One-Pot Synthesis of Symmetric 1,7-Dicarbonyl Compounds Via. a Tandem Radical Addition - Elimination Addition Reaction

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S1 One-Pot Synthesis of Symmetric 1,7-Dicarbonyl Compounds Via a Tandem Radical Addition - Elimination Addition Reaction Zhongyan Huang and Jiaxi Xu* State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China. Fax: (+86)10-64435565 E-mail: jxxu@mail.buct.edu.cn Contents...S1 Ananlytic data of known O-ethyl S-carbonylmethyl xanthates 1 and allyl sulfur compounds 2...S2 Copies of 1 H and 13 C NMR spectra of unknown O-ethyl S-carbonylmethyl xanthates 1...S5 Copies of 1 H and 13 C NMR spectra of unknown allylbutylsulfoxide 2d...S10 Copies of 1 H and 13 C NMR spectra of symmetric 1,7-dicarbonyl compounds 3...S11

S2 Ananlytic data of known O-ethyl S-carbonylmethyl xanthates 1 and allyl sulfur compounds 2 O-Ethyl S-[2-phenyl-2-oxoethyl] carbonodithioate (1a). Pale yellow solid, yield: 1.08 g, 90%, m.p. 32 33 o C, Lit. 1 m.p. 31 32 o C. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 1.39 (t, J = 7.1 Hz, 3H, CH 3 ), 4.63 (q, J = 7.1 Hz, 2H, CH 2 ), 4.66 (s, 2H, CH 2 ), 7.50 (t, J = 7.6 Hz, 2H, ArH), 7.61 (t, J = 7.6 Hz, 1H, ArH), 8.01 (d, J = 7.6 Hz, 2H, ArH). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.6 (CH 3 ), 43.5 (CH 2 ), 70.6 (CH 2 ), 128.4 (CH), 128.7 (CH), 133.7 (CH), 135.7 (CH), 166.4 (C), 192.2 (C=O), 213.2 (C=S). O-Ethyl S-[2-(4-methoxyphenyl)-2-oxoethyl] carbonodithioate (1b). Pale yellow solid, yield: 1.20 g, 89%, m.p. 69 70 o C, Lit. 1 m.p. 68 69 o C. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 1.40 (t, J = 7.1 Hz, 3H, CH 3 ), 3.88 (s, 3H, CH 3 ), 4.62 (s, 2H, CH 2 ), 4.64 (q, J = 7.1 Hz, 2H, CH 2 ), 7.50 (d, J = 8.6 Hz, 2H, ArH), 8.01 (d, J = 8.6 Hz, 2H, ArH). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.6 (CH 3 ), 43.1 (CH 2 ), 55.2 (CH 3 ), 70.2 (CH 2 ), 113.6 (CH), 128.5 (C), 130.4 (CH), 163.7 (C), 190.3 (C=O), 213.2 (C=S). O-Ethyl S-(2-oxopropyl) carbonodithioate (1c). 2 Pale yellow liquid, yield: 0.81 g, 91%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 1.39 (t, J = 7.1 Hz, 3H, CH 3 ), 2.30 (s, 3H, CH 3 ), 3.97 (s, 2H, CH 2 ), 4.67 (q, J = 7.1 Hz, 2H, CH 2 ). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.7 (CH 3 ), 29.1 (CH 3 ), 45.9 (CH 2 ), 70.6 (CH 2 ), 200.8 (C=O), 212.9 (C=S). S-(3-Chloro-2-oxopropyl) O-ethyl carbonodithioate (1d). White solid 1.12 g, yield: 70%, m.p. 52 53 o C, Lit. 3 49 50 o C. 1 H NMR (400 MHz, CDCl 3 ) (δ, ppm) 1.43 (t, J = 7.1 Hz, 3H, CH 3 ), 4.15 (s, 2H, CH 2 ), 4.30 (s, 2H, CH 2 ), 4.64 (q, J = 7.1 Hz, 2H, CH 2 ). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.6, 42.8, 47.8, 71.2, 195.6, 212.7. S-(2-Ethoxyl-2-oxoethyl) O-ethyl carbonodithioate (1e). 4 Pale yellow liquid, yield: 0.92 g, 88%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 1.29 (t, J = 7.1 Hz, 3H, CH 3 ), 1.42 (t, J = 7.1 Hz, 3H, CH 3 ), 3.92 (s, 2H, CH 2 ), 4.22 (q, J = 7.1 Hz, 2H, CH 2 ), 4.64 (q, J = 7.1 Hz, 2H, CH 2 ). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.6 (CH 3 ), 14.1 (CH 3 ), 37.8 (CH 2 ), 61.8 (CH 2 ), 70.5 (CH 2 ), 167.8 (C=O), 212.5 (C=S). O-Ethyl S-(2-phenoxy-2-oxoethyl) carbonodithioate (1f). 5 Pale yellow liquid, yield: 1.18 g, 92%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 1.43 (t, J = 7.1 Hz, 3H, CH 3 ), 4.13 (s, 2H, CH 2 ), 4.67 (q, J = 7.1 Hz, 2H, CH 2 ), 7.11 (d, J = 7.6 Hz, 2H, ArH), 7.23 (t, J = 7.6 Hz, 2H, ArH), 7.38 (t, J = 7.6 Hz, 2H, ArH). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.6 (CH 3 ), 37.9 (CH 2 ), 70.8 (CH 2 ), 121.2 (CH), 126.1 (CH), 129.4 (CH), 150.6 (C), 166.5 (C=O), 212.3 (C=S). O-Ethyl S-[2-oxo-2-(oxazolidin-2-on-3-yl)ethyl] carbonodithioate (1l). Pale yellow solid, yield: 1.11 g, 89%, m.p. 100 101 o C, Lit. 6 m.p. 96 o C. 1 H NMR (CDCl 3, 400

S3 MHz) (δ, ppm) 1.43 (t, J = 7.1 Hz, 3H, CH 3 ), 4.07 (t, J = 8.0 Hz, 2H, CH 2 ), 4.49 (t, J = 8.1 Hz, 2H, CH 2 ), 4.57 (s, 2H, CH 2 ), 4.65 (q, J = 7.1 Hz, 2H, CH 2 ). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.6 (CH 3 ), 39.3 (CH 2 ), 42.6 (CH 2 ), 62.4 (CH 2 ), 70.6 (CH 2 ), 153.4 (C=O), 166.7 (C=O), 212.7 (C=S). S-(Cyanomethyl) O-ethyl carbonodithioate (1m). 7 Pale yellow liquid, yield: 0.71 g, 88%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 1.47 (t, J = 7.1 Hz, 3H, CH 3 ), 3.89 (s, 2H, CH 2 ), 4.72 (q, J = 7.1 Hz, 2H, CH 2 ). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 13.6 (CH 3 ), 21.3 (CH 2 ), 71.5 (CH 2 ), 115.2 (CN), 208.9 (C=S). Allyl methylsulfone (2a). 8 Colorless liquid, yield: 10.5 g, 87%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 2.87 (s, 3H, CH 3 ), 3.74 (d, J = 7.6 Hz, 2H, CH 2 ), 5.48 (d, J = 17.2 Hz, 1H in CH 2 ), 5.52 (d, J = 10.2 Hz, 1H in CH 2 ), 5.92-6.02 (m, 1H, CH). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 38.9 (CH 3 ), 59.3 (CH 2 ), 124.6 (CH 2 ), 125.2 (CH). Allyl ethylsulfone (2b). 9 Colorless liquid, from sodium ethanesulphinate (2.50 g, 21.5 mmol), yield: 1.75 g, 60%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 1.39 (t, J = 7.1 Hz, 3H, CH 3 ), 3.00 (q, J = 7.1 Hz, 2H, CH 2 ), 3.71 (d, J = 7.6 Hz, 2H, CH 2 ), 5.43-5.51 (m, 2H, CH 2 ), 5.95 (ddt, J = 14.4, 10.4, 7.6 Hz, 1H, CH). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 6.4 (CH 3 ), 45.6 (CH 2 ), 56.8 (CH 2 ), 124.3 (CH 2 ), 125.1 (CH). Allyl phenylsulfone (2c). 10 Colorless liquid, yield: 15.6 g, 85%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 3.81 (d, J = 7.6 Hz, 2H, CH 2 ), 5.15 (d, J = 17.2 Hz, 1H in CH 2 ), 5.33 (d, J = 10.0 Hz, 1H in CH 2 ), 5.74 5.84 (m, 1H, CH), 7.56 (t, J = 7.6 Hz, 2H, ArH), 7.65 (t, J = 7.6 Hz, 1H, ArH), 7.88 (d, J = 7.6 Hz, 2H, ArH). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 60.8 (CH 2 ), 124.5 (CH), 124.6 (CH 2 ), 128.4 (CH), 129.0 (CH), 133.7 (CH), 138.2 (C). Allyl phenylsulfoxide (2e). 11 Colorless liquid, yield: 0.83 g, 50%. 1 H NMR (CDCl 3, 400 MHz) (δ, ppm) 3.52 (dd, J = 12.8, 7.6 Hz, 1H in CH 2 ), 3.58 (dd, J = 12.8, 7.6 Hz, 1H in CH 2 ), 5.16 (d, J = 17.2 Hz, 1H in CH 2 ), 5.20 (d, J = 10.0 Hz, 1H in CH 2 ), 5.59 5.70 (m, 1H, CH), 7.51 7.67 (m, 4H, ArH), 7.87 (d, J = 7.6 Hz, 1H, ArH). 13 C NMR (CDCl 3, 100 MHz) (δ, ppm) 60.8 (CH 2 ), 123.8 (CH), 124.6 (CH 2 ), 125.1 (CH), 128.4 (CH), 131.0 (CH), 142.7 (C). References 1 B. Batanero, O. Picazo and E. Barba, J. Org. Chem. 2001, 66, 320 322. 2 V. Liautard, F. Robert and Y. Landais, Org. Lett. 2011, 13, 2658 2661. 3 M. De Greef and S. Z. Zard, Org. Lett. 2007, 9, 1773 1776. 4 A. Kapat, E. Nyfeler, G. Giuffredi and P. Renaud, J. Am. Chem. Soc. 2009, 131, 17746 17747. 5 E. Godineau and Y. Landais, J. Am. Chem. Soc. 2007, 129, 12662 12663. 6 E. Bacqué, F. Pautrat and S. Z. Zard, Chem. Commun. 2002, 2312 2313.

S4 7 S. Kakaei, N. Chen and J. X. Xu, Tetrahedron 2013, 69, 302 309. 8 G. C. Tsui and M. Lautens, Angew. Chem., Int. Ed. 2010, 49, 8938 8941. 9 R. J. Palmer and C. J. M. Stirling, J. Am. Chem. Soc. 1980, 102, 7888 7892. 10 G. A. Russell and L. L. Herold, J. Org. Chem. 1985, 50, 1037 1040. 11 K. Bahrami, M. M. Khodaei and M. Sheikh Arabi, J. Org. Chem. 2010, 75, 6208 6213.

S5 Copies of 1 H and 13 C NMR spectra of unknown O-ethyl S-carbonylmethyl xanthates 1 S-[2-(4-Chlorophenoxy)-2-oxoethyl] O-ethyl carbonodithioate (1g)

S6 O-Ethyl S-[2-(4-nitrophenoxy)-2-oxoethyl] carbonodithioate (1h)

S7 S-(2-Benzyloxy-2-oxoethyl) O-ethyl carbonodithioate (1i)

S8 S-(2-Diphenylamino-2-oxoethyl) O-ethyl carbonodithioate (1j)

S9 O-Ethyl S-[2-(methanesulfonylphenylamino)-2-oxoethyl] carbonodithioate (1k)

S10 Copies of 1 H and 13 C NMR spectra of unknown allylbutylsulfoxide 2d Allylbutylsulfoxide (2d)

S11 Copies of 1 H and 13 C NMR spectra of symmetric 1,7-dicarbonyl compounds 3 S-(1,7-Dioxo-1,7-diphenylheptan)-4-yl O-ethyl carbonodithioate (3a)

S12 S-[1,7-Dioxo-1,7-di (4-methoxyphenyl)heptan]-4-yl O-ethyl carbonodithioate (3b)

S13 S-(1,7-Dioxononan)-5-yl O-ethyl carbonodithioate (3c)

S14 S-(1,7-Dichloro-1,7-dioxononan)-5-yl O-ethyl carbonodithioate (3d)

S15 S-(1,7-Diethoxyl-1,7-dioxoheptan)-4-yl O-ethyl carbonodithioate (3e)

S16 S-(1,7-Dioxo-1,7-diphenoxyheptan)-4-yl O-ethyl carbonodithioate (3f)

S17 S-[1,7-Di(4-chloro-phenoxy)-1,7-dioxoheptan]-4-yl O-ethyl carbonodithioate (3g)

S18 S-[1,7-Di(4-nitro-phenoxy)-1,7-dioxoheptan]-4-yl O-ethyl carbonodithioate (3h)

S19 S-(1,7-Dibenzyloxy-1,7-dioxoheptan)-4-yl O-ethyl carbonodithioate (3i)

S20 S-{[1,7-Di(diphenylamino)-1,7-dioxo]heptan}-4-yl O-ethyl carbonodithioate (3j)

S21 S-[1,7-Di(methanesulfonylphenylamino)-1,7-dioxoheptan]-4-yl O-ethyl carbonodithioate (3k)

S22 S-[1,7-Dioxo-1,7-di(2-oxooxazolidin-3-yl)heptan]-4-yl O-ethyl carbonodithioate (3l)

S23 S-(1,5-Dicyanopentan-3-yl) O-ethyl carbonodithioate (3m)

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