Abstract
Charged molecules and intermediates display unique reactivity and properties. In this context, studies on original cationic [4] and [6]helicenes will be presented. These compounds display original chemical and electronic properties thanks to the extended delocalization provided by the triarylcarbenium framework.[1] Molecular engineering towards novel reactivities and properties, electronic and chiroptical in particular, will be reported.[2]
Also, a focus will be given on metal-catalyzed decompositions of -diazocarbonyls – and those involving CpRu complexes [3] particular. An attention will be given to routes affording ylide intermediates and then functionally rich heterocyclic derivatives. A large variety of stereoselective and enantiospecific transformations are available through these metal carbene reactions and subsequent ylide transformations. Mechanistic investigations will be detailed during the lecture.
References
[1] J. Bosson, N. Bisballe, B. W. Laursen, J. Lacour, in Helicenes. Synthesis, Properties and Applications (Eds.: J. Crassous, I. G. Stara, I. Stary), Wiley-VCH, 2022, pp. 127-165.
[2] a) B. Fabri, D. F. De Rosa, D. J. Black, R. Mucci, A. Krimovs, R. Pal, J. Lacour, Chem. Eur. J. 2025, 31, e202501212; b) S. G. Stenspil, A. H. Olsson, R. Mucci, M. Pink, C. Besnard, G. Pescitelli, J. Lacour, A. H. Flood, B. W. Laursen, Angew .Chem. Int. Ed. 2024, e202412320; c) B. Fabri, T. Funaioli, L. Frédéric, C. Elsner, E. Bordignon, F. Zinna, L. Di Bari, G. Pescitelli, J. Lacour, J. Am. Chem. Soc. 2024, 146, 8308–8319; d) R. Tarrieu, I. Hernández Delgado, F. Zinna, V. Dorcet, S. Colombel-Rouen, C. Crévisy, O. Baslé, J. Bosson, J. Lacour, Chem. Commun. 2021, 75, 3793-3796; e) J. Bosson, G. M. Labrador, C. Besnard, D. Jacquemin, J. Lacour, Angew. Chem. Int. Ed. 2021, 60, 8733-8738; f) H. Li, R. Duwald, S. Pascal, S. Voci, C. Besnard, J. Bosson, L. Bouffier, J. Lacour, N. Sojic, Chem. Commun. 2020, 56, 9771-9774; g) R. Duwald, J. Bosson, S. Pascal, S. Grass, F. Zinna, C. Besnard, L. Di Bari, D. Jacquemin, J. Lacour, Chem. Sci. 2020, 11, 1165-1169.
[3] a) O. Viudes, C. Besnard, A. F. Siegle, O. Trapp, T. Bürgi, G. Pescitelli, J. Lacour, J. Am. Chem. Soc. 2025, 147, 21121-21130; b) C. Montagnon, J. R. Bultel, C. Besnard, L. Guénée, J. Lacour, Chem. Eur. J. 2024, e202401522; c) Y. Nikolova, B. Fabri, P. Moneva Lorente, A. Guarnieri-Ibáñez, A. de Aguirre, Y. Soda, G. Pescitelli, F. Zinna, C. Besnard, L. Guénée, D. Moreau, L. Di Bari, E. Bakker, A. I. Poblador-Bahamonde, J. Lacour, Angew. Chem. Int. Ed. 2022, 61, e202210798; d) J. Viñas-Lóbez, G. Levitre, A. De Aguirre, C. Besnard, A. I. Poblador-Bahamonde, J. Lacour, ACS Org. Inorg. Au 2021, 1, 11-17; e) T. Achard, C. Tortoreto, A. I. Poblador-Bahamonde, L. Guénée, T. Bürgi, J. Lacour, Angew. Chem. Int. Ed. 2014, 53, 6140–6144; f) C. Tortoreto, T. Achard, W. Zeghida, M. Austeri, L. Guénée, J. Lacour, Angew. Chem. Int. Ed. 2012, 51, 5847-5851.