Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones

Csókás, Dániel; Siitonen, Juha H.; Pihko, Petri M.; Pápai, Imre

doi:10.1021/acs.orglett.0c01008

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Csókás, D., Siitonen, J. H., Pihko, P. M., & Pápai, I. (2020). Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones. Organic Letters, 22(12), 4597-4601. https://doi.org/10.1021/acs.orglett.0c01008

Julkaistu sarjassa

Organic Letters

Tekijät

Csókás, Dániel |

Siitonen, Juha H. |

Pihko, Petri M. |

Pápai, Imre

Päivämäärä

2020

Oppiaine

Orgaaninen kemia Organic Chemistry

Tekijänoikeudet

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.

Julkaisija

American Chemical Society

ISSN Hae Julkaisufoorumista

1523-7060

Lisätietoja rahoituksesta

Financial support from the Academy of Finland (project #259532), Jenny and Artturi Wihuri Foundation (research grant to J.H.S.), University of Jyväskylä (postgraduate fellowship to J.H.S), and NKFIH Hungary (grant K-112028) is gratefully acknowledged.

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