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

Published inAngewandte Chemie. International edition in English, vol. 61, no. 41, e202210798
Publication date2022-10-10
First online date2022-08-09
Abstract

Chiral quinacridines react up to four times, step-by-step, with α-diazomalonates under RuII and RhII catalysis. By selecting the catalyst, [CpRu(CH3CN)3][PF6] (Cp=cyclopentadienyl) or Rh2(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 Brønsted 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.

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Keywords
  • Carbenes
  • C−H Insertion
  • Helicenes
  • Late-Stage Functionalization
  • Photophysical Properties
Funding
  • European Commission - Helical systems for chiral organic light emitting diodes [859752]
Citation (ISO format)
NIKOLOVA, Yana et al. Chemo‐ and Regioselective Multiple C(sp<sup>2</sup>)−H Insertions of Malonate Metal Carbenes for Late‐Stage Functionalizations of Azahelicenes. In: Angewandte Chemie. International edition in English, 2022, vol. 61, n° 41, p. e202210798. doi: 10.1002/anie.202210798
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Article (Published version)
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ISSN of the journal0570-0833
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Technical informations

Creation10/06/2022 7:27:00 AM
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