A retro-Claisen approach to dolabriferol.

Org Lett

School of Chemistry, Physics and Earth Sciences, Flinders University, G. P. O. Box 2100, S.A. 5001, Australia.

Published: April 2006


Category Ranking

98%

Total Visits

921

Avg Visit Duration

2 minutes

Citations

20

Article Abstract

[reaction: see text] The protected precursor 30 to dolabriferol was generated by a DBU-induced, ester-forming, retro-Claisen process. The required linear carbon chain present in 22 was synthesized by a stereoselective lithium aldol reaction. The necessary aldehyde and ketone fragments were synthesized using stereocontrolled aldol reactions with the ethyl (S)-lactate derived ketone 13.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ol060347sDOI Listing

Publication Analysis

Top Keywords

retro-claisen approach
4
approach dolabriferol
4
dolabriferol [reaction
4
[reaction text]
4
text] protected
4
protected precursor
4
precursor dolabriferol
4
dolabriferol generated
4
generated dbu-induced
4
dbu-induced ester-forming
4

Similar Publications

Article Synopsis
  • * The study reveals new methods for processing methyl groups in terpenoids, through a combination of silylation and oxidation, leading to various transformations such as substitution and integration of the methyl carbon.
  • * These processes not only allow for the creation of novel chemical structures with expanded rings but also show potential applications in medicinal chemistry by adding functional groups to complex compounds.
View Article and Find Full Text PDF

Volatile lanthanide coordination complexes are critical to the generation of new optical and magnetic materials. One of the most common precursors for preparing volatile lanthanide complexes is the hydrate with the general formula Ln(hfac)(HO) ( = 3 for La-Nd, = 2 for Sm) (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato). We have investigated the synthesis of Ln(hfac)(HO) using more environmentally sustainable mechanochemical approaches.

View Article and Find Full Text PDF

An IBX/NIS-induced intramolecular oxidative annulation of Mannich-type substrates is reported. This metal-free approach involving iodination, NH-oxidation, intramolecular C-N bond formation, and retro-Claisen-Schmidt sequence provides the construction of imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine as well as imidazo[1,2-a]pyrazine frameworks with yields up to 93%. In addition, a sequential one-pot process is also presented.

View Article and Find Full Text PDF
Article Synopsis
  • A new method for creating benzene structures without using transition metals involves self-condensation of enaminodiones.
  • This process yields functionalized acyl-substituted phenols and catechols in 29-97% yields while maintaining high chemoselectivity and mild conditions.
  • The reaction is a base-promoted [4+2] annulation that includes forming cyclohexanones and undergoing multiple transformations, including double Michael addition and aromatization.
View Article and Find Full Text PDF

In the course of a total synthesis effort directed toward the natural product curcusone C, the Stoltz group discovered an unexpected thermal rearrangement of a divinylcyclopropane to the product of a formal Cope/1,3-sigmatropic shift sequence. Since the involvement of a thermally forbidden 1,3-shift seemed unlikely, theoretical studies involving two approaches, the "trial-and-error" testing of various conceivable mechanisms (Houk group) and an "automatic" approach using the Maeda-Morokuma AFIR method (Morokuma group) were applied to explore the mechanism. Eventually, both approaches converged on a cascade mechanism shown to have some partial literature precedent: Cope rearrangement/1,5-sigmatropic silyl shift/Claisen rearrangement/retro-Claisen rearrangement/1,5-sigmatropic silyl shift, comprising a quintet of five sequential thermally allowed pericyclic rearrangements.

View Article and Find Full Text PDF