzoquinone, addition of an allyl group, and ring-closing metathesis of the isopropenyl and allyl groups.
View Article and Find Full Text PDFSynthetic studies toward the kempane diterpenes. Construction of a key tricyclic intermediate.
Org Biomol Chem
October 2005
Department of Chemistry, Memorial University of Newfoundland, St. John's, Newfoundland and Labrador, Canada A1B 3X7.
A synthetic sequence is described for construction of the tricyclic portion (35) of kempane diterpenes. The central stereochemistry was established by a Diels-Alder addition of 2,6-dimethyl-para-benzoquinone to a 5-membered, dithiane-protected diene, and the addition of acetylide, with very high chemoselectivity, provided a suitably functionalized handle that will be incorporated into the final seven-membered ring. The remaining stereogenic centres about the decalin moiety were established by a series of equilibration and reduction steps.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!