Chiral quinacridines react up to four times, step-by-step, with alpha-diazomalonates under Ru-II and Rh-II catalysis. By selecting the catalyst, [CpRu(CH3CN)(3)][PF6] (Cp=cyclopentadienyl) or Rh-2(oct)(4), chemo and regioselective insertions of derived metal carbenes are achieved in favor of mono- or bis-functionalized malonate derivatives, respectively, (r.r.>49 : 1, up to 77 % yield, 12 examples). This multi-introduction of malonate groups is particularly useful to tune optical and chemical properties such as absorption, emission or Bronsted acidity but also cellular bioimaging. Density-functional theory further elucidates the origin of the carbene insertion selectivity and also showcases the importance of conformations in the optical response.

Chemo- and Regioselective Multiple C(sp2 )-H Insertions of Malonate Metal Carbenes for Late-Stage Functionalizations of Azahelicenes

Pescitelli, Gennaro;Zinna, Francesco;Di Bari, Lorenzo;Lacour, Jérôme
2022-01-01

Abstract

Chiral quinacridines react up to four times, step-by-step, with alpha-diazomalonates under Ru-II and Rh-II catalysis. By selecting the catalyst, [CpRu(CH3CN)(3)][PF6] (Cp=cyclopentadienyl) or Rh-2(oct)(4), chemo and regioselective insertions of derived metal carbenes are achieved in favor of mono- or bis-functionalized malonate derivatives, respectively, (r.r.>49 : 1, up to 77 % yield, 12 examples). This multi-introduction of malonate groups is particularly useful to tune optical and chemical properties such as absorption, emission or Bronsted acidity but also cellular bioimaging. Density-functional theory further elucidates the origin of the carbene insertion selectivity and also showcases the importance of conformations in the optical response.
2022
Nikolova, Yana; Fabri, Bibiana; Moneva Lorente, Pau; Guarnieri-Ibáñez, Alejandro; de Aguirre, Adiran; Soda, Yoshiki; Pescitelli, Gennaro; Zinna, Franc...espandi
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/1156343
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