Iron-Catalyzed Contrasteric Functionalization of Allenic C(sp2)-H Bonds: Synthesis of α-Aminoalkyl 1,1-Disubstituted Allenes

J Am Chem Soc. 2021 Sep 22;143(37):14998-15004. doi: 10.1021/jacs.1c07512. Epub 2021 Sep 7.

Abstract

An iron-catalyzed C-H functionalization of simple monosubstituted allenes is reported. An efficient protocol for this process was made possible by the use of a newly developed electron-rich and sterically hindered cationic cyclopentadienyliron dicarbonyl complex as the catalyst and N-sulfonyl hemiaminal ether reagents as precursors to iminium ion electrophiles. Under optimized conditions, the use of a mild, functional-group-tolerant base enabled the conversion of a range of monoalkyl allenes to their allenylic sulfonamido 1,1-disubstituted derivatives, a previously unreported and contrasteric regiochemical outcome for the C-H functionalization of electronically unbiased and directing-group-free allenes.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkadienes / chemical synthesis*
  • Alkadienes / chemistry
  • Catalysis
  • Hydrocarbons / chemical synthesis*
  • Hydrocarbons / chemistry
  • Hydrogen Bonding
  • Iron / chemistry*
  • Models, Molecular
  • Molecular Structure

Substances

  • Alkadienes
  • Hydrocarbons
  • Iron