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Dehydroborylation of Terminal Alkynes Using Lithium Aminoborohydrides
P Veeraraghavan Ramachandran1, Henry J Hamann1
1Herbert C. Brown Center for Borane Research, Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907, USA.
Abstract:
Dehydrogenative borylation of terminal alkynes has recently emerged as an atom-economical one-step alternative to traditional alkyne borylation methodologies. Using lithium aminoborohydrides, formed in situ from the corresponding amine-boranes and n-butyllithium, a variety of aromatic and aliphatic terminal alkyne substrates were successfully borylated in high yield. The potential to form mono-, di-, and tri-B-alkynylated products has been shown, though the mono-product is primarily generated using the presented condition. The reaction has been demonstrated at large (up to 50 mmol) scale, and the products are stable to column chromatography as well as acidic and basic aqueous conditions. Alternately, the dehydroborylation can be achieved by treating alkynyllithiums with amine-boranes. In that respect, aldehydes can act as starting materials by conversion to the 1,1-dibromoolefin and in situ rearrangement to the lithium acetylide.
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