Synlett, Inhaltsverzeichnis Synlett 2023; 34(04): 369-373DOI: 10.1055/a-1982-5185 letter Palladium-Catalyzed C(sp2)–H Silylation via a Native-Amine-Directed Strategy Yintao Yan‡ a School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, P. R. of China , Xuan Wang‡ a School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, P. R. of China , Jianhua Li∗ b Lianhe Chemical Technology Co., Ltd., Jiangkou Avenue, Taizhou, Zhejiang 318020, P. R. of China , Chao Jiang ∗ a School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094, P. R. of China› InstitutsangabenArtikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract A palladium-catalyzed C(sp2)–H silylation of morpholinones to afford silyl morpholinones is reported. The native secondary amine, which is tolerated in the reaction, is able to promote the C–H activation and silylation of the aryl group. The substrates are monosilylated selectively and tolerate various functional groups. The resulting silyl morpholinone derivatives are potentially useful in pharmaceuticals and agrochemicals. Key words Key wordspalladium - C–H activation - C(sp2)–H Silylation - morpholinone - organosilicon compounds Volltext Referenzen References and Notes 1a Colvin EW. Silicon Reagents in Organic Synthesis . Academic Press; London: 1988 1b Rappoport Z, Apeloig Y. Chemistry of Organosilicon Compounds . Wiley-VCH; New York: 2001 1c Rochow EG. Silicon and Silicones . Springer; New York: 1987 1d Corey JY, Braddock-Wilking J. Chem. Rev. 1999; 99: 175 1e Mochida K, Shimizu M, Hiyama T. J. Am. Chem. Soc. 2009; 131: 8350 2a Liang Y, Zhang SG, Xi ZF. J. Am. Chem. Soc. 2011; 133: 9204 2b Cheng C, Hartwig JF. Science 2014; 343: 853 2c Nakao Y, Hiyama T. Chem. Soc. 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Upon completion, the reaction mixture was cooled to room temperature and diluted with EtOAc, filtered through a plug of Celite, and the solvent was removed under vacuum. After purification by column chromatography (hexane–EtOAc = 10:1 as eluent), 2a was obtained as a white solid (18.9 mg, 65%). Analytical Data for Compound 2a White solid; mp 80.5 °C; Rf = 0.41 (hexane–EtOAc = 10:1). 1H NMR (500 MHz, CDCl3): δ = 7.71 (dd, J = 7.0, 1.4 Hz, 1 H), 7.34–7.30 (m, 1 H), 7.27–7.21 (m, 2 H), 3.76 (d, J = 11.6 Hz, 1 H), 3.73 (d, J = 11.5 Hz, 1 H), 1.61 (s, 3 H), 1.24 (s, 3 H), 0.95 (s, 3 H), 0.40 (s, 9 H). 13C NMR (126 MHz, CDCl3): δ = 174.4, 148.2, 138.8, 138.0, 128.7, 126.7, 125.1, 73.4, 64.4, 51.4, 30.6, 28.9, 27.4, 4.0. HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H26NO2Si+: 292.1733; found: 292.1731. 22a Zhu RY, Liu LY, Yu JQ. J. Am. Chem. Soc. 2017; 139: 12394 22b Zhu RY, Li ZQ, Park HS, Senanayake CH, Yu JQ. J. Am. Chem. Soc. 2018; 140: 3564 22c Smalley AP, Gaunt MJ. J. Am. Chem. Soc. 2015; 137: 10632 Zusatzmaterial Zusatzmaterial Supporting Information
