Formation of Aminocyclopentadienes from Silyldihydropyridines: Ring Contractions Driven by Anion Stabilization

Morgan M Walker; Shuming Chen; Brandon Q Mercado; K N Houk; Jonathan A Ellman

doi:10.1002/anie.201800596

Formation of Aminocyclopentadienes from Silyldihydropyridines: Ring Contractions Driven by Anion Stabilization

Angew Chem Int Ed Engl. 2018 May 28;57(22):6605-6609. doi: 10.1002/anie.201800596. Epub 2018 Apr 26.

Authors

Morgan M Walker¹, Shuming Chen², Brandon Q Mercado¹, K N Houk², Jonathan A Ellman¹

Affiliations

¹ Department of Chemistry, Yale University, 225 Prospect St., New Haven, CT, 06520, USA.
² Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095-1569, USA.

Abstract

Highly functionalized aminocyclopentadienes can be formed through the rearrangement of anions generated from readily prepared 6-silyl-1,2-dihydropyridines by desilylation with fluoride. The scope and generality of the reaction was defined, and diverse transformations were performed on the highly functionalized products. A mechanism and driving force for the rearrangement were identified from experiments and DFT calculations.

Keywords: amines; density functional calculations; reaction mechanisms; rearrangement; ring contraction.

Publication types

Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Anions / chemistry
Cyclopentanes / chemical synthesis*
Cyclopentanes / chemistry
Density Functional Theory
Dihydropyridines / chemistry*

Substances

Anions
Cyclopentanes
Dihydropyridines

Grants and funding

R35 GM122473/GM/NIGMS NIH HHS/United States