Supporting Information Rhodium(III)-Catalyzed Synthesis of Naphthols via C-H Activation of Sulfoxonium Ylides Youwei Xu,, Xifa Yang,, Xukai Zhou,, Lingheng Kong,, and Xingwei Li*, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China University of Chinese Academy of Sciences, Beijing 100049, China Email: xwli@dicp.ac.cn Table of Contents I. General Information... S2 II. Synthesis of Substrates... S2 (a) General procedure for preparation of sulfoxonium ylides... S2 (b) General procedures for the reaction... S2 III. Characterization Data... S3 IV. Gram-Scale Preparation and Transformations... S13 (a) Gram-Scale Preparation of 3aa... S13 (b) Transformations of 3aa... S14 V. Mechanistic Studies... S15 VI. References... S17 VII. NMR Spectra of Products... S18 S1
I. General Information All chemicals were obtained from commercial sources and were used as received unless otherwise noted. All reactions were carried out using Schlenk techniques or in a nitrogen-filled glove box in absolute ethanol. NMR Spectra were recorded on a 400 MHz NMR spectrometer in the solvent indicated. The chemical shift is given in dimensionless δ values and is frequency referenced relative to TMS in 1 H and 13 C NMR spectroscopy. The following abbreviations were used to describe peak splitting patterns when appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = double of doublet, dt = double of triplet, td = triple of doublet. HRMS data were obtained via ESI mode with TOF mass analyzer. Column chromatography was performed on silica gel (300-400 mesh) using ethyl acetate (EA)/petroleum ether (PE). II. Synthesis of Substrates (a) General procedure for preparation of sulfoxonium ylides Ylides 1a-1p were prepared according to the reported procedures. 1 To a stirred solution of potassium tert-butoxide (3.0 g, 27.2 mmol) in THF (30 ml) was added trimethylsulfoxonium iodide (5.0 g, 20.6 mmol) at room temperature. The resulting mixture is refluxed for 2h. Then reaction mixture is cooled to 0 C, followed by addition of acyl chlorides (7 mmol) in THF (5 ml). The reaction was allowed to room temperature and stirred for 3h. Next, the solvent was evaporated and water (15 ml) and ethyl acetate (20 ml) were added to the resulting slurry. The layers were separated and the aqueous layer was washed with ethyl acetate (2 x 30 ml) and the organic layers were combined. The organic solution was dried over anhydrous sodium sulphate (Na 2SO 4), filtered over a sintered funnel and evaporated to dryness. The crude product was purified by flash chromatography over silica gel using EtOAc/MeOH (95:5) to afford the corresponding sulfoxonium ylides. (b) General procedures for naphthol synthesis A pressure tube was charged with [Cp*Rh(MeCN) 3](SbF 6) 2 (10.0 mg, 6 mol %), Zn(OAc) 2 (3.7 mg, 10 mol %), sulfoxonium ylides (1, 0.2 mmol), alkyne (2, 0.22 mmol) and DCE (4 ml). The reaction mixture was stirred under N 2 condition at 80 C for 16 h. After that, the solvent was removed under reduced pressure and the residue was purified by silica gel chromatography using PE/EA to afford the product. S2
III. Characterization Data 3,4-diphenylnaphthalen-1-ol 2 White solid, 55.7 mg, yield: 94% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.29 (brs, 1H), 8.36 (d, J = 7.7 Hz, 1H), 7.53 (d, J = 8.6 Hz, 1H), 7.50 7.46 (m, 1H), 7.43 7.39 (m, 1H), 7.31 7.21 (m, 3H), 7.18 7.10 (m, 7H), 7.03 (s, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 152.4, 142.4, 139.4, 138.9, 134.0, 131.9, 129.9, 129.2, 127.8, 127.5, 126.5, 126.4, 126.2, 126.2, 124.5, 124.3, 122.1, 110.2. 6-methyl-3,4-diphenylnaphthalen-1-ol White solid, 57.1 mg, yield: 92% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.18 (brs, 1H), 8.26 (d, J = 9.1 Hz, 1H), 7.33 7.22 (m, 5H), 7.15 7.10 (m, 7H), 6.96 (s, 1H), 2.34 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 152.4, 142.5, 139.6, 139.0, 136.0, 134.3, 131.9, 129.9, 128.7, 127.7, 127.5, 126.6, 126.3, 126.1, 125.3, 122.5, 122.1, 109.6, 21.2. HRMS (ESI): calculated for C 23H 17O - 309.1285, found 309.1283. 6-(tert-butyl)-3,4-diphenylnaphthalen-1-ol White solid, 67.3 mg, yield: 95% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.16 (brs, 1H), 8.30 (d, J = 8.8 Hz, 1H), 7.62 7.58 (m, 2H), 7.30 7.23 (m, 3H), 7.18 7.11 (m, 7H), 6.98 (s, 1H), 1.25 (s, 9H). 13 C NMR (100 MHz, acetone-d 6) δ 152.3, 148.9, 142.6, 139.6, 138.9, 134.0, 131.9, 129.9, 129.3, 127.7, 127.5, 126.3, 126.1, 123.3, 122.5, 121.9, 121.4, 109.8, 34.6, 30.5. HRMS (ESI): calculated for C 26H 23O - 351.1754, found 351.1752. 6-methoxy-3,4-diphenylnaphthalen-1-ol Yellow solid, 61.4 mg, yield: 94% (purified by silica gel chromatography using PE/EA 10:1). 1 H S3
NMR (400 MHz, acetone-d 6) δ 9.16 (brs, 1H), 8.27 (d, J = 9.1 Hz, 1H), 7.30 7.20 (m, 3H), 7.18 7.09 (m, 8H), 6.91 (d, J = 2.5 Hz, 1H), 6.88 (s, 1H), 3.65 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 158.4, 152.5, 142.6, 139.7, 139.7, 135.5, 131.8, 129.8, 128.3, 127.8, 127.5, 126.4, 126.1, 123.8, 119.5, 116.3, 108.5, 105.4, 54.4. HRMS (ESI): calculated for C 23H 17O - 2 325.1234, found 325.1233. 3,4,6-triphenylnaphthalen-1-ol Yellow solid, 70.4 mg, yield: 95% (purified by silica gel chromatography using PE/EA 20:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.39 (brs, 1H), 8.46 (d, J = 8.6 Hz, 1H), 7.82 7.78 (m, 2H), 7.56 (d, J = 7.5 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.31 7.11 (m, 11H), 7.07 (s, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 152.5, 142.4, 141.2, 139.6, 139.3, 139.0, 134.4, 132.0, 129.9, 129.6, 128.9, 127.8, 127.6, 127.4, 127.1, 126.5, 126.2, 124.2, 124.0, 123.5, 123.0, 110.5. HRMS (ESI): calculated for C 28H 19O - 371.1441, found 371.1442. 6-fluoro-3,4-diphenylnaphthalen-1-ol White solid, 59.6 mg, yield: 95% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.45 (brs, 1H), 8.41 (dd, J = 9.0, 6.3 Hz, 1H), 7.33 7.25 (m, 4H), 7.16 7.12 (m, 8H), 7.02 (s, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 161.4 (d, J C-F = 243.6 Hz), 152.6, 142.0, 140.5, 139.0, 135.3 (d, J C-F = 8.8 Hz), 131.7, 129.8, 128.8 (d, J C-F = 5.2 Hz), 128.0, 127.6, 126.7, 126.4, 125.3 (d, J C-F = 9.3 Hz), 121.3, 114.3 (d, J C-F = 25.3 Hz), 109.8 (d, J C-F = 1.9 Hz), 109.4 (d, J C-F = 22.3 Hz). HRMS (ESI): calculated for C 22H 14FO - 313.1034, found 313.1036. 6-chloro-3,4-diphenylnaphthalen-1-ol White solid, 58.1 mg, yield: 88% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.54 (brs, 1H), 8.35 (d, J = 8.8 Hz, 1H), 7.51 7.45 (m, 2H), 7.35 7.27 (m, 3H), 7.20 7.14 (m, 7H), 7.05 (s, 1H). 1 H NMR (400 MHz, CDCl 3) δ 8.23 (d, J = 8.9 Hz, 1H), 7.60 (d, J = 1.8 Hz, 1H), 7.41 (dd, J = 8.9, 1.9 Hz, 1H), 7.30 7.24 (m, 3H), 7.16 7.09 (m, 7H), 6.90 (s, 1H), 5.90 (brs, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 152.5, 141.9, 140.6, 138.7, 134.9, 132.3, 131.8, 129.8, 128.5, 128.0, 127.6, 126.8, 126.4, 125.0, 124.9, 124.5, 122.6, 110.8. HRMS (ESI): calculated for C 22H 14ClO - 329.0739, found 329.0739. S4
6-bromo-3,4-diphenylnaphthalen-1-ol White solid, 64.8 mg, yield: 86% (purified by silica gel chromatography using PE/EA 20:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.52 (brs, 1H), 8.28 (d, J = 8.9 Hz, 1H), 7.68 (d, J = 1.8 Hz, 1H), 7.59 (dd, J = 8.9, 1.9 Hz, 1H), 7.34 7.27 (m, 3H), 7.21 7.12 (m, 7H), 7.07 (s, 1H). 1 H NMR (400 MHz, CDCl 3) δ 8.14 (d, J = 8.9 Hz, 1H), 7.77 (d, J = 1.8 Hz, 1H), 7.55 (dd, J = 8.9, 1.9 Hz, 1H), 7.30 7.24 (m, 3H), 7.18 7.08 (m, 7H), 6.89 (s, 1H), 5.39 (brs, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 152.6, 141.9, 140.5, 138.6, 135.3, 131.8, 129.9, 128.5, 128.2, 128.0, 127.6 (two signals overlapped), 126.8, 126.4, 124.5, 122.7, 120.8, 110.9. HRMS (ESI): calculated for C 22H 14BrO - 373.0234, found 373.0233. 3,4-diphenyl-6-(trifluoromethyl)naphthalen-1-ol White solid, 69.2 mg, yield: 95% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.70 (br, 1H), 8.56 (d, J = 8.8 Hz, 1H), 7.91 (s, 1H), 7.72 (dd, J = 8.8, 1.6 Hz, 1H), 7.36 7.27 (m, 3H), 7.21 7.14 (m, 8H). 13 C NMR (100 MHz, acetone-d 6) δ 152.5, 141.7, 140.8, 138.4, 132.9, 131.8, 130.1, 129.8, 128.0, 127.7 (q, J C-F = 31.6 Hz), 127.7, 127.0, 126.5, 125.5, 124.7 (q, J C-F = 271.5 Hz), 123.9, 123.7 (q, J C-F = 4.7 Hz), 119.8 (q, J C-F = 3.1 Hz), 112.6. HRMS (ESI): calculated for C 23H 14F 3O - 363.1002, found 363.1001. 6-nitro-3,4-diphenylnaphthalen-1-ol Yellow solid, 25.3 mg, yield: 37% (purified by silica gel chromatography using PE/EA 10:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.86 (br, 1H), 8.53 8.49 (m, 2H), 8.21 (dd, J = 9.2, 2.3 Hz, 1H), 7.38 7.31 (m, 3H), 7.26 7.18 (m, 8H). 13 C NMR (100 MHz, acetone-d 6) δ 152.5, 146.3, 141.5, 141.3, 138.0, 132.9, 131.8, 131.2, 129.8, 128.1, 127.8, 127.2, 126.7, 126.4, 124.4, 122.7, 117.6, 114.0. HRMS (ESI): calculated for C 22H 14NO - 3 340.0979, found 340.0977. S5
7-methyl-3,4-diphenylnaphthalen-1-ol White solid, 58.1 mg, yield: 94% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.14 (br, 1H), 8.14 (s, 1H), 7.43 (d, J = 8.7 Hz, 1H), 7.29 7.20 (m, 4H), 7.15 7.10 (m, 7H), 7.00 (s, 1H), 2.50 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 152.0, 142.5, 139.6, 137. 9, 134.1, 132.3, 131.8, 129.9, 129.1, 128.6, 127.7, 127.5, 126.3, 126.2, 126.0, 124.4, 121.1, 110.3, 20.8. HRMS (ESI): calculated for C 23H 17O - 309.1285, found 309.1283. 7-bromo-3,4-diphenylnaphthalen-1-ol White solid, 73.6 mg, yield: 98% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.59 (brs, 1H), 8.49 (d, J = 1.8 Hz, 1H), 7.53 (dd, J = 9.1, 2.0 Hz, 1H), 7.45 (d, J = 9.1 Hz, 1H), 7.31 7.25 (m, 3H), 7.15 7.14 (m, 7H), 7.08 (s, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 151.5, 141.9, 139.7, 138.8, 132.5, 131.8, 129.8, 129.6, 129.4, 128.6, 127.9, 127.6, 126.7, 126.4, 125.4, 124.3, 118.4, 111.5. HRMS (ESI): calculated for C 22H 14BrO - 373.0234, found 373.0234. 8-chloro-3,4-diphenylnaphthalen-1-ol Yellow solid, 62.3 mg, yield: 94% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.20 (brs, 1H), 7.52 (dd, J = 7.4, 1.1 Hz, 1H), 7.46 (dd, J = 8.6, 1.1 Hz, 1H), 7.32 7.26 (m, 4H), 7.20 7.14 (m, 7H), 7.10 (s, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 153.0, 141.5, 140.0, 139.4, 136.7, 131.8, 129.9, 129.7, 129.6, 127.9, 127.9, 127.6, 126.7, 126.4, 126.2, 126.0, 120.8, 113.5. HRMS (ESI): calculated for C 22H 14ClO - 329.0739, found 329.0740. 8-fluoro-3,4-diphenylnaphthalen-1-ol White solid, 60.5 mg, yield: 96% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR S6
(400 MHz, acetone-d 6) δ 8.97 (brs, 1H), 7.37 7.23 (m, 5H), 7.19 7.13 (m, 8H), 7.05 (s, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 159.4 (d, J C-F = 254.1 Hz), 152.1 (d, J C-F = 3.0 Hz), 141.7, 140.4, 139.3, 136.8 (d, J C-F = 3.5 Hz), 131.7, 129.7, 129.2 (d, J C-F = 3.0 Hz), 127.9, 127.6, 126.7, 126.4, 126.3 (d, J C-F =9.2 Hz), 122.7 (d, J C-F = 4.3 Hz), 114.1 (d, J C-F = 10.2 Hz), 112.6 (d, J C-F = 1.8 Hz), 109.8 (d, J C-F = 21.8 Hz). HRMS (ESI): calculated for C 22H 14FO - 313.1034, found 313.1033. 8-methyl-3,4-diphenylnaphthalen-1-ol Yellow solid, 21.3 mg, yield: 34% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.07 (brs, 1H), 7.34 7.32 (m, 1H), 7.30 7.24 (m, 3H), 7.23 7.19 (m, 2H), 7.16 7.11 (m, 7H), 6.99 (s, 1H), 3.01 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 154.8, 142.2, 140.2, 138.7, 135.7, 135.3, 131.9, 129.8, 129.7, 127.7, 127.5 (two overlapping signals), 126. 3, 126.1, 125.9, 124.8, 123.5, 111.6, 24.5. HRMS (ESI): calculated for C 23H 17O - 309.1285, found 309.1284. 4,5-diphenylbenzo[b]thiophen-7-ol White solid, 20.2 mg, yield: 33% (purified by silica gel chromatography using PE/EA 20:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.43 (brs, 1H), 7.61 (d, J = 5.4 Hz, 1H), 7.29 7.22 (m, 3H), 7.20 7.15(m, 7H), 7.09 (d, J = 5.4 Hz, 1H), 6.93 (s, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 151.1, 141.8, 141.7, 139.9, 138.6, 131.0, 130.1, 127.8, 127.7, 127.6, 127.1, 126.7, 126.4, 126.2, 124.3, 110.8. HRMS (ESI): calculated for C 20H 13OS - 301.0693, found 301.0693. 3,4-di-p-tolylnaphthalen-1-ol White solid, 60.3 mg, yield: 93% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.18 (brs, 1H), 8.34 (d, J = 8.2 Hz, 1H), 7.52 (d, J = 8.4 Hz, 1H), 7.48 7.35 (m, 2H), 7.11 6.96 (m, 9H), 2.31 (s, 3H), 2.22 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 152.2, 139.6, 138.8, 136.5, 135.7, 135.5, 134.3, 131.7, 129.8, 129.1, 128.5, 128.3, 126.4, 126.3, 124.4, 124.2, 122.0, 110.4, 20.4, 20.2. HRMS (ESI): calculated for C 24H 19O - 323.1441, found 323.1441. S7
3,4-bis(4-(tert-butyl)phenyl)naphthalen-1-ol White solid, 80.2 mg, yield: 98% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.21 (brs, 1H), 8.34 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 8.4 Hz, 1H), 7.48 7.40 (m, 2H), 7.32 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.4 Hz, 2H), 7.07 7.04 (m, 5H), 1.31 (s, 9H), 1.24 (s, 9H). 13 C NMR (100 MHz, acetone-d 6) δ 152.3, 149.0, 148.6, 139.5, 138.9, 136.5, 134.1, 131.6, 129.6, 129.2, 126.4, 126.3, 124.5, 124.3, 124.2, 122.0, 110.3, 34.1, 34.0, 30.8, 30.7. HRMS (ESI): calculated for C 30H 31O - 407.2380, found 407.2380. 3,4-bis(4-methoxyphenyl)naphthalen-1-ol Yellow solid, 64.1 mg, yield: 90% (purified by silica gel chromatography using PE/EA 10:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.16 (brs, 1H), 8.33 (d, J = 8.1 Hz, 1H), 7.55 (d, J = 8.3 Hz, 1H), 7.47 7.37 (m, 2H), 7.08 7.01 (m, 5H), 6.85 (d, J = 8.4 Hz, 2H), 6.73 (d, J = 8.5 Hz, 2H), 3.77 (s, 3H), 3.71 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 158.3, 158.2, 152.2, 138.7, 134.8, 134.5, 132.8, 131.6, 131.0, 128.8, 126.4, 126.3, 124.3, 124.2, 122.0, 113.2, 113.0, 110.5, 54.5, 54.5. HRMS (ESI): calculated for C 24H 19O - 3 355.1340, found 355.1339. 3,4-bis(4-fluorophenyl)naphthalen-1-ol White solid, 62.0 mg, yield: 93% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.36 (brs, 1H), 8.37 8.35 (m, 1H), 7.52 7.48 (m, 2H), 7.46 7.42 (m, 1H), 7.17 7.13 (m, 4H), 7.09 7.04 (m, 2H), 7.01 (s, 1H), 6.98 6.93 (m, 2H). 13 C NMR (100 MHz, S8
acetone-d 6) δ 161.6 (d, J C-F = 243.9 Hz), 161.4(d, J C-F = 244.0 Hz), 152.6, 138.5, 138. 4, 138.2, 135.4, 135.4, 134.0, 133.6 (d, J C-F = 8.0 Hz), 131.7 (d, J C-F = 8.0 Hz), 128.2, 126.8, 126.0, 124.7, 124.3, 122.2, 114.6 (d, J C-F = 21.3 Hz), 114.4 (d, J C-F = 21.4 Hz), 110.0. HRMS (ESI): calculated for C 22H 13F 2O - 331.0940, found 331.0941. 3,4-bis(4-bromophenyl)naphthalen-1-ol Yellow solid, 82.8 mg, yield: 91% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.39 (brs, 1H), 8.36 (d, J = 8.1 Hz, 1H), 7.54 7.45 (m, 5H), 7.40 (d, J = 8.2 Hz, 2H), 7.13 7.10 (m, 4H), 6.99 (s, 1H). 1 H NMR (400 MHz, CDCl 3) δ 8.31 (d, J = 8.2 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 7.51 (t, J = 7.3 Hz, 1H), 7.45 7.42 (m, 3H), 7.31 (d, J = 8.3 Hz, 2H), 7.02 (d, J = 8.2 Hz, 2H), 6.96 (d, J = 8.3 Hz, 2H), 6.88 (s, 1H), 6.60 (brs, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 152.9, 141.3, 138.4, 137.7, 133.8, 133.7, 131.9, 131.0, 130.8, 127.8, 127.0, 125.9, 124.9, 124.4, 122.2, 120.4, 120.2, 109.8. HRMS (ESI): calculated for C 22H 13Br 2O - 450.9339, found 450.9339. 3,4-bis(4-(trifluoromethyl)phenyl)naphthalen-1-ol Yellow solid, 76.0 mg, yield: 88% (purified by silica gel chromatography using PE/EA 20:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.53 (brs, 1H), 8.40 (d, J = 8.2 Hz, 1H), 7.66 (d, J = 8.0 Hz, 2H), 7.57 7.54 (m, 3H), 7.52 7.46 (m, 2H), 7.42 7.37 (m, 4H), 7.05 (s, 1H). 1 H NMR (400 MHz, CDCl 3) δ 8.32 (d, J = 8.3 Hz, 1H), 7.59 7.53 (m, 4H), 7.50 7.45 (m, 3H), 7.30 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.1 Hz, 2H), 6.90 (s, 1H), 5.56 (brs, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 153.2, 146.0, 143.4, 137.7, 133.5, 132.6, 130.6, 128.5, 128.2, 127.9, 127.3, 125.8, 125.2, 124.8 (q, J C-F = 3.8 Hz), 124.6 (q, J C-F = 3.7 Hz), 124.6, 124.5 (q, J C-F = 271.3 Hz), 124.5 (q, J C-F = 271.5 Hz), 122.3, 109.7. HRMS (ESI): calculated for C 24H 13F 6O - 431.0876, found 431.0878. S9
3,4-bis(3-fluorophenyl)naphthalen-1-ol Yellow solid, 60.6 mg, yield: 91% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.41 (brs, 1H), 8.38 (d, J = 8.4 Hz, 1H), 7.54 7.44 (m, 3H), 7.38 7.33 (m, 1H), 7.27 7.21 (m, 1H), 7.08 7.01 (m, 4H), 6.98 6.92 (m, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 162.5 (d, J C-F = 244.6 Hz), 162.1 (d, J C-F = 243.8 Hz), 152.9, 144.5 (d, J C-F = 7.9 Hz), 141.7 (d, J C-F = 7.9 Hz), 137.7, 137.7, 133.6, 129.6 (d, J C-F = 8.6 Hz), 129.5 (d, J C-F = 8.5 Hz), 128.0 (d, J C-F = 2.8 Hz), 127.0, 126.0, 125.9 (d, J C-F = 2.8 Hz), 125.0, 124.4, 122.2, 118.5 (d, J C-F = 21.0 Hz), 116. 5 (d, J C-F = 21.8 Hz), 113.5 (d, J C-F = 21.0 Hz), 113.2 (d, J C-F = 21.1 Hz), 109.8. HRMS (ESI): calculated for C 22H 13F 2O - 331.0940, found 331.0938. 3,4-di-m-tolylnaphthalen-1-ol White solid, 62.3 mg, yield: 96% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.21 (brs, 1H), 8.34 (d, J = 8.4 Hz, 1H), 7.53 (d, J = 8.5 Hz, 1H), 7.49 7.45 (m, 1H), 7.42 7.38 (m, 1H), 7.17 (t, J = 7.5 Hz, 1H), 7.07 7.01 (m, 5H), 6.96 6.93 (m, 3H), 2.26 (s, 3H), 2.19 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 152.3, 142.3, 139.4, 138.8, 137.0, 136.8, 134.1, 132.5, 130.7, 129.3, 128.9, 127.6, 127.4, 127.0, 127.0, 126.8, 126.4, 126.4, 124.4, 124.2, 122.0, 110.3, 20.6, 20.5. HRMS (ESI): calculated for C 24H 19O - 323.1441, found 323.1444. 3,4-bis(2-fluorophenyl)naphthalen-1-ol White solid, 65.8 mg, yield: 99% (purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.42 (brs, 1H), 8.38 (d, J = 8.2 Hz, 1H), 7.55 7.42 (m, 3H), 7.34 7.29 (m, 1H), 7.25 7.15 (m, 3H), 7.10 6.97 (m, 5H). 13 C NMR (100 MHz, acetone-d 6) δ 160.6 (d, J C-F = 244.0 Hz), 159.5 (d, J C-F = 244.8 Hz), 152.9, 134.1, 133.7, 133.4 (d, J C-F = 3.2 Hz), 131.8 (d, J C-F = 3.1 S10
Hz), 129.3 (d, J C-F = 24.9 Hz), 129.2(d, J C-F = 25.1 Hz), 127.0, 126.5, 126.3, 125.7, 125.0, 124.6, 124.1, 123.7 (d, J C-F = 3.5 Hz), 123. 6 (d, J C-F = 3.6 Hz), 122.3, 115.1 (d, J C-F = 22.4 Hz), 115.0 (d, J C-F = 22.6 Hz), 110.1. HRMS (ESI): calculated for C 22H 13F 2O - 331.0940, found 331.0942. 3,4-di(thiophen-2-yl)naphthalen-1-ol Yellow solid, 55.2 mg, yield: 89% (purified by silica gel chromatography using PE/EA 20:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.47 (brs, 1H), 8.33 8.30 (m, 1H), 7.64 7.58 (m, 2H), 7.50 7.47 (m, 2H), 7.36 (d, J = 4.6 Hz, 1H), 7.28 (s, 1H), 7.19 7.17 (m, 1H), 7.04 6.98 (m, 2H), 6.95 6.93 (m, 1H). 13 C NMR (100 MHz, acetone-d 6) δ 153.6, 143.2, 139.7, 135.6, 133.4, 130.0, 127.2, 127.1, 127.0, 126.9, 126.7, 126.6, 126.3, 125.0, 124.3, 122.0, 120.3, 109.3. HRMS (ESI): calculated for C 18H 11OS - 2 307.0257, found 307.0255. methyl-4-hydroxy-2-phenyl-1-naphthoate Yellow solid, 21.0 mg, yield: 38% (purified by silica gel chromatography using PE/EA 20:1 to 10:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.64 (brs, 1H), 8.34 (dd, J = 8.3, 0.7 Hz, 1H), 7.97 (d, J = 8.3 Hz, 1H), 7.63 7.59 (m, 1H), 7.57 7.53 (m, 1H), 7.49 7.43 (m, 4H), 7.41 7.38 (m, 1H), 7.00 (s, 1H), 3.61 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 169.5, 154.4, 141.5, 139.5, 131.8, 128.4, 128.2, 127.8, 127.5, 125.2, 124.9, 123.7, 122.3, 121.9, 109.4, 51.2. HRMS (ESI): calculated for C 18H 13O - 3 277.0870, found 277.0869. methyl-4-hydroxy-1-phenyl-2-naphthoate White solid, 15.1 mg, yield: 27% (purified by silica gel chromatography using PE/EA 20:1 to 10:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.43 (brs, 1H), 8.35 (d, J = 8.4 Hz, 1H), 7.60 7.56 (m, 1H), 7.52 7.40 (m, 5H), 7.32 (s, 1H), 7.28 7.25 (m, 2H), 3.50 (s, 3H). 1 H NMR (400 MHz, CDCl 3) δ 8.29 (d, J = 7.9 Hz, 1H), 7.58 7.54 (m, 2H), 7.47 7.40 (m, 5H), 7.29 7.26 (m, 3H), 6.26 (brs, 1H), 3.58 (s, S11
3H). 13 C NMR (100 MHz, acetone-d 6) δ 168.2, 152.5, 139.3, 133.7, 132.2, 130.2, 129.1, 127.8, 127.1, 127.0, 126.9, 126.3, 126.2, 122.1, 107.1, 100.0, 51.1. HRMS (ESI): calculated for C 18H 13O 3-277.0870, found 277.0869. methyl 2-(4-hydroxy-2-phenylnaphthalen-1-yl)benzoate Yellow solid, 62.4 mg, yield: 88%, 6:1 (only the major isomer was shown, purified by silica gel chromatography using PE/EA 20:1). 1 H NMR (400 MHz, acetone-d 6) δ 9.19 (brs, 1H), 8.34 (d, J = 8.3 Hz, 1H), 7.85 (d, J = 7.7 Hz, 1H), 7.46 7.43 (m, 2H), 7.39 7.34 (m, 2H), 7.29 (d, J = 8.4 Hz, 1H), 7.19 7.09 (m, 7H), 7.01 (s, 1H), 3.41 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 167.0, 152.3, 142.4, 140.5, 138.1, 133.7 (two signals overlapped), 132.9, 131.3, 129.6, 129.6, 128.7, 127.5, 127.0, 126.4, 126.3, 125.6, 124.3, 124.1, 122.1, 110.2, 51.0. HRMS (ESI): calculated for C 24H 17O 3-353.1183, found 353.1183. 4-methyl-3-phenylnaphthalen-1-ol Colorless oil, 39.0 mg, yield: 83%, >20:1 (only the major isomer was shown, purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 8.96 (brs, 1H), 8.32 (dd, J = 8.3, 0.8 Hz, 1H), 8.04 (d, J = 8.4 Hz, 1H), 7.60 7.56 (m, 1H), 7.52 7.44 (m, 3H), 7.39 7.36 (m, 3H), 6.86 (s, 1H), 2.46 (s, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 151.0, 142.9, 139.2, 134.1, 129.5, 128.1, 126.7, 126.5, 124.6, 124.4, 124.3, 122.4, 121.3, 110.2, 14.9. HRMS (ESI): calculated for C 17H 13O - 233.0972, found 233.0970. 4-ethyl-3-phenylnaphthalen-1-ol Colorless oil, 40.0 mg, yield: 80%, 17:1 (only the major isomer was shown, purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 8.96 (brs, 1H), 8.33 (dd, J = 8.3, 0.9 Hz, 1H), 8.08 (d, J = 8.5 Hz, 1H), 7.59 7.55 (m, 1H), 7.50 7.43 (m, 3H), 7.40 7.35 (m, 3H), 6.79 (s, 1H), 2.91 (q, J = 7.5 Hz, 2H), 1.16 (t, J = 7.5 Hz, 3H). 13 C NMR (100 MHz, acetone-d 6) δ S12
150.8, 143.1, 139.1, 133.0, 129.0, 128.1, 128.0, 126.8, 126.5, 125.0, 124.3, 124.2, 122.7, 110.3, 21.6, 15.6. HRMS (ESI): calculated for C 18H 15O - 247.1128, found 247.1126. 3-phenyl-4-propylnaphthalen-1-ol Colorless oil, 44.7 mg, yield: 85%, 17:1 (only the major isomer was shown, purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 8.99 (brs, 1H), 8.33 (dd, J = 8.3, 0.9 Hz, 1H), 8.07 (d, J = 8.5 Hz, 1H), 7.58 7.54(m, 1H), 7.49 7.43 (m, 3H), 7.39 7.34 (m, 3H), 6.80 (s, 1H), 2.90 2.82 (m, 2H), 1.65 1.55 (m, 2H), 0.84 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 150.9, 143.2, 139.4, 133.3, 129.2, 128.0, 126.7, 126.7, 126.5, 124.9, 124.5, 124.2, 122.6, 110.3, 30.8, 24.7, 13.8. HRMS (ESI): calculated for C 19H 17O - 261.1285, found 261.1284. 4-butyl-3-phenylnaphthalen-1-ol Yellow oil, 44.4 mg, yield: 80%, 14:1 (only the major isomer was shown, purified by silica gel chromatography using PE/EA 30:1). 1 H NMR (400 MHz, acetone-d 6) δ 8.95 (brs, 1H), 8.33 (dd, J = 8.3, 0.9 Hz, 1H), 8.08 (d, J = 8.5 Hz, 1H), 7.58 7.54 (m, 1H), 7.49 7.43 (m, 3H), 7.39 7.34 (m, 3H), 6.80 (s, 1H), 2.91 2.87 (m, 2H), 1.61 1.53 (m, 2H), 1.32 1.23 (m, 2H), 0.79 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, acetone-d 6) δ 150.8, 143.3, 139.3, 133.3, 129.2, 128.0, 126.8, 126.7, 126.4, 124.9, 124.4, 124.2, 122.6, 110.3, 33.7, 28.2, 22.7, 13.2. HRMS (ESI): calculated for C 20H 19O - 275.1441, found 275.1441. IV. Gram-Scale Preparation and Transformations (a) Gram-Scale Preparation of 3aa A pressure tube was charged with [Cp*Rh(MeCN) 3](SbF 6) 2 (255 mg, 6 mol %), Zn(OAc) 2 (94 mg, 10 mol %), sulfoxonium ylides (1.0 g, 5.1 mmol), alkyne (1.1 equiv). and DCE (80 ml). The reaction mixture was stirred under N 2 condition at 80 C for 24 h. After that, the solvent was removed under reduced pressure and the residue was purified by silica gel chromatography using PE/EA to afford S13
product 3aa as a white solid (1.38 g, 91%). (b) Transformations of 3aa Naphthol 3aa (296.4 mg, 1.0 mmol) was dissolved in DCM (5.0 ml) and then cooled to -78 o C. Triethylamine (TEA, 253.0 μl, 1.5 mmol) was added, followed by addition of trifluoromethanesulfonic anhydride (Tf 2O, 208.0 μl, 1.5 mmol) within 5 minutes via a syringe. The resulting solution was gradually warmed to room temperature and stirred for 2 h until 3aa had been completely consumed as determined by TLC. The solvent was then removed under reduced pressure to get the crude product, which was purified by flash column chromatography on silica gel, eluted by ethyl acetate/hexane = 1:100 to afford the pure product 4a as a yellow solid (404.0 mg, 94% yield). 2 4a (42.8 mg, 0.1 mmol), phenylacetylene (33.0 μl, 0.3 mmol), bis(triphenylphosphine)palladium(ii) dichloride (Pd(PPh 3) 2Cl 2, 7.0 mg, 0.01 mmol), copper(i) bromide (CuBr, 0.7 mg, 0.005 mmol), diisopropylethylamine (DIPEA, 52.0 μl, 0.3 mmol), and DMF (1.0 ml) were added to a pressure tube. The reaction mixture was heated to 80 C under N 2 condition for 5 h until 4a had been completely consumed as determined by TLC. Work-up: the reaction mixture was cooled down to room temperature and then diluted with ethyl acetate (50 ml). The organic phase was washed with brine (4*10 ml) and dried with MgSO 4. The solvent was removed under reduced pressure to get the crude product, which was purified by flash column chromatography on silica gel, eluted by PE to afford the pure product as a white solid (90% yield). 3 1 H NMR (400 MHz, CDCl 3) δ 8.56 (d, J = 8.3 Hz, 1H), 7.92 (s, 1H), 7.73 7.68 (m, 3H), 7.62 (t, J = 7.3 Hz, 1H), 7.48 7.39 (m, 4H), 7.35 7.30 (m, 3H), 7.23 7.17 (m, 7H). 13 C NMR (100 MHz, CDCl 3) δ 141.2, 138.6, 138.5, 138.1, 132.7, 132.6, 132.5, 131.7, 131.3, 130.0, 128.4, 128.4, 127.8, 127.7, 127.3, 126.9, 126.7, 126.5, 126.4, 126.2, 123.4, 120.5, 94.4, 87.5. 4a (42.8 mg, 0.1 mmol), ethyl acrylate (106.4 μl, 1.0 mmol), palladium(ii) aceate (Pd(OAc) 2, 4.4 mg, 0.02 mmol), triphenylphosphine (PPh 3, 15.7 mg, 0.06 mmol), potassium carbonate (K 2CO 3, 27.6 S14
mg, 0.2 mmol), and toluene (1.0 ml) were added to a pressure tube. The reaction mixture was heated at 110 C under N 2 condition for 6 h until 4a had been completely consumed as determined by TLC. The reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure to get the crude product, which was purified by flash column chromatography on silica gel, eluted by PE/EA = 40:1 to afford the pure product as a white solid (85% yield). 3 1 H NMR (400 MHz, CDCl 3) δ 8.62 (d, J = 15.8 Hz, 1H), 8.29 (d, J = 8.4 Hz, 1H), 7.87 (s, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.61 7.57 (m, 1H), 7.48 7.44 (m, 1H), 7.34 7.29 (m, 3H), 7.20 7.14 m, 7H), 6.61 (d, J = 15.7 Hz, 1H), 4.33 (q, J = 7.1 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz, CDCl 3) δ 166.9, 141.5, 141.3, 140.0, 138.6, 138.3, 133.0, 131.3, 131.2, 130.7, 130.0, 127.9, 127.7, 127.7, 127.4, 127.0, 126.5, 126.5, 126.5, 123.3, 121.2, 60.6, 14.3. HRMS (ESI): calculated for C 27H 23O + 2 379.1693, found 379.1690. V. Mechanistic Studies A pressure tube was charged with Zn(OAc) 2 (1.8 mg, 10 mol %), sulfoxonium ylides (19.6 mg, 0.1 mmol), CD 3OD (36 mg, 10 eq), and DCE (2 ml). The reaction mixture was stirred under N 2 condition at 80 C for 12 h. After that, the solvent was removed under reduced pressure and the residue was purified by silica gel chromatography using EA to afford compound, which was characterized by 1 H NMR spectroscopy. 1 H NMR analysis of 1a revealed no deuteration at the 2-position of phenyl ring or the α-position of the carbonyl. S15
A pressure tube was charged with [Cp*Rh(MeCN) 3](SbF 6) 2 (5 mg, 6 mol %), Zn(OAc) 2 (1.8 mg, 10 mol %), sulfoxonium ylides (19.6 mg, 0.1 mmol), CD 3OD (36 mg, 10 eq) and DCE (2 ml). The reaction mixture was stirred under N 2 condition at 80 C for 1 h. After that, the solvent was removed under reduced pressure and the residue was purified by silica gel chromatography using EA to afford compound, which was characterized by 1 H NMR spectroscopy. 1 H NMR analysis of 1a revealed 7% deuteration at the 2-position of phenyl ring and 10% deuteration the α-position of the carbonyl. Two pressure tubes were charged with [Cp*Rh(MeCN) 3](SbF 6) 2 (10.0 mg, 6 mol %), Zn(OAc) 2 (3.7 mg, 10 mol %), sulfoxonium ylides (1a or 1a-d5, 0.2 mmol), alkyne (2g, 0.22 mmol) and DCE (4 ml). The reaction mixture was stirred under N 2 condition at 80 C for 15 min. After that, the reaction was S16
cooled to 0 o C rapidly and was quenched with pentane. Then the solvent was removed under vacuum and the residue was purified by silica gel chromatography using PE/EA to afford compound 3ag and 3ag-d4 (20% yield in total). The KIE value was determined to be k H/k D = 1.3 on the basis of 1 H NMR analysis. VI. References (1) (a) Vaitla, J.; Bayer, A.; Hopmann, K. H. Angew. Chem., Int. Ed. 2017, 56, 4277; (b) Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1965, 87, 1353; (c) Wang, D.; Schwinden, M. D.; Radesca, L.; Patel, B.; Kronenthal, D.; Huang, M. H.; Nugent, W. A. J. Org. Chem. 2004, 69, 1629; (d) Dias, R. M. P.; Burtoloso, A. C. B. Org. Lett. 2016, 18, 3034; (d) Phelps, A. M.; Chan, V. S.; Napolitano, J. G.; Krabbe, S. W.; Schomaker, J. M.; Shekhar, S. J. Org. Chem. 2016, 81, 4158. (2) Chai, G.; Lu, Z.; Fu, C.; Ma, S. Chem. Eur. J. 2009, 15, 11083. (3) Peng, S.; Wang, L.; Wang, J. Chem. Eur. J. 2013, 19, 13322. S17
VII. NMR Spectra of Products S18
S19
S20
S21
S22
S23
S24 H2O
S25
S26
S27
S28
S29
S30
S31
S32
S33
H 2O CD 3COCD 3 S34
S35
S36
S37
S38 H 2O
H 2O CD 3COCD 3 S39
H 2O CD 3COCD 3 S40
S41
S42
S43
S44
S45
S46 H 2O CD 3COCD 3
H 2O CD 3COCD 3 S47
S48
S49
S50
S51
S52
S53
S54
S55
S56