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Metalated nitriles: SNi' cyclizations with a propargylic electrophile.


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.

SUBMITTER: Lu P 

PROVIDER: S-EPMC4480775 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature

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Metalated nitriles: S<sub>N</sub>i' cyclizations with a propargylic electrophile.

Lu Ping P   Pakkala Venkata S VS   Evanseck Jeffrey D JD   Fleming Fraser F FF  

Tetrahedron letters 20150601 23


A rare 5-exo-dig S<sub>N</sub>i' cyclization with magnesiated and lithiated nitriles affords a <i>cis-</i>fused hydrindane bearing an exocyclic allene. The cyclization of the dilithiated nitrile pits a stereoelectronic preference for a <i>trans-</i>hydrindane against a cyclization through a less strained transition structure to the corresponding <i>cis</i>-hydrindane. Computational modeling suggests that the dilithiated nitrile cyclizes to a <i>cis-</i>hydrindane because the preferred transition  ...[more]

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