Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals

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  • J. Andrew P. Maitland
    Department of Chemistry Chemistry Research Laboratory University of Oxford 12 Mansfield Road Oxford OX1 3TA UK
  • Jamie A. Leitch
    Department of Chemistry Chemistry Research Laboratory University of Oxford 12 Mansfield Road Oxford OX1 3TA UK
  • Ken Yamazaki
    Department of Chemistry Chemistry Research Laboratory University of Oxford 12 Mansfield Road Oxford OX1 3TA UK
  • Kirsten E. Christensen
    Department of Chemistry Chemistry Research Laboratory University of Oxford 12 Mansfield Road Oxford OX1 3TA UK
  • Doyle J. Cassar
    Oncology R&D AstraZeneca Cambridge CB4 0WG UK
  • Trevor A. Hamlin
    Department of Theoretical Chemistry Amsterdam Institute of Molecular and Life Sciences (AIMMS) Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands
  • Darren J. Dixon
    Department of Chemistry Chemistry Research Laboratory University of Oxford 12 Mansfield Road Oxford OX1 3TA UK

Description

<jats:title>Abstract</jats:title><jats:p>A reagent‐controlled stereodivergent carbocyclisation of aryl aldimine‐derived, photocatalytically generated, α‐amino radicals possessing adjacent conjugated alkenes, affording either bicyclic or tetracyclic products, is described. Under net reductive conditions using commercial Hantzsch ester, the α‐amino radical species underwent a single stereoselective cyclisation to give trans‐configured amino‐indane structures in good yield, whereas using a substituted Hantzsch ester as a milder reductant afforded cis‐fused tetracyclic tetrahydroquinoline frameworks, resulting from two consecutive radical cyclisations. Judicious choice of the reaction conditions allowed libraries of both single and dual cyclisation products to be synthesised with high selectivity, notable predictability, and good‐to‐excellent yields. Computational analysis employing DFT revealed the reaction pathway and mechanistic rationale behind this finely balanced yet readily controlled photocatalytic system.</jats:p>

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