Dearomative cycloaddition reaction serves as a blueprint for creating sp3-rich three-dimensional molecular topology from flat-aromatic compounds. However, severe reactivity and selectivity issues make this process arduous. Herein, we describe visible-light...
A facile synthesis of mono-, 1,1-and 1,2disubstituted cyclopropanes via visible light-mediated photoredox/nickel dual catalysis is demonstrated. The challenging intramolecular C(sp 3 )−C(sp 3 ) cross-electrophile coupling of readily available unactivated 1,3-dialkyl electrophiles was performed under mild conditions that allowed traditionally reactive functional groups to be included. Mechanistic inspection and control experiments revealed the importance of dual catalysis and that the reaction proceeds via a stepwise oxidative addition followed by an intramolecular S N 2 reaction.
Dearomative cycloaddition reaction serves as a blueprint for creating three-dimensional molecular topology from flat-aromatic compounds. However, severe reactivity and selectivity issues make this process challenging. Herein, we describe visible-light energy-transfer catalysis for the intermolecular dearomative [4+2] cycloaddition reaction of feed-stock naphthalene molecules with vinyl benzenes. Tolerating a wide range of functional groups, a variety of structurally diverse 2-acyl naphthalenes and styrenes could easily be converted to a diverse range of bicyclo[2.2.2]octa-2,5-diene scaffolds in high yields and selectivities. The late-stage modification of pharmaceutical agents further demonstrated the broad potentiality of this methodology. The efficacy of the introduced methods was further highlighted by the post-synthetic diversification of the products. Furthermore, photoluminescence, electrochemical, kinetic, and control experiments support the energy transfer catalysis
1,2-Dicarbofunctionalization of unactivated olefin has
been reported
under photoredox/nickel dual catalysis. The mildness of the visible-light-mediated
reaction allows the use of various alkyl and aryl electrophiles with
several sensitive functional groups. The protocol was equally applied
for late-stage diversification of drugs and biologically active molecules.
Investigations elucidated the importance of photoredox/nickel dual
catalysis and α-amino-radical-mediated halogen atom transfer
and provided us with the nickel complexes involved in the reaction.
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