Enantioselective Synthesis of Fused Cycloheptadienes by a Tandem Intramolecular Cyclopropanation/Cope Rearrangement Sequence
The Journal of Organic Chemistry1999Vol. 64(23), pp. 8501–8508
Citations Over TimeTop 10% of 1999 papers
Abstract
The asymmetric induction in the intramolecular cyclopropanations of allyl vinyldiazoacetates catalyzed by tetrakis[N-[4-dodecylphenyl)sulfonyl]-(S)-prolinato]dirhodium [Rh2(S-DOSP)4] is very dependent on the allyl substitution pattern. The reactions of cis-alkenes result in much higher asymmetric induction than trans-alkenes while the highest enantioselectivity was obtained with a disubstituted terminal alkene. The intramolecular cyclopropanation of dienylmethyl vinyldiazoacetates results in the synthesis of fused cycloheptadiene ring systems with full control of relative stereochemistry and variable enantioselectivity. The synthetic utility of this process was demonstrated by a short synthesis of 5-epi-tremulenolide in 93% ee.
Related Papers
- → A Simple Organocatalytic Enantioselective Cyclopropanation of α,β‐Unsaturated Aldehydes(2007)195 cited
- → An enantioselective approach to (−)-platencin via catalytic asymmetric intramolecular cyclopropanation(2010)36 cited
- → Asymmetric synthesis of the tremulane skeleton by a tandem cyclopropanation/cope rearrangement(1996)50 cited
- → Gold-Catalyzed Addition of Propargyl Acetates to Olefins via O-Acyl Migration/Cyclopropanation Sequence: Insight into the Diastereoselective Formation of the Alkene(2023)6 cited
- → ChemInform Abstract: Expedient Synthesis of Fused Azepine Derivatives Using a Sequential Rhodium(II)‐Catalyzed Cyclopropanation/1‐Aza‐Cope Rearrangement of Dienyltriazoles.(2015)