Supporting Information. for. Highly Selective Hydroiodation of Alkynes Using. Iodine-Hydrophosphine Binary System

Supporting Information for Highly Selective Hydroiodation of Alkynes Using Iodine-Hydrophosphine Binary System Shin-ichi Kawaguchi and Akiya Ogawa * Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan ogawa@chem.osakafu-u.ac.jp CONTENTS page General Comments S2 General Procedure for 2-iodo-1-alkenes S2 The Spectral and Analytical Data S3 References S6 NMR Spectra Copies of 1 H NMR and 13 C NMR spectra of compounds (2a-2m, 3a) S7-34 S1

General Comments. Diphenyl(oct-1-ynyl)phosphine oxide (1n) 1 was synthesized according to the literature. Other materials were obtained from commercial supplies. Alkynes were purified by distillation before use. Other materials were used without further purification. 1 H NMR spectra were recorded on JEOL JNM-ECP-500 (500 MHz) FT NMR system, JEOL JNM-400 (400 MHz) FT NMR system, or JEOL JNM-ECX400 (100 MHz) FT NMR in CDCl 3 with Me 4 Si as an internal standard. 13 C NMR spectra were taken on JEOL JNM-ECP-500 (125 MHz) FT NMR system or JEOL JNM-ECX400 (100 MHz) FT NMR system in CDCl 3. 31 P NMR spectra were taken on a JEOL JNM- ECP-500 (200 MHz) FT NMR system in CDCl 3 with 85% H 3 PO 4 solution as an external standard. IR spectra were determined on a Perkin Elmer Model 1600 spectrometer. resolution mass spectra were obtained on SHIMADZU GCMS-QP5000. Low High resolution mass spectra were obtained on JEOL JMS-DX303 in the analytical section of Osaka University or Kyoto-Nrara Advanced Nanotechnology Network. General Procedure for 2-Iodo-1-alkenes Using Iodide-Hydrophosphine Binary System. Condition (A): under a nitrogen atmosphere, diphenylphosphine oxide (60.6 mg, 0.3 mmol) was placed in a Schlenk tube at room temperature, followed by CDCl 3, iodine (38.1 mg, 0.15 mmol), and alkyne or alkene (0.2 mmol). The mixture was stood statically for 16 h at room temperature, and then EtOH (100 ml) was added to quench the reaction. After a while, the crude solution turned colorless from pale purple and white solid of Ph 2 P(O)OH was precipitated. The precipitate was filtered, and the crude solution was purified by preparative TLC (silica gel). Eluent: 2a-2g, 2l, and 2m: hexane = 100%; 3a: hexane/acoet = 1/1. Condition (B): under a nitrogen S2

atmosphere, diphenylphosphine oxide (40.4 mg, 0.2 mmol) was placed in a Schlenk tube, followed by CDCl 3, iodine (25.4 mg, 0.10 mmol), and alkyne (0.6 mmol). The mixture was stood statically for 16 h at 0 o C to room temperature, turning pale yellow solution from purple, and then EtOH (100 ml) was added to quench the reaction. After a while, the crude solution turned colorless from pale yellow and white solid of Ph 2 P(O)OH was precipitated. The precipitate was filtered, and the crude solution was purified by preparative TLC. Eluent: 2h-2k: hexane = 100%. The Spectral and Analytical Data. 2-Iodooct-1-ene (2a) 2) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 0.89 (t, J = 6.9 Hz, 3H), 1.23 1.33 (m, 6H), 1.45 1.53 (m, 2H), 2.38 (t, J = 7.3 Hz, 2H), 5.69 (d, J = 0.9 Hz, 1H), 6.01 (d, J = 0.9 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 14.2, 22.7, 28.0, 29.1, 31.6, 45.4, 113.0, 125.2; MS (EI), m/z (%) = 238 (M +, 2), 111 (M + I, 19). 2-Iodododec-1-ene (2b) 3) : colorless oil; 1 H NMR (500 MHz, CDCl 3 ) δ 0.87 (t, J = 6.9 Hz, 3H), 1.20 1.32 (m, 14H), 1.46 1.52 (m, 2H), 2.37 (t, J = 7.4 Hz, 2H), 5.67 (d, J = 0.9 Hz, 1H), 6.00 (d, J = 1.4 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 14.1, 22.7, 28.2, 29.1, 29.30, 29.31, 29.5, 29.6, 31.9, 45.3, 112.8, 125.1. 2-Iodooctane (2c) 4) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 0.89 (t, J = 7.3 Hz, 3H), 1.20 1.55 (m, 8H), 1.55 1.68 (m, 1H), 1.79 1.91 (m, 1H), 1.92 (d, J = 7.4 Hz, 3H), 4.19 (se, J = 7.3 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 14.2, 22.7, 28.5, 29.0, 29.8 31.0, 31.7, 43.0; MS (EI), m/z (%) = 240 (M +, 1), 113 (M + I, 23). 5-Chloro-2-iodopent-1-ene (2d) 5) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 1.99 (qin, J = 6.8 Hz, 2H), 2.57 (t, J = 7.0 Hz, 2H), 3.55 (t, J = 6.4 Hz, 2H), 5.76 (d, J = 1.5 S3

Hz, 1H), 6.12 (d, J = 1.5 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 31.4, 42.1, 43.0, 109.7, 127.0; MS (EI), m/z (%) = 230 (M +, 13), 103 (M + I, 22), 67 (M + I Cl, 100). 5-Cyano-2-iodopent-1-ene (2e) 6) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 1.89 (qin, J = 6.9 Hz, 2H), 2.36 (t, J = 7.1 Hz, 2H), 2.55 (t, J = 7.0 Hz, 2H), 5.81 (s, 1H), 6.17 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 15.4, 24.4, 43.3, 108.6, 119.0, 127.9; MS (EI), m/z (%) = 221 (M +, 13), 94 (M + I, 30), 67 (M + I CN, 100). 2,5-Diiodopent-1-ene (2f) 6) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 1.97 2.06 (m, 2H), 2.52 (t, J = 6.8 Hz, 2H), 3.18 (t, J = 6.8 Hz, 2H), 5.77 (d, J = 1.2 Hz, 1H), 6.15 (d, J = 1.2 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 4.8, 31.9, 45.3, 109.4, 127.2; MS (EI), m/z (%) = 322 (M +, 3), 195 (M + I, 56), 67 (M + 2I, 100). Ethyl 5-iodo-5-hexenoate (2g): colorless oil; IR (NaCl) 897, 1111, 1165, 1732, 2980; 1 H NMR (400 MHz, CDCl 3 ) δ 1.26 (t, J = 7.3 Hz, 3H), 1.87 (qin, J = 7.3 Hz, 2H), 2.31 (t, J = 7.3 Hz, 2H), 2.44 (t, J = 7.3 Hz, 2H), 4.13 (q, J = 7.3 Hz, 2H), 5.73 (s, 1H), 6.05 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 14.3, 24.2, 32.5, 44.4, 60.4, 111.0, 126.4, 173.1; HRMS (FAB) Calcd for C 8 H 13 O 2 I: 267.9960, Found: 267.9965. (1-Iodoethenyl)benzene (2h) 7) : colorless oil; 1 H NMR (500 MHz, CDCl 3 ) δ 6.08 (d, J = 1.9 Hz, 1H), 6.46 (d, J = 1.9 Hz, 1H), 7.21 7.38 (m, 3H), 7.45 7.55 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 107.4, 127.3, 128.1, 128.8, 132.1, 141.6; MS (EI), m/z (%) = 230 (M +, 6), 103 (M + I, 100). 1-(1-Iodoethenyl)-4-pentylbenzene (2i): colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 0.89 (t, J = 7.1 Hz, 3H), 1.28 1.38 (m, 4H), 1.54 1.65 (m, 2H), 2.60 (t, J = 7.6 Hz, 2H), 6.03 (s, 1H), 6.43 (s, 1H), 7.11 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8.3 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 14.0, 22.5, 31.0, 31.4, 35.5, 107.7, 126.4, 128.0, 128.2, 139.0, 143.9; MS (EI), m/z (%) = 300 (M +, 3), 173 (M +, 100). S4

4-Bromo-1-(1-iodoethenyl)benzene (2j) 8) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 6.08 (d, J = 0.9 Hz, 1H), 6.45 (d, J = 1.4 Hz, 1H), 7.36 (d, J = 8.8 Hz, 2H), 7.42 (d, J = 8.9 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 105.7, 123.1, 128.0, 129.7, 131.4, 140.7; MS (EI), m/z (%) = 310 (M + +2, 3), 308 (M +, 3), 183 (M + +2 I, 56), 181 (M +, I 62), 102 (M + I Br, 100). 1-(1-Iodoethenyl)-4-methoxybenzene (2k) 9) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 3.81 (s, 3H), 5.99 (d, J = 1.8 Hz, 1H), 6.37 (d, J = 1.8 Hz, 1H), 6.82 (d, J = 9.2 Hz, 2H), 7.46 (d, J = 8.7 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 55.5, 107.4, 113.5, 125.7, 129.5, 134.3, 160.1; MS (EI), m/z (%) = 260 (M +, 3), 133 (M + I, 100). 1-(1-Iodoethenyl)-4-(trifluoromethyl)benzene (2l) 10) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 6.18 (d, J = 2.0 Hz, 1H), 6.54 (d, J = 2.0 Hz, 1H), 7.54 7.64 (m, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 105.0, 125.3 (q, J C F = 3.8 Hz), 126.8 (q, J C F = 271.9 Hz), 128.5, 129.3, 130.2 (q, J C F = 149.8 Hz), 145.2; MS (EI), m/z (%) = 298 (M +, 6), 171 (M + I, 100). (Z)-4-Iodo-4-octene (2m) 11) : colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 0.85 (t, J = 7.4 Hz, 3H), 0.91 (t, J = 7.4 Hz, 3H), 1.38 1.58 (m, 4H), 2.07 (q, J = 7.3 Hz, 2H), 2.41 (t, J = 7.1 Hz, 2H), 5.44 (t, J = 6.7 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 12.6, 13.7, 21.7, 22.5, 38.3, 47.1, 109.6, 134.8; MS (EI), m/z (%) = 238 (M +, 20). (E)-2-Iodido-1-(diphenylphosphinyl)-1-octene (3a): yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 0.89 (t, J = 6.7 Hz, 3H), 1.21 1.40 (m, 6H), 1.52 1.68 (m, 2H), 2.74 (t, J = 7.3 Hz, 2H), 6.95 (d, J H-P = 18.6 Hz, 1H), 7.38 7.57 (m, 6H), 7.70 7.83 (m, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 14.0, 22.5, 27.9, 29.2, 31.4, 50.0 (d, J C P = 13.2 Hz), 128.2 (d, J C P = 111.1 Hz), 128.6 (d, J C P = 12.3 Hz), 131.3 (d, J C P = 9.9 Hz), 131.6 (d, J C P = 10.7 Hz), 131.7 (d, J C P = 2.5 Hz), 133.0 (d, J C P = 107.0 Hz); 31 P NMR (CDCl 3 ) δ 24.7; HRMS (EI) Calcd for C 20 H 24 OPI: 438.0609, Found: 438.0613. S5

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