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

Article Article scientifique Article Chemo‐ and Regioselective Multiple C(sp2)−H Insertions of Malonate Metal Carbenes for Late‐Stage Functionalizations of Azahelicenes eng 2022-08-09 2022-10-10 author Nikolova Yana 934861 author Fabri Bibiana 0000-0003-3466-3120 947651 author Moneva Lorente Pau 805360 author Guarnieri Ibanez Alejandro José 777995 author de Aguirre Adiran 935526 author Soda Yoshiki 0000-0003-2288-4778 904281 author Pescitelli Gennaro author Zinna Francesco author Besnard Céline 682138 author Guenee Laure 115015 author Moreau Dimitri 751508 author Di Bari Lorenzo author Bakker Eric 716236 author Poblador Bahamonde Amalia Isabel 797442 author Lacour Jérôme 0000-0001-6247-8059 99165 e202210798 10.1002/anie.202210798 35943860 0570-0833 https://onlinelibrary.wiley.com/doi/10.1002/anie.202210798 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. Carbenes C−H Insertion Helicenes Late-Stage Functionalization Photophysical Properties Dewey 540 European Commission Helical systems for chiral organic light emitting diodes 859752 HEL4CHIROLED EU H2020 36 Département de chimie organique 141 40 Département de chimie minérale, analytique et appliquée 145 39 Département de biochimie 144 false 760 Groupe Lacour 1055 Groupe Poblador Bahamonde https://doi.org/10.26037/yareta:py3o7ztvrnfdtcatka6yfrz27e Angewandte Chemie. International edition in English 61 41 bafd8176-fd05-4b2e-a683-f872db3ee864 Article (Published version) Public file.pdf 6286912 application/pdf Vignette Public anie202210798-toc-0001-m.jpg 95905 image/jpeg openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée Faculté des sciences / Section de chimie et biochimie / Département de biochimie

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Chemo‐ and Regioselective Multiple C(sp²)−H Insertions of Malonate Metal Carbenes for Late‐Stage Functionalizations of Azahelicenes	Angewandte Chemie. International edition in English			2022	246	172

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Nikolova, Yana