Synthesis, Inhaltsverzeichnis Synthesis 2022; 54(22): 5128-5138DOI: 10.1055/s-0037-1610790 paper A General Way to Spiro-Annulated 2-Benzoxepines via Rh2(esp)2-Catalyzed [5+2] Cycloaddition of Diazo Arylidene Succinimides to Ketones Anastasia Vepreva a Saint Petersburg State University, Petersburg, 199034, Russian Federation , Grigory Kantin a Saint Petersburg State University, Petersburg, 199034, Russian Federation , Mikhail Krasavin ∗ a Saint Petersburg State University, Petersburg, 199034, Russian Federation b Immanuel Kant Baltic Federal University, Kaliningrad 236041, Russian Federation , Dmitry Dar’in ∗ a Saint Petersburg State University, Petersburg, 199034, Russian Federation › Institutsangaben Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract The formation of spirocyclic 2-benzoxepines by Rh2(esp)2-catalyzed decomposition of diazo arylidene succinimides in the presence of ketones was investigated. This transformation, which is a formal [5+2] cycloaddition of styryl rhodium carbenes to the carbonyl group, occurs in high yields under mild conditions, with high carbonyl substrate tolerance and diastereoselectivity. The developed general method opens access to rare spiro (hetero)cyclic scaffolds with great potential in drug discovery. Key words Key wordsspirocyclic scaffold - 2-benzoxepines - cyclic α-diazocarbonyl compounds - conjugated carbonyl ylide - electrocyclization Volltext Referenzen References 1 Chupakhin E, Babich O, Prosekov A, Asyakina L, Krasavin M. Molecules 2019; 24: 4165 2 Hiesinger K, Dar’in D, Proschak E, Krasavin M. J. Med. Chem. 2021; 64: 150 3 Zheng Y, Tice CM, Singh SB. Bioorg. Med. Chem. Lett. 2014; 24: 3673 4 Solovyev I, Eremeyeva M, Zhukovsky D, Dar’in D, Krasavin M. Tetrahedron Lett. 2021; 62: 152671 5 Dar’in D, Kantin G, Bakulina O, Inyutina A, Chupakhin E, Krasavin M. J. Org. Chem. 2020; 85: 15586 6 Laha D, Bhat RG. Asian J. Org. Chem. 2020; 9: 918 7 Inyutina A, Dar’in D, Kantin G, Krasavin M. Org. Biomol. Chem. 2021; 19: 5068 8 Inyutina A, Kantin G, Dar’in D, Krasavin M. J. Org. Chem. 2021; 86: 13673 9a Wurst JM, Liu G, Tan DS. J. Am. Chem. Soc. 2011; 133: 7916 9b Liu G, Wurst JM, Tan DS. Org. Lett. 2009; 11: 3670 10 Butkevich AN, Corbu A, Meerpoel L, Stansfield I, Angibaud P, Bonnet P, Cossy J. Org. Lett. 2012; 14: 4998 11a Maier CA, Wünsch B. Eur. J. Org. Chem. 2003; 714 11b Maestrup EG, Wiese C, Schepmann D, Brust P, Wünsch B. Bioorg. Med. Chem. 2011; 19: 393 12 Bohme H, Hitzel V. Arch. Pharm. 1974; 306: 948 13 Boerth JA, Hummel JR, Ellman JA. Angew. Chem. Int. Ed. 2016; 55: 1 14 Hamaguchi M, Takahashi K, Oshima T, Tamura H. Tetrahedron Lett. 2003; 44: 4339 15a Chupakhin EG, Kantin GP, Dar’in DV, Krasavin M. Mendeleev Commun. 2021; 31: 36 15b Chupakhin E, Gecht M, Ivanov A, Kantin G, Dar’in D, Krasavin M. Synthesis 2021; 53: 1292 Zusatzmaterial Zusatzmaterial Supporting Information
