Synlett, Table of Contents Synlett 2015; 26(09): 1233-1237DOI: 10.1055/s-0034-1378691 letter © Georg Thieme Verlag Stuttgart · New York Rhodium-Catalyzed Addition–Spirocyclization of Arylboronic Esters Containing β-Aryl α,β-Unsaturated Ester Moiety Takanori Matsuda* Department of Applied Chemistry, Tokyo University of Science, 1–3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan Email: mtd@rs.tus.ac.jp , Satoshi Yasuoka Department of Applied Chemistry, Tokyo University of Science, 1–3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan Email: mtd@rs.tus.ac.jp , Shoichi Watanuki Department of Applied Chemistry, Tokyo University of Science, 1–3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan Email: mtd@rs.tus.ac.jp , Keisuke Fukuhara Department of Applied Chemistry, Tokyo University of Science, 1–3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan Email: mtd@rs.tus.ac.jp › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract In this study, we developed a rhodium(I)-catalyzed spirocyclization. The reaction includes 1,4-rhodium migration and provides a route for forming spirocyclic 1-indanones. Key words Key wordsaddition - boron - cyclization - rhodium - spiro compounds Full Text References References and Notes For reviews, see: 1a Ma S, Gu Z. Angew. Chem. Int. Ed. 2005; 44: 7512 1b Shi F, Larock R. Top. Curr. Chem. 2010; 292: 123 2a Oguma K, Miura M, Satoh T, Nomura M. J. Am. Chem. Soc. 2000; 122: 10464 2b Matsuda T, Shigeno M, Murakami M. J. Am. Chem. Soc. 2007; 129: 12086 2c Sasaki K, Nishimura T, Shintani R, Kantchev EA. B, Hayashi T. Chem. Sci. 2012; 3: 1278 2d Sasaki K, Hayashi T. Tetrahedron: Asymmetry 2012; 23: 373 2e Prakash P, Jijy E, Shimi M, Aparna PS, Suresh E, Radhakrishnan KV. RSC Adv. 2013; 3: 19933 2f Shintani R, Iino R, Nozaki K. J. Am. Chem. Soc. 2014; 136: 7849 3a Hayashi T, Inoue K, Taniguchi N, Ogasawara M. J. Am. Chem. Soc. 2001; 123: 9918 3b Miura T, Sasaki T, Nakazawa H, Murakami M. J. Am. Chem. 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Lett. 2013; 42: 1076 3q Matsuda T, Watanuki S. Org. Biomol. Chem. 2015; 13: 702 4 Matsuda T, Suda Y, Takahashi A. Chem. Commun. 2012; 48: 2988 For analogous 1,3- and 1,5-rhodium migrations, see: 5a Tobisu M, Hasegawa J, Kita Y, Kinuta H, Chatani N. Chem. Commun. 2012; 48: 11437 5b Zhang J, Zhao P, Liu J.-F, Ugrinov A, Pillai AF. X, Sun Z.-M. J. Am. Chem. Soc. 2013; 135: 17270 5c Ishida N, Shimamoto Y, Yano T, Murakami M. J. Am. Chem. Soc. 2013; 135: 19103 6 The corresponding intermolecular reaction was reported, see ref. 3o. For general reviews on rhodium(I)-catalyzed addition reactions of arylboronic acids, see: 7a Hayashi T, Yamasaki K. Chem. Rev. 2003; 103: 2829 7b Miura T, Murakami M. Chem. Commun. 2007; 217 7c Youn SW. Eur. J. Org. Chem. 2009; 2597 7d Edwards HJ, Hargrave JD, Penrose SD, Frost CG. Chem. Soc. Rev. 2010; 39: 2093 7e Tian P, Dong H.-Q, Lin G.-Q. ACS Catal. 2012; 2: 95 8a Lautens M, Mancuso J. Org. Lett. 2002; 4: 2105 8b Lautens M, Mancuso J. J. Org. 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Rev. 2014; 43: 412 12 (E)-Methyl 5-[2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl]-3-phenylpent-2-enoate (4a): White solid; mp 104–105 °C; 1H NMR (CDCl3, 301 MHz): δ = 0.98 (s, 6 H), 3.01–3.09 (m, 2 H), 3.31–3.40 (m, 2 H), 3.65 (s, 4 H), 3.78 (s, 3 H), 6.08 (s, 1 H), 7.15–7.22 (m, 1 H), 7.32–7.42 (m, 5 H), 7.51–7.57 (m, 2 H), 7.71–7.76 (m, 1 H). 13C NMR (CDCl3, 75.6 MHz): δ = 21.8, 31.5, 34.8, 35.2, 51.1, 72.0, 116.9, 125.1, 126.9, 128.4, 128.7, 129.9, 130.3, 134.8, 141.6, 147.6, 160.8, 166.7. HRMS (ESI) calcd for C23H27BNaO4 [M + Na]+ 401.1895; found: 401.1895. IR: 2960, 1712, 1301, 1161, 766 cm−1. General Procedure for Rhodium-Catalyzed Spirocyclization of Arylboronic Esters: To a Schlenk tube under nitrogen were added [Rh(OH)(cod)]2 (1.2 mg, 2.6 μmol, 5 mol% Rh), 1,2-bis(diphenylphosphino)benzene (DPPBZ, 2.3 mg, 5.2 μmol), arylboronic ester 4 (0.100 mmol), and xylene (1.0 mL). The solution was stirred for 5 min. at rt, and the mixture was heated at 140 °C for 2 h. After cooling to r.t., the reaction mixture was filtered through a plug of Florisil® washing with hexane–EtOAc (3:1), and the filtrate was concentrated. The residue was purified by preparative TLC on silica gel (hexane–EtOAc) to afford 2. 1,1′-Spirobi[indan]-3-one (2a): According to the general procedure, 4a (37.9 mg, 0.100 mmol), [Rh(OH)(cod)]2 (1.2 mg, 2.6 μmol), and DPPBZ (2.3 mg, 5.2 μmol) were treated in xylene (1.0 mL). Purification by preparative TLC on silica gel afforded 2a (19.7 mg, 0.084 mmol, 84%) as a colorless oil. 1H NMR (CDCl3, 300 MHz): δ = 2.37 (ddd, J = 12.7, 7.0, 5.5 Hz, 1 H), 2.52 (dt, J = 12.8, 8.2 Hz, 1 H), 2.85 (d, J = 18.9 Hz, 1 H), 3.00 (d, J = 18.9 Hz, 1 H), 3.10–3.20 (m, 2 H), 6.78 (d, J = 7.2 Hz, 1 H), 7.14 (dt, J = 0.8, 7.4 Hz, 1 H), 7.21 (dd, J = 7.3, 1.0 Hz, 1 H), 7.23–7.29 (m, 1 H), 7.32 (d, J = 7.2 Hz, 1 H), 7.37–7.46 (m, 1 H), 7.54– 7.62 (m, 1 H), 7.75–7.82 (m, 1 H); 13C NMR (CDCl3, 75.5 MHz): δ = 31.3, 42.9, 52.4, 54.5, 122.8, 123.1, 124.6, 125.1, 127.2, 127.3, 127.9, 135.4, 136.1, 143.3, 148.9, 161.5, 205.7. HRMS (ESI) calcd for C17H14NaO [M + Na]+ 257.0937; found: 257.0937. IR: 2948, 1716, 1602, 1236, 758 cm–1. 13 Asymmetric reaction: 4a (37.8 mg, 0.100 mmol), [Rh(OH)(cod)]2 (1.1 mg, 2.4 μmol), and (R)-BINAP (3.1 mg, 5.0 μmol) were reacted in xylene (1.0 mL) at 140 °C. Purification by preparative TLC on silica gel yielded 2a (10.1 mg, 0.043 mmol, 43%); 52% ee determined by HPLC analysis (CHIRALCEL® OJ-H column, hexane–i-PrOH (90:10), 1.0 mL/min, t minor = 7.7 min, t major = 10.0 min). Supplementary Material Supplementary Material Supporting Information
