Synlett, Inhaltsverzeichnis Synlett 2018; 29(04): 503-508DOI: 10.1055/s-0036-1590939 letter © Georg Thieme Verlag Stuttgart · New York Selective 7-endo-Cyclization of 3-Aza-5-alkenols through Oxidative Pd(II)-Catalyzed Olefin Oxyarylation Silvia Gazzola a Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Via Valleggio 11, 22100, Como, Italy eMail: gianluigi.broggini@uninsubria.it , Egle M. Beccalli b DISFARM, Sezione di Chimica Generale e Organica ‘A. Marchesini’ Università degli Studi di Milano, Via Venezian 21, 20133 Milano, Italy , Tea Borelli a Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Via Valleggio 11, 22100, Como, Italy eMail: gianluigi.broggini@uninsubria.it , Carlo Castellano c Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy , Daria Diamante a Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Via Valleggio 11, 22100, Como, Italy eMail: gianluigi.broggini@uninsubria.it , Gianluigi Broggini* a Dipartimento di Scienza e Alta Tecnologia, Università dell’Insubria, Via Valleggio 11, 22100, Como, Italy eMail: gianluigi.broggini@uninsubria.it › Institutsangaben Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract 3-Aza-5-alkenols undergo selective 7-endo-trig cyclization when treated with a catalytic Pd(II) species, CuCl2 and ArSnBu3 giving 7-aryl-substituted oxazepanes. The intramolecular alkoxylation occurs with formation of a seven-membered ring only when associated with an arylating step. Otherwise, 6-exo-trig reactions, providing morpholine derivatives, were observed. Key words Key wordspalladium - heterocycles - domino reactions - Wacker reaction - homogeneous catalysis - cyclization - oxyarylation Volltext Referenzen References and Notes 1a Yang L. Huang H. Chem. Rev. 2015; 115: 3468 1b Huang H. Ji X. Wu W. Jiang H. Chem. Soc. Rev. 2015; 44: 155 1c Butt NA. Zhang W. Chem. Soc. Rev. 2015; 44: 7929 1d Liu C. Yuan J. Gao M. Tang S. Li W. Shi R. Lei A. Chem. Rev. 2015; 115: 12138 1e Chen F. Wang T. Jiao N. Chem. Rev. 2014; 114: 8613 1f Yamamoto Y. Chem. Rev. 2012; 112: 4736 1g Marinetti A. Jullien H. Voituriez A. Chem. Soc. Rev. 2012; 41: 4884 1h Liu C. Zhang H. Shi W. Lei A. Chem. Rev. 2011; 111: 1780 1i Yeung CS. Dong VM. Chem. Rev. 2011; 111: 1215 1j Zhang M. Adv. Synth. Catal. 2009; 351: 2243 2a McDonald RI. Liu G. Stahl SS. Chem. 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Then the solvent was evaporated under reduced pressure, and water (10 mL) was added. The aqueous layer was extracted with CH2Cl2 (3 × 10 mL), and the organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica column chromatography to afford the corresponding oxazepane 3. 13 Spectroscopic Data of 7-Phenyl-4-(4-nitrobenzenesulfonyl)-1,4-oxazepane (3b) 1H NMR (400 MHz, CDCl3): δ = 1.92–2.03 (m, 1 H), 2.24–2.31 (m, 1 H), 3.27 (ddd, J = 13.2, 10.0, 2.8 Hz, 1 H), 3.35–3.42 (m, 1 H), 3.54–3.59 (m, 1 H), 3.67 (dt, J = 13.6, 2.8 Hz, 1 H), 3.73 (ddd, J = 12.4, 7.6, 4.4 Hz, 1 H), 4.08 (dt, J = 13.2, 3.2 Hz, 1 H), 4.62 (dd, J = 9.6, 4.4 Hz, 1 H), 7.14–7.28 (m, 5 H), 7.94 (d, J = 8.4, 2 H), 8.33 (d, J= 8.4 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 37.9 (t), 46.3 (t), 51.7 (t), 69.9 (t), 81.6 (d), 124.5 (d), 125.5 (d), 127.6 (d), 128.1 (d), 128.5 (d), 142.4 (s), 149.9 (s), 150.0 (s). MS: m/z = 362 [M+]. Anal. Calcd for C17H18N2O5S: C, 56.34; H, 5.01; N, 7.73. Found: C, 56.11; H, 5.27; N, 7.48. 14 CCDC 1519865 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. 15a Semmelhack MF. Bodurow C. J. Am. Chem. Soc. 1984; 106: 1496 15b Semmelhack MF. Zhang N. J. Org. Chem. 1989; 54: 4483 15c Liu C. Widenhoefer RA. J. Am. Chem. Soc. 2004; 126: 10250 16a Lai J.-Y. Shi X.-X. Gong Y.-S. Dai L.-X. J. Org. Chem. 1993; 58: 4775 16b Broggini G. Beccalli EM. Borelli T. Brusa F. Gazzola S. Mazza A. Eur. J. Org. Chem. 2015; 4261 17 Michael FE. Sibbald PA. Cochran BM. Org. Lett. 2008; 10: 793 18 Broggini G. Barbera V. Beccalli EM. Borsini E. Galli S. Lanza G. Zecchi G. Adv. Synth. Catal. 2012; 354: 159 19a Rajabi J. Lorion MM. Ly VL. Liron F. Oble J. Prestat G. Poli G. Chem. Eur. J. 2014; 20: 1539 19b Manick AD. Duret G. Tran DN. Berhal F. Prestat G. Org. Chem. Front. 2014; 1: 1058 19c Martínez C. Wu Y. Weinstein AB. Stahl SS. Liu G. Muñiz K. J. Org. Chem. 2013; 78: 6309 19d Alexanian EJ. Lee C. Sorensen EJ. J. Am. Chem. Soc. 2005; 127: 7690 20 Spectroscopic Data of 7-[4-(Benzyloxy)phenyl]-4-(4-methylbenzenesulfonyl)-1,4-oxazepane (10) 1H NMR (400 MHz, CDCl3): δ = 1.93–1.99 (m, 1 H), 2.16–2.21 (m, 1 H), 2.37 (s, 3 H), 3.15–3.19 (m, 1 H), 3.23–3.29 (m, 1 H), 3.48–3.54 (m, 1 H), 3.58–3.70 (m, 2 H), 3.99 (dt, J = 12.8, 2.9 Hz, 1 H), 4.54 (dd, J = 5.6, 9.6 Hz, 1 H), 4.97 (s, 2 H), 6.85 (d, J = 8.1 Hz, 2 H), 7.12 (d, J = 8.1 Hz, 2 H), 7.24–7.35 (m, 7 H), 7.63 (d, J = 8.1 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 21.5 (q), 37.6 (t), 46.2 (t), 51.7 (t), 69.8 (t), 70.0 (t), 81.1 (d), 114.8 (d), 126.9 (d), 127.0 (d), 127.4 (d), 127.9 (d), 128.6 (d), 129.8 (d), 135.3 (s), 135.9 (s), 136.9 (s), 143.4 (s), 158.1 (s). MS: m/z = 437 [M+]. Anal. Calcd for C25H27NO4S: C, 68.63; H, 6.22; N, 3.20. Found: C, 68.74; H, 5.98; N, 3.47. 21a Kalyani D. Sanford MS. J. Am. Chem. Soc. 2008; 130: 2150 21b Kalyani D. Satterfield AD. Sanford MS. J. Am. Chem. Soc. 2010; 132: 8419 22 For the transmetalation process between Bu3SnAr and palladium(II) species, see: Stille JK. Angew. Chem., Int. Ed. Engl. 1986; 25: 508 23a Tamaru Y. Hojo M. Higashimura H. Yoshida Z.-I. Angew. Chem. Int. Ed. Engl. 1986; 25: 735 23b Gligorich KM. Cummings SA. Sigman MS. J. Am. Chem. Soc. 2007; 129: 14193 23c Urkalan KB. Sigman MS. Angew. Chem. Int. Ed. 2009; 48: 3146 23d Werner EW. Urkalan KB. Sigman MS. Org. Lett. 2010; 12: 2848 23e Satterfield AD. Kubota A. Sanford MS. Org. Lett. 2011; 13: 1076 Zusatzmaterial Zusatzmaterial Supporting Information
