Title

Metalated nitriles: SNi′ cyclizations with a propargylic electrophile

Citation for published article

Lu, P., Pakkala, V. S., Evanseck, J. D., & Fleming, F. F. (2015). Metalated nitriles: SN cyclizations with a propargylic electrophile. Tetrahedron Letters, 56(23), 3216–3219. https://doi.org/10.1016/j.tetlet.2015.01.013

DOI

10.1016/j.tetlet.2015.01.013

Document Type

Journal Article

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.

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