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Title

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

Authors
Pescitelli, Gennaro
Zinna, Francesco
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Published in Angewandte Chemie. International edition in English. 2022, vol. 61, no. 41, e202210798
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.
Keywords CarbenesC−H InsertionHelicenesLate-Stage FunctionalizationPhotophysical Properties
Identifiers
PMID: 35943860
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Structures
Research groups Groupe Lacour
Groupe Poblador Bahamonde
Project
European Commission: HEL4CHIROLED
Citation
(ISO format)
NIKOLOVA, Yana et al. Chemo‐ and Regioselective Multiple C(sp2)−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 https://archive-ouverte.unige.ch/unige:164073

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Deposited on : 2022-10-10

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