Asymmetric [4 + 3] Cycloadditions between Vinylcarbenoids and Dienes: Application to the Total Synthesis of the Natural Product (−)-5-epi-Vibsanin E
- 15 May 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 131 (23), 8329-8332
- https://doi.org/10.1021/ja9019484
Abstract
The total synthesis of (−)-5-epi-vibsanin E (2) has been achieved in 18 steps. The synthesis combines the rhodium-catalyzed [4 + 3] cycloaddition between a vinylcarbenoid and a diene to rapidly generate the tricyclic core with an effective end game strategy to introduce the remaining side-chains. The [4 + 3] cycloaddition occurs by a cyclopropanation to form a divinylcyclopropane followed by a Cope rearrangement to form a cycloheptadiene. The quaternary stereogenic center generated in the process can be obtained with high asymmetric induction when the reaction is catalyzed by the chiral dirhodium complex, Rh2(S-PTAD)4.Keywords
This publication has 34 references indexed in Scilit:
- End game strategies towards the total synthesis of vibsanin E, 3-hydroxyvibsanin E, furanovibsanin A, and 3-O-methylfuranovibsanin ABeilstein Journal of Organic Chemistry, 2008
- Enantioselective Total Synthesis of Guanacastepene N Using an Uncommon 7-Endo Heck Cyclization as a Pivotal StepJournal of the American Chemical Society, 2006
- Towards the Total Synthesis of Vibsanin E, 15‐O‐Methylcyclovibsanin B,3‐Hydroxyvibsanin E, Furanovibsanin A, and 3‐O‐Methylfuranovibsanin AEuropean Journal of Organic Chemistry, 2006
- Highly Enantio‐ and Diastereoselective Construction of 1,2‐Disubstituted Cyclopentane Compounds by Dirhodium(II) Tetrakis[N‐phthaloyl‐(S)‐tert‐leucinate]‐Catalyzed C-H Insertion Reactions of α‐Diazo EstersAdvanced Synthesis & Catalysis, 2005
- Total Synthesis of Guanacastepene A: A Route to Enantiomeric ControlThe Journal of Organic Chemistry, 2005
- A total synthesis of guanacastepene CChemical Communications, 2005
- Formal Synthesis of (±)-Guanacastepene AThe Journal of Organic Chemistry, 2003
- Tandem Asymmetric Cyclopropanation/Cope Rearrangement. A Highly Diastereoselective and Enantioselective Method for the Construction of 1,4-CycloheptadienesJournal of the American Chemical Society, 1998
- Dephosphorylating “Ylide Diketone”‐Rearrangement of the ArylcarbonyloxyalkylidenephosphoranesAngewandte Chemie-International Edition, 1983
- Synthesis and Properties ofN-[1-(Arylcarbonyloxy)alkyl]pyridinium SaltsAngewandte Chemie-International Edition, 1982