Metalated nitriles: S_Ni′ cyclizations with a propargylic electrophile

Citation for published article

Coupled Hemodynamics and Oxygen Diffusion in Abdominal Aortic Aneurysm: A Computational Sensitivity Study

DOI

10.1016/j.tetlet.2015.01.013

Authors

Ping Lu, Duquesne University
Venkata S. Pakkala, Duquesne University
Jeffrey D. Evanseck, Duquesne University
Fraser F. Fleming, Duquesne University

Document Type

Journal Article

Publication Date

5-25-2015

Publication Title

Tetrahedron Letters

Keywords

5-exo-Dig, Hydrindane, Metalated nitriles, S i′ cyclization N

School

Bayer School of Natural and Environmental Sciences

Abstract

© 2015. Abstract A rare 5-exo-dig SNi′ cyclization with magnesiated and lithiated nitriles affords a cis-fused hydrindane bearing an exocyclic allene. The cyclization of the dilithiated nitrile pits a stereoelectronic preference for a trans-hydrindane against a cyclization through a less strained transition structure to the corresponding cis-hydrindane. Computational modeling suggests that the dilithiated nitrile cyclizes to a cis-hydrindane because the preferred transition structure positions the lithium cation in a cone of electron density that bridges the nitrile-bearing carbon, an alkoxide, and an electron-rich alkyne functionality.

Repository Citation

Lu, P., Pakkala, V., Evanseck, J., & Fleming, F. (2015). Metalated nitriles: S_Ni′ cyclizations with a propargylic electrophile. Tetrahedron Letters. https://doi.org/10.1016/j.tetlet.2015.01.013