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Olefin Amine (OLA) Reagents for the Synthesis of Bridged Bicyclic and Spirocyclic Saturated N-Heterocycles by Catalytic Hydrogen Atom Transfer (HAT) Reactions.
Journal article

Olefin Amine (OLA) Reagents for the Synthesis of Bridged Bicyclic and Spirocyclic Saturated N-Heterocycles by Catalytic Hydrogen Atom Transfer (HAT) Reactions.

  • Wang YY Laboratorium für Organische Chemie, Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir Prelog Weg 3 , Zürich 8093 , Switzerland.
  • Bode JW Laboratorium für Organische Chemie, Department of Chemistry and Applied Biosciences , ETH Zürich , Vladimir Prelog Weg 3 , Zürich 8093 , Switzerland.
  • 2019-05-24
Published in:
  • Journal of the American Chemical Society. - 2019
Colloid and Surface Chemistry
Biochemistry
General Chemistry
Catalysis
English Spiro- and bridged bicyclic structures are in demand for their sp3-rich frameworks that offer unique physiochemical properties and precisely positioned substituent groups. In order to rapidly access such molecules in a cross-coupling fashion we describe olefin amine (OLA) reagents for the transformation of aldehydes and ketones into all three topological types of bicyclic N-heterocycles: bridged, spiro-, and fused rings. The OLA reagents are easily prepared and allow the synthesis of complex molecular frameworks under operationally simple conditions that tolerate a wide array of functional groups. Investigations into the Mn or Fe promoted reaction pathway support a metal hydride hydrogen atom transfer (MH-HAT) to generate a C-centered radical that undergoes addition to an unactivated imine, leading to an N-centered radical. A catalytic cycle featuring regeneration of the metal catalyst by O2 and a second HAT to form the unprotected saturated N-heterocycle appears to be operative.
Language
  • English
Open access status
closed
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Persistent URL
https://sonar.ch/global/documents/283454
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