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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.