6533b859fe1ef96bd12b6ee4
RESEARCH PRODUCT
Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones
Juha H. SiitonenDániel CsókásPetri M. PihkoImre Pápaisubject
StemonaLetterisomeriaStereochemistrytransition states010402 general chemistry01 natural sciencesBiochemistryenolatesheterocyclic compoundsPhysical and Theoretical Chemistryorgaaniset yhdisteetkemialliset reaktiotbiology010405 organic chemistryChemistryorganic chemicalsOrganic ChemistryselectivityTotal synthesisMethylationbiology.organism_classification0104 chemical sciencesalkaloiditchemical structureorganic reactionsStereoselectivitydescription
A stereoselectivity model inspired by the total synthesis of stemona alkaloids is developed to explain why enolate-derived 3,4-fused butyrolactones are methylated with a preference for syn alkylation. The model shows how conformational locking present in nonplanar enolate structures favors syn over anti methylation, due to less significant structural distortions in the syn pathway. The developed model was also successfully used to rationalize selectivities of previously documented methylation reactions. peerReviewed
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2020-04-01 | Organic Letters |