Synlett, Table of Contents Synlett 2019; 30(14): 1662-1666DOI: 10.1055/s-0037-1610716 cluster © Georg Thieme Verlag Stuttgart · New YorkCatalyst-Controlled Regio- and Stereoselective Bromolactonization with Chiral Bifunctional Sulfides Authors Author Affiliations Ayano Tsuchihashi Seiji Shirakawa * Department of Environmental Science, Graduate School of Fisheries and Environmental Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan Email: seijishirakawa@nagasaki-u.ac.jp Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Published as part of the Cluster Organosulfur and Organoselenium Compounds in Catalysis Abstract Highly regioselective 5-exo bromolactonizations of stilbene-type carboxylic acids bearing electron-withdrawing substituents are achieved for the first time via the use of chiral bifunctional sulfide catalysts possessing a urea moiety. The chiral phthalide products are obtained in moderate to good enantioselectivities as the result of 5-exo cyclizations. Key words Key wordsasymmetric synthesis - lactonization - organocatalysis - regioselectivity - sulfides Full Text References References and Notes For reviews on organocatalysis, see: 1a Dalko PI, Moisan L. Angew. Chem. Int. Ed. 2001; 40: 3726 1b Dalko PI, Moisan L. Angew. Chem. Int. Ed. 2004; 43: 5138 1c MacMillan DW. C. Nature 2008; 455: 304 1d Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications. Dalko PI. Wiley-VCH; Weinheim: 2013 For reviews on chiral sulfide catalysts, see: 2a Aggarwal VK. Synlett 1998; 329 2b Aggarwal VK, Winn CL. Acc. Chem. Res. 2004; 37: 611 2c McGarrigle EM, Myers EL, Illa O, Shaw MA, Riches SL, Aggarwal VK. Chem. Rev. 2007; 107: 5841 2d Gómez Arrayás R, Carretero JC. Chem. Commun. 2011; 47: 2207 2e Luo J, Liu X, Zhao X. 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For a reaction using another reactive brominating reagent, see Scheme S3 in the Supporting Information. 11 For other control experiments, see Scheme S4 in the Supporting Information. 12 Asymmetric Bromolactonizations; General Procedure A solution of substrate 1 (0.10 mmol) and catalyst (S)-4d (10 mol%, 0.010 mmol) in CH2Cl2 (2 mL) was cooled to 0 °C. After stirring for 10 min, N-bromosuccinimide (NBS) (0.12 mmol) was added and the resulting mixture was stirred for 24 h at 0 °C. The mixture was quenched with saturated aqueous Na2SO3 (4.0 mL) at 0 °C, stirred for 10 min at 0 °C, diluted with CH2Cl2 (2 mL) and H2O (2 mL) and then warmed to room temperature. The organic materials were extracted with CH2Cl2 (3 × 5 mL) and the combined extracts dried over Na2SO4 and concentrated. (The 1H NMR analysis of the crude reaction mixture was performed at this stage to determine the regioselectivity of the bromolactonization products.) The residue was purified by flash column chromatography on silica gel (hexane/EtOAc as eluent) to give product 2. The enantioselectivity of the product 2 was determined by HPLC analysis on a chiral stationary phase. Compound 2a5 Yield: 31.9 mg (86%); colorless oil; [α]D 21 +4.4 (c = 0.87, CHCl3); 82:18 er; HPLC (Daicel Chiralpak IC-3, hexane/2-propanol = 10:1, flow rate = 0.5 mL/min, 230 nm): t R = 59.3 min (major) and 68.8 min (minor). IR (neat): 1769, 1324, 1286, 1167, 1124, 1114, 1067, 1018 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.85 (d, J = 7.2 Hz, 1 H), 7.67–7.71 (m, 2 H), 7.53–7.60 (m, 5 H), 5.96 (d, J = 6.4 Hz, 1 H), 5.16 (d, J = 6.4 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 168.9, 146.0, 140.1, 134.1, 131.1 (q, J = 32.1 Hz), 130.2, 129.0, 126.5, 126.0 (q, J = 2.5 Hz), 125.7 (m), 123.7, 123.6 (q, J = 272 Hz), 82.1, 51.8. Supplementary Material Supplementary Material Supporting Information (PDF)
