Carbolithiation of chloro-substituted alkynes: a new access to vinyl carbenoids.

Chemistry

Laboratoire COBRA, CNRS UMR 6014 & FR 3038, Univ. Rouen, INSA Rouen, 76821 Mt St Aignan Cedex (France).

Published: August 2014

AI Article Synopsis

  • The study explores how chloro-substituted alkynes undergo intramolecular carbolithiation to form exocyclic alkylidene carbenoids, which exhibit both nucleophilic and electrophilic properties.
  • A specific stereoselective reaction known as 5-exo-dig addition is the primary outcome, suggesting a preference in the formation process.
  • This selectivity is likely influenced by a significant interaction between lithium and chlorine that occurs prior to reaching the transition state.

Article Abstract

The intramolecular carbolithiation of a series of chloro-substituted alkynes leads to exocyclic alkylidene carbenoids of which both nucleophilic and electrophilic characters can be drove. A sole stereoselective 5-exo-dig addition takes place, probably because of a strong and persisting Li-Cl interaction arising before the transition state.

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Source
http://dx.doi.org/10.1002/chem.201403605DOI Listing

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