Nickel Catalyzed C O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains

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1 Supporting Information Nickel Catalyzed C O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains Xiangqian Liu, Jiaqi Jia and Magnus Rueping * RWTH Aachen University, Institute of Organic Chemistry, Landoltweg 1, D Aachen, Germany. Magnus.Rueping@rwth-aachen.de Table of Contents General Methods Preparation of alkylzinc bromides General procedure for the decarbonylative alkylation of phenyl esters General procedure for the alkylation of pivaloyl esters Characterization of the products General procedures for the application of NiCl 2 catalyst References NMR spectra S1

2 General Methods. Unless otherwise noted, all commercially available compounds were used as provided without further purification. Solvents for chromatography were technical grade and distilled prior to use. Dry toluene, 1,2-dichloroethane (DCE), chloroform and chlorobenzene used in reactions were obtained by distilling over calcium hydride and were stored over activated molecular sieves (4 Å). Dry isopropyl ether (ipr 2 O), diethyl ether (Et 2 O), tetrahydrofuran (THF) and toluene used in reactions were obtained by distilling over sodium-benzophenone ketyl. Analytical thin-layer chromatography (TLC) was performed on Macherey-Nagel silica gel 60 aluminium plates with F-254 indicator, visualized by UV irradiation. Column chromatography was performed using Macherey-Nagel silica gel (particle size mm). 1 H-NMR and 13 C-NMR spectra were recorded on a vnmrs-400 or vnmrs-600 spectrometer in CDCl 3 with residual proton signal of the deuterated solvents as internal reference (δh = 7.26 ppm and δc = 77 ppm for CDCl 3 ). Data are reported in the following order: chemical shift (δ) in ppm; multiplicities are indicated s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), dd (doublet of doublet), tt (triplet of triplet), dt (doublet of triplet), td (triplet of doublet); coupling constants (J) are in Hertz (Hz). IR spectra were recorded on a Jasco FT/IR-420 spectrometer and are reported in terms of frequency of absorption (cm -1 ). Mass spectra were acquired on a Finnigan SSQ7000 (EI/CI) spectrometer and high resolution mass spectra on a Finnigan MAT 95 (EI/CI) or on a ThermoFisher Scientific LTQ Orbitrap XL (ESI). Melting points were recorded on a Büchi 560 Melting Point Apparatus. S2

3 Preparation of alkylzinc bromide: In a dry and argon-flushed Schlenk tube equipped with a magnetic stir bar, freshly cut lithium (139 g, 20 mmol) and naphthalene (2.6 g, 20 mmol) are dissolved in THF (20 ml). The mixture is stirred for 2 hours at room temperature, until all lithium is consumed. A solution of dry ZnCl 2 (1.36 g, 10 mmol) in THF (20 ml) is added dropwise. The obtained active zinc was washed several times with fresh THF to remove naphthalene. Alkyl bromide (10 mmol) was then added and the reaction was heated to 70 C for 5 h (GC analysis was used to determine the conversion). The concentration of the organozinc reagent was determined by titration following the procedure of Knochel [1] : A flame-dried 4 ml vial was charged with I 2 (127.0 mg, 0.50 mmol) and flushed with argon. The iodine was dissolved in 2.0 ml of a 0.5M solution of LiCl in anhydrous THF. The solution was cooled to 0 C using an ice bath and the organozinc reagent was added dropwise until the brown red/brownish color had disappeared. General procedure for the decarbonylative alkylation of phenyl esters (General Procedure 1): Typical procedure for the nickel-catalyzed decarbonylative alkylation of phenyl ester 1a. An oven-dried tube with a teflon sealed screwcap was charged with a magnetic stir bar, catalyst [Ni(cod) 2 ] (6.8 mg, mmol), dcype (10.6 mg, mmol), 1a (62 mg, 0.25 mmol) and ipr 2 O (0.7 ml) in a glovebox filled with argon. The reaction mixture was stirred at room temperature for 5 min, then n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was added slowly. The tube was sealed, removed from the glovebox, and the mixture stirred at 150 C for 18 h. After cooling to room temperature, the mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2-pentylnaphthalene as a colorless oil. S3

4 General procedure for the alkylation of pivaloyl esters (General Procedure 2): Typical procedure for the nickel-catalyzed alkylation of 2-naphthyl pivalate 2a. An oven-dried tube with a teflon sealed screwcap was charged with a magnetic stir bar, catalyst [Ni(cod) 2 ] (3.4 mg, mmol), dcype (5.3 mg, mmol), 2a (57 mg, 0.25 mmol) and ipr 2 O (0.7 ml) in a glovebox filled with argon. The reaction mixture was stirred at room temperature for 5 min, then n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was added slowly. The tube was sealed, removed from the glovebox, and the mixture stirred at 70 C for 18 h. After cooling to room temperature, the mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2- n pentylnaphthalene as a colorless oil. 2-Pentylnaphthalene According to the general procedure 1 or 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.64 (s, 1H), (m, 2H), 7.36 (dd, J = 8.4, 1.6 Hz, 1H), 2.80 (t, J = 7.6 Hz, 2H), (m, 2H), (m, 4H), 0.94 (t, J = 6.9 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 140.4, 133.6, 131.9, 127.7, 127.6, 127.5, 127.4, 126.3, 125.8, 124.9, 36.1, 31.5, 31.1, 22.6, The physical data were identical in all respects to those previously reported. 2 1-Pentylnaphthalene According to the general procedure 1 or 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 8.09 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 7.8 Hz, 1H), 7.74 (d, J = 8.2 Hz, 1H), (m, 1H), (m, 1H), 7.43 (t, J = 7.6 Hz, 1H), 7.36 (d, J = 6.9 Hz, 1H), 3.10 (t, J = 7.9 Hz, 2H), (m, 2H), (m, 4H), 0.96 (t, J = 7.1 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 139.0, , 131.9, 128.7, 126.4, 125.8, 125.6, 125.5, 125.3, 123.9, 33.1, 32.0, 30.6, 22.6, The physical data were identical in all respects to those previously reported. 3 S4

5 2-Methoxy-6-pentylnaphthalene According to the general procedure 1, white solid was obtained after column chromatography, m.p o C. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.55 (s, 1H), 7.31 (dd, J = 8.4, 1.8 Hz, 1H), (m, 2H), 3.92 (s, 3H), 2.75 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 4H), (m, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ157.0, 138.1, 132.8, 129.1, 128.9, 127.9, 126.6, 126.1, 118.5, 105.6, 55.3, 35.9, 31.5, 31.2, 22.6, 14.1; IR (ATR): ~ = 2923, 2331, 2082, 1912, 1603, 1464, 1386, 1231, 1031, 818, 689; MS (EI): m/z (%) = 229 ([M+H] +, 20), 228 ([M] +, 99), 172 (18), 171 (100), 128 (14); HRMS (EI+, m/z): calculated for C 16 H 21 O [M+H] + : ; found: Pentyl-1,1'-biphenyl According to the general procedure 1 or 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.60 (d, J = 7.1 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.34 (t, J = 7.4 Hz, 1H), 7.27 (d, J = 8.2 Hz, 2H), 2.66 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 4H), 0.93 (t, J = 7.0 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 142.1, 141.2, 138.5, 128.8, 128.7, , , 126.9, 35.6, 31.6, 31.2, 22.6, The physical data were identical in all respects to those previously reported. 4 3-Pentyl-1,1'-biphenyl According to the general procedure 1 or 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.61 (dt, J = 8.1, 1.6 Hz, 2H), 7.45 (t, J = 7.7 Hz, 2H), (m, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.19 (d, J = 7.5 Hz, 1H), 2.69 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 4H), 0.92 (t, J = 7.1 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 143.4, 141.5, 141.2, 128.7, 128.6, 127.4, 127.3, 127.2, 127.1, 124.5, 36.1, 31.6, 31.3, 22.6, The physical data were identical in all respects to those previously reported. 5 S5

6 4-(tert-Butyl)-4'-pentyl-1,1'-biphenyl According to the general procedure 1, white solid was obtained after column chromatography, m.p o C. 1 H NMR (400 MHz, CDCl 3 ) δ7.53 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.2 Hz, 2H), 7.45 (d, J = 8.6 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 2.64 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 13H), 0.91 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 149.9, 141.8, 138.4, 138.3, 128.7, 126.8, 126.6, 125.6, 35.6, 34.5, 31.6, 31.4, 31.2, 22.6, 14.1; IR (ATR): ~ = 2931, 2666, 2342, 2094, 1743, 1601, 1460, 1366, 1209, 818; MS (EI): m/z (%) = 281 ([M+H] +, 25), 280 ([M] +, 68), 266 (22), 265 (100), 223 (15), 208 (14), 193 (18); HRMS (ESI +, m/z): calculated for C 21 H 28 [M] + : ; found: ,3-Dimethoxy-5-pentylbenzene According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 6.35 (d, J = 2.3 Hz, 2H), 6.30 (t, J = 2.3 Hz, 1H), 3.78 (s, 6H), 2.55 (t, J = 7.4 Hz, 2H), (m, 2H), (m, 4H), 0.90 (t, J = 7.0 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ160.7, 145.4, 106.5, 97.5, 55.2, 36.3, 31.5, 31.0, 22.5, 14.0; IR (ATR): ~ = 2931, 2666, 2342, 2094, 1743, 1601, 1460, 1366, 1209, 818; MS (EI): m/z (%) = 209 ([M+H] +, 20), 208 ([M] +, 83), 166 (28), 165 (17), 152 (100), 151 (21); The physical data were identical in all respects to those previously reported. 6 N,N-Dimethyl-4-pentylaniline According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.08 (d, J = 8.4 Hz, 2H), 6.75 (d, J = 7.3 Hz, 2H), 2.92 (s, 6H), 2.52 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 4H), 0.89 (t, J = 6.5 Hz, 3H); IR (ATR): ~ = 3449, 2920, 2339, 2093, 1743, 1614, 1508, 1344, 1155, 944, 801; MS (EI): m/z (%) = 192 ([M+H] +, 6), 191 ([M] +, 33), 135 (10), 134 (100), 118 (22), 91 (10); The physical data were identical in all respects to those previously reported. 7 S6

7 (4-Pentylphenyl)(phenyl)methanone According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.80 (dd, J = 8.1, 1.1 Hz, 2H), 7.74 (d, J = 8.1 Hz, 2H), 7.58 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.7 Hz, 2H), 7.29 (d, J = 8.1 Hz, 2H), 2.69 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 5H), 0.91 (t, J = 6.9 Hz, 3H); 13C NMR (151 MHz, CDCl 3 ) δ 196.5, 148.2, 137.9, 135.0, 132.1, 130.3, 129.9, 128.3, 128.2, 36.0, 31.45, 30.9, 22.5, 14.0; IR (ATR): ~ = 2914, 2664, 2340, 2092, 1639, 1446, 1277, 929, 711; MS (EI): m/z (%) = 253 ([M+H] +, 25), 252 ([M] +, 87), 196 (16), 195 (17), 176 (19), 175 (100), 167 (39), 105 (42); HRMS (EI+, m/z): calculated for C 18 H 21 O [M+H] + : ; found: (3-Pentylphenyl)(phenyl)methanone According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.81 (d, J = 7.1 Hz, 2H), 7.63 (s, 1H), 7.59 (t, J = 6.6 Hz, 2H), 7.48 (t, J = 7.8 Hz, 2H), 7.39 (dt, J = 14.9, 7.6 Hz, 2H), 2.67 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 4H), 0.89 (t, J = 7.0 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 197.0, 143.2, 137.8, 137.6, 132.6, 132.3, 130.1, 129.9, 128.2, 128.1, 127.6, 35.8, 31.4, 31.1, 22.5, 14.0; IR (ATR): ~ = 2926, 2660, 2338, 2096, 1808, 1657, 1449, 1280, 965, 709; MS (EI): m/z (%) = 253 ([M+H] +, 4), 252 ([M] +, 12), 195 (17), 175 (13), 115 (20), 105 (67), 77(100); HRMS (EI+, m/z): calculated for C 18 H 20 ONa [M+Na] + : ; found: N-Methyl-3-pentyl-N-phenylbenzamide According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.21 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 2H), 7.03 (d, J = 7.5 Hz, 3H), 3.50 (s, 3H), 2.42 (t, J = 7.6 Hz, 2H), (m, 2H), (m, 2H), (m, 2H), 0.85 (t, J = 7.3 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 170.9, 145.1, 142.3, 135.7, 129.7, 129.0, 128.8, 127.6, 126.9, 126.4, 126.1, 38.3, S7

8 35.6, 31.2, 30.8, 22.5, 14.0.; IR (ATR): ~ = 3316, 2927, 2328, 2090, 1882, 1636, 1459, 1358, 1079, 725; MS (EI): m/z (%) = 282 ([M+H] +, 23), 281 ([M] +, 88), 176 (12), 175 (100), 91 (27), 77 (24); HRMS (EI+, m/z): calculated for C 19 H 23 ONNa [M+Na] + : ; found: Pentyl-2-phenylquinoline According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 8.25 (d, J = 7.1 Hz, 1H), (m, 2H), 8.05 (d, J = 8.3 Hz, 1H), (m, 2H), (m, 3H), 7.47 (t, J = 7.3 Hz, 1H), 3.13 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 4H), 0.93 (t, J = 7.1 Hz, 3H); IR (ATR): ~ = 3806, 3048, 2931, 2656, 2335, 2096, 1741, 1596, 1453, 1355, 1221, 1027, 882, 763, 690; MS (EI): m/z (%) = 276 ([M+H] +, 86), 275 ([M] +,98), 246 (17), 232 (100), 219 (82), 216 (24); The physical data were identical in all respects to those previously reported. 8 2-Pentyl-5-styrylfuran According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.45 (d, J = 7.5 Hz, 2H), 7.33 (t, J = 7.6 Hz, 2H), 7.22 (t, J = 7.3 Hz, 1H), 6.96 (d, J = 16.2 Hz, 1H), 6.84 (d, J = 16.2 Hz, 1H), 6.25 (d, J = 3.0 Hz, 1H), 6.02 (d, J = 2.9 Hz, 1H), 2.66 (t, J = 7.6 Hz, 2H), (m, 2H), (m, 4H), 0.92 (t, J = 6.8 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 156.8, 151.6, 137.4, 128.6, 127.2, 126.1, 125.4, 116.8, 109.7, 106.9, 31.4, 28.2, 27.7, 22.4, 14.0; IR (ATR): ~ = 2929, 2340, 2093, 1740, 1594, 1461, 1371, 954, 763; MS (EI): m/z (%) = 241 ([M+H] +, 17), 240 ([M] +, 81), 184 (21) 183 (100), 153 (13), 115 (12); HRMS (ESI +, m/z): calculated for C 17 H 20 O [M] + : ; found: Methyl-5-pentyl-1H-indole According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ S8

9 7.44 (s, 1H), 7.26 (d, J = 8.3 Hz, 1H), 7.09 (dd, J = 8.4, 1.4 Hz, 1H), 7.03 (d, J = 2.5 Hz, 1H), 6.43 (d, J = 2.7 Hz, 1H), 3.78 (s, 3H), 2.72 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 4H), 0.92 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 135.3, 133.8, 128.8, 128.6, 122.6, 119.9, 108.8, 100.4, 36.0, 32.8, 32.0, 31.6, 22.6, 14.1; IR (ATR): ~ = 3457, 3016, 2924, 2857, 2322, 2099, 1853, 1739, 1566, 1490, 1451, 1347, 1237, 1081, 1009, 876, 791, 715; MS (EI): m/z (%) = 202 ([M+H] +, 4), 201 ([M] +, 22), 145 (18), 144 (100). The physical data were identical in all respects to those previously reported. 9 2-iso-Butylnaphthalene According to the general procedure 1 or 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.61 (s, 1H), (m, 2H), 7.34 (dd, J = 8.4, 1.7 Hz, 1H), 2.67 (d, J = 7.2 Hz, 2H), (m, 1H), 0.98 (d, J = 6.6 Hz, 6H); 13 C NMR (101 MHz, CDCl 3 ) δ 139.3, 133.5, 131.9, 127.9, 127.6, 127.5, 127.4, 127.2, 125.7, 125.0, 45.6, 30.2, The physical data were identical in all respects to those previously reported Nonylnaphthalene According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.61 (s, 1H), (m, 2H), (m, 1H), 2.77 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 12H), (m, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 140.4, 133.6, 131.9, 127.7, 127.5, 127.4, 127.4, 126.2, 125.7, 124.9, 36.1, 31.9, 31.4, 29.5, 29.3, 29.3, 22.7, 14.1; IR (ATR): ~ = 3044, 2922, 2330, 1899, 1606, 1457, 1371, 1134, 749; MS (EI): m/z (%) = 255 ([M+H] +, 55), 254 ([M] +, 100), 155 (14), 154 (14), 142 (81), 141 (94), 23 (24). 2-(5-Methylhex-4-en-1-yl)naphthalene According to the general procedure 1 or 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.62 (s, 1H), (m, 2H), S9

10 7.34 (dd, J = 8.4, 1.6 Hz, 1H), (m, 1H), 2.78 (t, J = 7.7 Hz, 2H), 2.07 (q, J = 7.3 Hz, 2H), (m, 2H), 1.72 (s, 3H), 1.61 (s, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 140.2, 133.6, 131.9, 131.8, 127.7, 127.6, 127.4, 127.4, 126.3, 125.8, 125.0, 124.3, 35.6, 31.4, 27.6, 25.8, The physical data were identical in all respects to those previously reported. 9 2-(4-Phenoxybutyl)naphthalene According to the general procedure 1 or 2, White solid was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.62 (s, 1H), (m, 2H), 7.34 (dd, J = 8.4, 1.6 Hz, 1H), (m, 2H), (m, 3H), 3.98 (t, J = 6.1 Hz, 2H), 2.85 (t, J = 7.2 Hz, 2H), (m, 4H); 13 C NMR (101 MHz, CDCl 3 ) δ 159.0, 139.7, 133.6, 132.0, 129.4, 127.9, 127.6, 127.4, 127.3, 126.4, 125.9, 125.1, 120.5, 114.5, 67.6, 35.7, 28.9, The physical data were identical in all respects to those previously reported. 9 2-(4-Ethoxybutyl)naphthalene According to the general procedure 1, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.63 (s, 1H), (m, 2H), 7.35 (d, J = 8.1 Hz, 1H), (m, 4H), 2.81 (t, J = 7.4 Hz, 2H), (m, 2H), (m, 2H), 1.21 (t, J = 6.9 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 134.0, 133.6, 131.9, 127.8, 127.6, 127.4, 127.4, 126.4, 125.8, 125.0, 70.5, 66.1, 35.9, 29.5, 28.0, 15.2.; IR (ATR): ~ = 3047, 2930, 2858, 2320, 2103, 1907, 1741, 1600, 1449, 1369, 1111, 953, 810, 744; MS (EI): m/z (%) = 228 ([M] +, 57), 167 (42), 155 (13), 154 (79), 149 (100), 142 (18), 141 (57), 115 (22). The physical data were identical in all respects to those previously reported. 9 2-Cyclopentylnaphthalene According to the general procedure 1 or 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.67 (s, 1H), (m, 3H), (m, 1H), (m, 2H), (m, 2H), (m, 4H); 13 C NMR (101 MHz, CDCl 3 ) δ 144.0, S10

11 133.5, 132.0, 127.7, 127.5, 127.5, 126.2, 125.8, 125.0, 124.8, 46.0, 34.5, The physical data were identical in all respects to those previously reported Pentylphenanthrene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 8.75 (dd, J = 7.1, 2.4 Hz, 1H), 8.67 (d, J = 8.1 Hz, 1H), 8.13 (dd, J = 6.9, 2.5 Hz, 1H), (m, 1H), (m, 2H), (m, 3H), 3.12 (d, J = 7.8 Hz, 2H), (m, 2H), (m, 2H), (m, 2H), 0.95 (t, J = 7.2 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 137.0, 131.9, 131.3, 130.7, 129.6, 128.0, 126.5, 126.4, 126.0, 125.9, 125.8, 124.5, 123.2, 122.4, 33.5, 32.1, 30.0, 22.6, The physical data were identical in all respects to those previously reported. 12 1,7-Dipentylnaphthalene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.81 (s, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.68 (d, J = 7.8 Hz, 1H), (m, 3H), 3.07 (t, J = 7.8 Hz, 2H), 2.82 (t, J = 7.7 Hz, 2H), (m, 4H), (m, 8H), (m, 6H); 13 C NMR (101 MHz, CDCl 3 ) δ 140.1, 138.4, 132.3, 132.0, 128.6, 126.9, 126.1, 125.8, 124.6, 122.4, 36.5, 33.0, 32.0, 31.5, 31.2, 30.4, 22.60, 22.59, 14.07, 14.05; IR (ATR): ~ = 3460, 2929, 2321, 2093, 1740, 1603, 1453, 1368, 1216, 1091, 966, 825, 745; MS (EI): m/z (%) = 269 ([M+H] +, 44), 268 ([M] +, 100), 212 (35), 211 (82), 167 (14), 165 (14), 156 (13), 155 (72), 154 (45), 153 (42), 152 (19), 141 (44); HRMS (EI+, m/z): calculated for C 20 H 28 [M] + : ; found: Methoxy-7-pentylnaphthalene According to the general procedure 2, White solid was obtained after column chromatography, mp: C. 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (d, J = 4.5 Hz, 1H), 7.69 (d, J = 3.2 Hz, 1H), 7.53 (s, 1H), 7.20 (d, J = 8.3 Hz, 1H), (m, 2H), 3.93 (s, 3H), 2.76 (t, J = 7.7 Hz, 2H), 1.79 S11

12 1.65 (m, 2H), (m, 4H), 0.92 (t, J = 6.7 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 157.6, 141.1, 134.7, 129.1, 127.5, 127.4, 125.3, 125.2, 117.7, 105.4, 55.2, 36.1, 31.5, 31.1, 22.6, 14.0; IR (ATR): ~ = 3457, 2931, 2340, 2085, 1900, 1741, 1612, 1458, 1381, 1205, 1028, 965, 893, 833, 691, 613; MS (EI): m/z (%) = 229 ([M]+H +, 15), 228 ([M] +, 98), 173 (13), 172 (100), 171 (78), 141 (44), 128 (33); HRMS (EI+, m/z): calculated for C 16 H 20 O 1 [M] + : ; found: Trimethyl(6-pentylnaphthalen-2-yl)silane According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.97 (s, 1H), (m, 2H), 7.59 (s, 1H), 7.57 (dd, J = 8.1, 1.2 Hz, 1H), 7.34 (dd, J = 8.3, 1.8 Hz, 1H), 2.77 (d, J = 7.7 Hz, 2H), (m, 2H), (m, 4H), 0.90 (t, J = 6.9 Hz, 3H), 0.35 (s, 9H); 13 C NMR (151 MHz, CDCl 3 ) δ 140.9, 136.7, 133.8, 133.5, 131.4, 129.8, 127.8, 127.5, 126.4, 126.1, 36.1, 31.5, 31.0, 22.6, 14.1, The physical data were identical in all respects to those previously reported. 9 Methyl 3-pentyl-2-naphthoate According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 8.44 (s, 1H), 7.87 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.68 (s, 1H), 7.54 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H), 3.96 (s, 3H), 3.10 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 4H), 0.92 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 168.3, 140.1, 134.9, 131.8, 130.9, 128.9, 128.6, 128.1, 128.0, 127.0, 125.8, 52.0, 34.5, 31.9, 31.5, 22.6, 14.1; IR (ATR): ~ = 3245, 2934, 2331, 2092, 1719, 1448, 1357, 1265, 1203, 1130, 1056, 892, 750, 550; MS (EI): m/z (%) = 257 ([M]+H +, 18), 256 ([M] +, 85), 200 (52), 199 (53), 196 (19), 195 (37), 182 (16), 181 (31), 169 (37), 168 (22), 153 (19), 152 (25), 142 (13) 141 (100); HRMS (ESI +, m/z): calculated for C 17 H 21 O 2 [M+H] + : ; found: S12

13 N-(7-pentylnaphthalen-1-yl)pivalamide According to the general procedure 2, white solid was obtained after column chromatography, mp: C. 1 H NMR (600 MHz, CDCl 3 ) δ 7.93 (d, J = 7.5 Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.74 (s, 1H), 7.65 (d, J = 8.2 Hz, 1H), 7.50 (s, 1H), 7.41 (t, J = 7.8 Hz, 1H), 7.35 (dd, J = 8.4, 1.5 Hz, 1H), 2.79 (t, J = 7.8 Hz, 2H), (m, 2H), 1.45 (s, 9H), (m, 4H), 0.91 (t, J = 7.0 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 176.9, 141.0, 132.6, 131.8, 128.8, 127.4, 127.4, 125.3, 124.9, 120.9, 118.6, 39.9, 36.5, 31.5, 30.9, 27.9, 22.6, 14.0; IR (ATR): ~ = 3460, 3304, 2939, 2231, 2145, 1971, 1740, 1656, 1524, 1370, 1215, 1087, 1031, 900, 819, 749, 679; MS (EI): m/z (%) =298([M+H] +, 28), 297([M] +, 100), 214 (20), 213 (42), 157 (11), 156 (52), 154 (20), 128 (10), 57 (44); HRMS (ESI +, m/z): calculated for C 20 H 28 ON [M+H] + : ; found: Methoxy-4-pentylbenzene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.09 (d, J = 8.7 Hz, 2H), 6.82 (d, J = 8.6 Hz, 2H), 3.79 (s, 3H), (m, 2H), (m, 2H), (m, 4H), 0.89 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 157.6, 135.1, 129.2, 113.6, 55.3, 35.0, 31.5, 31.5, 22.6, The physical data were identical in all respects to those previously reported Pentylbenzo[d][1,3]dioxole According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 6.72 (d, J = 7.8 Hz, 1H), 6.67 (d, J = 1.7 Hz, 1H), 6.62 (dd, J = 7.9, 1.7 Hz, 1H), 5.91 (s, 2H), (m, 2H), (m, 2H), (m, 4H), 0.89 (t, J = 7.0 Hz, 4H); 13 C NMR (151 MHz, CDCl 3 ) δ 147.4, 145.3, 136.8, 121.0, 108.8, 108.0, 100.7, 35.7, 31.5, 31.4, 22.5, 14.0; IR (ATR): ~ = 3462, 2925, 2857, 2326, 2107, 1992, 1594, 1492, 1460, 1288, 1240, 1173, 1125, 1031, 926, 748, 664; MS (EI): m/z (%) = 193 ([M+H] +, 8), 192 ([M] +, 64), 136 S13

14 (15), 135 (100); HRMS (EI+, m/z): calculated for C 12 H 16 O 2 [M] + : ; found: Methoxy-2-pentylbenzene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 3.82 (s, 3H), (m, 2H), (m, 2H), (m, 4H), (m, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 157.4, 131.4, 129.7, 126.7, 120.3, 110.2, 55.3, 31.8, 30.1, 29.5, 22.6, 14.1; IR (ATR): ~ = 3461, 2936, 2316, 2094, 1739, 1453, 1374, 1218, 1030, 903, 744; MS (EI): m/z (%) = 179 ([M+H] +, 9), 178 ([M] +, 20), 149 (64) 59 (100); HRMS (EI+, m/z): calculated for C 12 H 18 O [M] + : ; found: Methyl 4-pentylbenzoate According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.95 (d, J = 8.2 Hz, 2H), 7.24 (d, J = 8.5 Hz, 2H), 3.90 (s, 3H), (m, 2H), (m, 2H), (m, 4H), 0.89 (t, J = 6.9 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 167.2, 148.5, 129.6, 128.4, 127.6, 51.9, 36.0, 31.4, 30.8, 22.5, The physical data were identical in all respects to those previously reported. 14 Methyl 2-pentylbenzoate According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (d, J = 7.7 Hz, 1H), 7.41 (t, J = 7.5 Hz, 1H), (m, 2H), 3.89 (s, J = 1.2 Hz, 3H), 2.94 (t, J = 7.8 Hz, 2H), (m, 2H), (m, 4H), 0.90 (t, J = 6.5 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ , 144.7, 131.8, 130.9, , 129.5, 125.6, 51.9, 34.4, 31.9, 31.5, 22.5, 14.0; IR (ATR): ~ = 3433, 2929, 2806, 2327, 2111, 1991, 1722, 1601, 1575, 1485, 1437, 1254, 1189, 1137, 1096, 1073, 964, 798, 748, 710, 663; MS (EI): m/z (%) = 207 ([M+H] +, 23), 206 ([M] +, 100), 176 (11), 175 (89), 150 (36), 149 (19), 145 (22), 132 (21), 131 S14

15 (82), 91 (44), 90(13); HRMS (ESI +, m/z): calculated for C 13 H 18 O 2 Na [M+Na] + : ; found: (6-Pentylnaphthalen-2-yl)-1H-pyrazole According to the general procedure 2, white solid was obtained after column chromatography, mp: C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.07 (s, 1H), 8.05 (d, J = 2.1 Hz, 1H), (m, 2H), 7.80 (d, J = 8.4 Hz, 1H), 7.78 (d, J = 1.5 Hz, 1H), 7.63 (s, 1H), 7.38 (dd, J = 8.4, 1.7 Hz, 1H), (m, 1H), 2.78 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 4H), (m, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 141.1, 140.7, 137.0, 132.1, 132.0, 128.9, 128.6, 127.8, 127.0, 126.2, 118.6, 116.3, 107.6, 36.0, 31.5, 31.0, 22.6, 14.0; IR (ATR): ~ = 2930, 2328, 2092, 1912, 1729, 1602, 1493, 1385, 1198, 1111, 1034, 884, 819, 754, 608; MS (EI): m/z (%) =265([M+H] +, 18), 264([M] +, 95), 208 (23), 207 (100), 140 (10), 139 (12); HRMS (ESI +, m/z): calculated for C 18 H 21 N 2 [M+H] + : ; found: Pentyl-N-Piv-indole According to the general procedure 2, white solid was obtained after column chromatography, mp: C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.41 (d, J = 8.5 Hz, 1H), 7.70 (d, J = 3.8 Hz, 1H), 7.35 (d, J = 1.1 Hz, 1H), 7.18 (dd, J = 8.6, 1.6 Hz, 1H), 6.56 (dd, J = 3.8, 0.4 Hz, 1H), 2.69 (t, J = 7.7 Hz, 2H), (m, 2H), 1.51 (s, 9H), (m, 4H), 0.89 (t, J = 7.0 Hz, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 176.9, 138.3, 135.1, 129.5, 125.8, 125.6, 119.8, 117.0, 108.1, 41.1, 35.8, 31.6, 31.5, 28.7, 22.6, 14.0; IR (ATR): ~ = 3823, 3379, 2931, 2325, 2092, 1897, 1703, 1448, 1311, 1194, 897, 746 ; MS (EI): m/z (%) =272 ([M+H] +, 54), 271 ([M] +, 79),187 (41), 131 (31), 130 (85), 129 (18), 85 (25), 57 (100); HRMS (ESI +, m/z): calculated for C 18 H 25 ONNa [M+Na] + : ; found: S15

16 8-Pentylquinoline According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 8.95 (dd, J = 4.1, 1.8 Hz, 1H), 8.13 (dd, J = 8.2, 1.8 Hz, 1H), 7.66 (dd, J = 8.1, 1.2 Hz, 1H), 7.56 (d, J = 7.0 Hz, 1H), 7.47 (t, J = 5.0 Hz, 1H), 7.38 (dd, J = 8.2, 4.1 Hz, 1H), 3.28 (t, J = 5.2 Hz, 2H), (m, 2H), (m, 4H), 0.90 (t, J = 7.2 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 149.2, 146.8, 141.6, 136.4, 128.6, 128.4, 126.3, 125.8, 120.7, 31.9, 31.4, 30.3, 22.7, 14.1; IR (ATR): ~ = 2931, 2322, 2098, 1914, 1737, 1598, 1487, 1377, 1255, 1041, 795, 990; MS (EI): m/z (%) =200 ([M+H] +, 14), 199 ([M] +, 63), 171 (14), 170 (100), 157 (19), 156 (60), 154 (18), 144 (10), 143 (80), 142 (23); HRMS (ESI +, m/z): calculated for C 14 H 18 N [M+H] + : ; found: Methyl-4-pentylquinoline According to the general procedure 2, white solid was obtained after column chromatography, mp: C. 1 H NMR (400 MHz, CDCl 3 ) δ 8.03 (d, J = 8.4 Hz, 1H), 7.98 (d, J = 8.2 Hz, 1H), 7.66 (t, J = 7.6 Hz, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.13 (s, 1H), 3.02 (t, J = 7.8 Hz, 2H), 2.71 (s, 3H), (m, 2H), (m, 4H), 0.92 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 158.6, 148.8, 147.9, 129.2, 129.0, 125.8, 125.3, 123.4, 121.6, 32.1, 31.9, 29.8, 25.2, 22.5, The physical data were identical in all respects to those previously reported Eethylnaphthalene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.65 (s, 1H), (m, 2H), 7.37 (dd, J = 8.4, 1.7 Hz, 1H), 2.84 (q, J = 7.6 Hz, 2H), 1.35 (t, J = 7.6 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 141.7, 133.7, 131.9, 127.8, 127.6, 127.4, 127.1, 125.8, 125.5, 125.0, 29.0, 15.5; The physical data were identical in all respects to those previously reported. 16 S16

17 2-(3-Phenylpropyl)naphthalene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.64 (s, 1H), (m, 2H), 7.36 (dd, J = 8.4, 1.7 Hz, 1H), (m, 2H), (m, 3H), 2.84 (t, J = 7.7 Hz, 2H), 2.72 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 142.2, 139.8, , 132.0, 128.5, 128.3, 127.8, 127.6, 127.4, 127.3, 126.4, 125.8, 125.8, 125.1, 35.6, 35.4, The physical data were identical in all respects to those previously reported. 9 2-(Hex-5-en-1-yl)naphthalene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.61 (s, 1H), (m, 2H), 7.33 (dd, J = 8.4, 1.7 Hz, 1H), (m, 1H), (m, 2H), 2.79 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 2H), (m, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 140.2, 138.8, 133.6, 131.9, 127.7, 127.6, 127.4, 126.3, 125.8, 125.0, 114.4, 35.9, 33.6, 30.8, IR (ATR): ~ = 3834, 3046, 2927, 2671, 2332, 2093, 1815, 1631, 1444, 1364, 1267, 1138, 893, 814, 744; MS (EI): m/z (%) = 211 ([M+H] +, 6), 210 ([M] +, 41), 167 (17), 154 (15), 143 (12), 142 (97), 141 (100), 115 (23); HRMS (EI+, m/z): calculated for C 16 H 18 [M] + : ; found: tert-butyldimethyl(3-(naphthalen-2-yl)propoxy)silane According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.82 (d, J = 8.0 Hz, 1H), (m, 2H), 7.65 (s, 1H), (m, 2H), 7.36 (d, J = 8.4 Hz, 1H), 3.69 (t, J = 6.3 Hz, 2H), 2.87 (t, J = 7.7 Hz, 2H), (m, 2H), 0.95 (s, 9H), 0.09 (s, 6H); 13 C NMR (151 MHz, CDCl 3 ) δ 139.7, 133.6, 131.9, 127.8, 127.6, 127.4, 127.4, 126.4, 125.8, 125.0, 62.3, 34.3, 32.2, 26.0, 18.4, -5.3; IR (ATR): ~ = 3781, 3466, 3054, 2936, 2859, 2737, 2644, 2399, 2284, 2078, 1993, 1919, 1732, 1600, 1466, 1365, 1252, 1096, 966, 834, 772, 742, 661; MS (EI): m/z (%) =301([M+H] +, 2), 200([M] +, 5), 245 (15), 244 (52), 243 (99), 168 (13), 167 (20), 142 (19), S17

18 141 (76), 128 (10), 115 (25), 89 (100), 75 (39) 73 (15), 59 (28), 57 (14); HRMS (ESI +, m/z): calculated for C 19 H 29 OSi [M+H] + : ; found: (Naphthalen-2-yl)propyl pivalate According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (600 MHz, CDCl 3 ) δ 7.81 (d, J = 7.9 Hz, 1H), (m, 2H), 7.62 (s, 1H), (m, 1H), 7.43 (td, J = 7.4 Hz, 1.0 Hz, 1H), 7.33 (dd, J = 8.4, 1.5 Hz, 1H), 4.12 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 7.8 Hz, 2H), (m, 2H), 1.23 (s, 9H); 13 C NMR (151 MHz, CDCl 3 ) δ 178.6, 138.7, 133.6, 132.0, 128.0, 127.6, 127.4, 127.1, 126.5, 126.0, 125.2, 63.6, 38.8, 32.3, 30.2, 27.2; IR (ATR): ~ = 3052, 2964, 2316, 2089, 1994, 1920, 1725, 1599, 1471, 1365, 1282, 1153, 1033, 951, 895, 854, 815, 744; MS (EI): m/z (%) =271([M+H] +, 13), 270([M] +, 53), 169 (36), 168 (100), 167 (76), 155 (12), 154 (14), 153 (49), 142 (16), 141 (84), 128 (16), 115 (38), 57 (71); HRMS (ESI +, m/z): calculated for C 18 H 22 O 2 Na [M+Na] + : ; found: Ethyl 6-(naphthalen-2-yl)hexanoate According to the general procedure 2, colorless oil was obtained after column chromatography; 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.61 (s, 1H), (m, 2H), 7.33 (dd, J = 8.4, 1.7 Hz, 1H), 4.13 (q, J = 7.1 Hz, 2H), 2.79 (t, J = 7.7 Hz, 2H), 2.31 (t, J = 7.5 Hz, 2H), (m, 4H), (m, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 173.7, 140.0, 133.6, 131.9, 127.8, 127.5, 127.4, 127.3, 126.3, 125.8, 125.0, 60.2, 35.8, 34.3, 30.9, 28.7, 24.8, The physical data were identical in all respects to those previously reported. 17 N,N-Diethyl-6-(naphthalen-2-yl)hexanamide According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.61 (s, 1H), 7.47 S18

19 7.37 (m, 2H), 7.33 (dd, J = 8.4, 1.7 Hz, 1H), 3.36 (q, J = 7.1 Hz, 2H), 3.27 (q, J = 7.1 Hz, 2H), 2.79 (t, J = 7.7 Hz, 2H), 2.28 (t, J = 7.7 Hz, 2H), (m, 4H), (m, 2H), 1.14 (t, J = 7.1 Hz, 3H), 1.10 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 172.1, 140.2, 133.6, 131.9, 127.6, 127.4, 127.4, 126.3, 125.8, 125.0, 41.9, 40.0, 35.9, 33.0, 31.2, 29.1, 25.3, 14.4, 13.1; IR (ATR): ~ = 3474, 2935, 2326, 2094, 1892, 1633, 1444, 1264, 1087, 751; MS (EI): m/z (%) =298 ([M+H] +, 20), 297 ([M] +, 100), 156 (27), 154 (13), 142 (53), 128 (32), 115 (59); HRMS (ESI +, m/z): calculated for C 20 H 28 ON [M+H] + : ; found: (5-Chloropentyl)naphthalene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.62 (s, 1H), (m, 2H), 7.34 (d, J = 8.4 Hz, 1H), 3.54 (t, J = 6.7 Hz, 2H), 2.80 (t, J = 7.6 Hz, 2H), (m, 2H), (m, 2H), (m, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 139.8, 133.6, 131.9, 127.8, 127.6, 127.4, 127.3, 126.3, 125.9, 125.1, 45.0, 35.9, 32.59, 30.6, 26.5; IR (ATR): ~ = 3793, 3460, 2931, 2319, 2093, 1740, 1443, 1366, 1217, 1123, 1028, 856, 887, 218, 742; MS (EI): m/z (%) =233 ([M+H] +, 4), 232 ([M] +, 28), 142 (42), 141 (100), 115 (19); HRMS (ESI +, m/z): calculated for C 15 H 17 ClNa [M+Na] + : ; found: Cyclohexylnaphthalene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.65 (s, 1H), (m, 3H), 2.68 (tt, J = 11.8, 3.3 Hz, 1H), 1.99 (d, J = 12.7 Hz, 2H), 1.90 (d, J = 12.6 Hz, 2H), (m, 1H), (m, 4H), (m, 1H); 13 C NMR (101 MHz, CDCl 3 ) δ 145.6, 133.7, 132.1, 127.7, 127.6, 127.5, 126.2, 125.7, 125.0, 124.5, 44.7, 34.4, 26.9, The physical data were identical in all respects to those previously reported Cyclopropylnaphthalene According to the general procedure 2, white solid was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, S19

20 3H), 7.53 (s, 1H), (m, 2H), 7.20 (dd, J = 8.5, 1.8 Hz, 1H), (m, 1H), (m, 2H), (m, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 141.4, 133.5, 131.9, 127.8, 127.6, 127.2, 125.9, 124.8, 124.6, 123.7, 15.6, 9.2. The physical data were identical in all respects to those previously reported Propylnaphthalene According to the general procedure 2, colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.63 (s, 1H), (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 2.78 (t, J = 7.6 Hz, 2H), (m, 2H), 1.01 (t, J = 7.3 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 140.2, 133.6, 131.9, 127.7, 127.6, 127.5, 127.4, 126.4, 125.8, 125.0, 38.2, 24.5, The physical data were identical in all respects to those previously reported (1-Ethoxy-1-oxopropan-2-yl)naphthalen-2-yl pivalate White solid was obtained after column chromatography, mp: C. 1 H NMR (600 MHz, CDCl 3 ) δ 7.81 (d, J = 8.8 Hz, 1H), (m, 2H), 7.49 (d, J = 1.8 Hz, 1H), 7.45 (dd, J = 8.5, 1.4 Hz, 1H), 7.18 (dd, J = 8.8, 2.1 Hz, 1H), (m, 2H), 3.86 (q, J = 7.1 Hz, 1H), 1.58 (d, J = 7.2 Hz, 3H), 1.40 (s, 9H), 1.20 (t, J = 7.1 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 177.3, 174.5, 148.7, , 131.4, 129.2, 127.9, 126.4, 126.0, 121.4, 118.2, 60.8, 45.6, 39.1, 27.2, 18.5, 14.1.; IR (ATR): ~ = 3450, 2975, 2323, 2099, 1992, 1911, 1735, 1605, 1466, 1373, 1323, 1246, 1108, 1027, 900, 802, 756, 664; MS (EI): m/z (%) = 329 ([M+H] +, 63), 328 ([M] +, 85), 255 (20), 245 (20), 244 (73), 172 (33), 171 (100), 170 (13), 153 (11), 142 (19), 141 (28), 115 (12), 57 (34); HRMS (EI+, m/z): calculated for C 20 H 24 O 4 [M] + : ; found: Ethyl 2-(6-pentylnaphthalen-2-yl)propanoate Colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.70 (s, 1H), 7.58 (s, 1H), 7.41 (dd, J = 8.5, 1.8 Hz, 1H), 7.33 S20

21 (dd, J = 8.4, 1.7 Hz, 1H), (m, 2H), 3.86 (q, J = 7.1 Hz, 1H), 2.75 (t, J = 7.7 Hz, 2H), (m, 2H), 1.58 (d, J = 7.2 Hz, 3H), (m, 4H), 1.20 (t, J = 7.1 Hz, 3H), 0.90 (t, J = 6.9 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ 174.6, 140.4, 137.2, 132.7, 131.9, , , 127.6, 126.0, 125.8, 125.7, 60.7, 45.6, 36.0, 31.5, 31.1, 22.6, 18.6, 14.1, 14.0; IR (ATR): ~ = 3143, 3052, 2928, 2858, 2657, 2331, 2183, 2113, 1991, 1958, 1913, 1731, 1605, 1501, 1456, 1372, 1324, 1244, 1181, 1096, 1064, 1025, 960, 886, 813, 728, 701, 668; MS (EI): m/z (%) = 299 ([M+H] +, 74), 298 ([M] +, 100), 242 (13), 241 (35), 226 (73), 225 (98), 181 (14), 169 (25), 168 (80), 167 (65), 166 (14), 165 (33), 155 (49), 154 (18), 153 (49), 141 (30), 139 (10), 115 (11); HRMS (ESI +, m/z): calculated for C 20 H 26 O 2 Na [M+Na] + : ; found: Ethyl 2-(6-iso-butylnaphthalen-2-yl)propanoate Colorless oil was obtained after column chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.70 (s, 1H), 7.55 (s, 1H), 7.42 (dd, J = 8.5, 1.8 Hz, 1H), 7.30 (dd, J = 8.4, 1.7 Hz, 1H), (m, 2H), 3.86 (q, J = 7.1 Hz, 1H), 2.63 (d, J = 7.2 Hz, 2H), (m, 1H), 1.58 (d, J = 7.2 Hz, 3H), 1.21 (t, J = 7.1 Hz, 3H), 0.93 (d, J = 6.6 Hz, 6H); 13 C NMR (101 MHz, CDCl 3 ) δ 174.6, 139.2, 137.3, 132.6, 131.9, 128.2, 127.8, 127.4, 126.9, 125.8, 125.7, 60.8, 45.6, 45.6, 30.2, 22.4, 18.6, 14.1; IR (ATR): ~ = 3447, 2948, 2320, 2093, 1893, 1728, 1610, 1458, 1329, 1171, 887, 805, 681; MS (EI): m/z (%) = 285 ([M+H] +, 26), 284 ([M] +, 94), 242 (9), 241 (50), 212 (22), 211 (100), 169 (12), 168 (50), 167 (28), 165 (13), 155 (12), 153 (20), 141 (11); HRMS (ESI +, m/z): calculated for C 19 H 24 O 2 Na [M+Na] + : ; found: (6-iso-Pentylnaphthalen-2-yl)propanoic acid White solid was obtained after column chromatography, mp: C. 1 H NMR (600 MHz, CDCl 3 ) δ (m, 3H), 7.58 (s, 1H), 7.42 (dd, J = 8.4, 1.8 Hz, 1H), 7.33 (dd, J = 8.4, 1.6 Hz, 1H), 3.89 (q, J = 7.1 Hz, 1H), 2.76 (t, J = 7.7 Hz, 2H), (m, 2H), 1.60 (d, J = 7.2 Hz, 3H), (m, 4H), 0.90 (t, J = 6.9 Hz, 3H); 13 C NMR (151 S21

22 MHz, CDCl 3 ) δ 180.6, 140.6, 136.2, 132.8, 131.8, 127.9, 127.8, 127.6, 126.0, 125.6, 45.4, 36.0, 31.4, 31.0, 22.6, 18.1, 14.0; IR (ATR): ~ = 2928, 2094, 1703, 1438, 1227, 1077, 898, 815, 676; MS (EI): m/z (%) = 271 ([M+H] +, 22), 270 ([M] +, 100), 226 (15), 225 (80), 214 (21), 213 (45), 168 (18), 167 (13), 153 (11), 141 (11); HRMS (ESI +, m/z): calculated for C 18 H 22 O 2 Na [M+Na] + : ; found: (6-iso-Butylnaphthalen-2-yl)propanoic acid White solid was obtained after column chromatography, mp: C. 1 H NMR (600 MHz, CDCl 3 ) δ (m, 3H), 7.55 (s, 1H), 7.42 (dd, J = 8.5, 1.8 Hz, 1H), 7.29 (dd, J = 8.4, 1.6 Hz, 1H), 3.90 (q, J = 7.1 Hz, 1H), 2.62 (d, J = 7.2 Hz, 2H), (m, 1H), 1.60 (t, J = 7.3 Hz, 3H), 0.92 (d, J = 6.6 Hz, 6H); 13 C NMR (151 MHz, CDCl 3 ) δ 179.6, 139.4, 136.3, 132.7, 131.9, , 128.0, 127.5, 126.9, 126.0, 125.6, 45.5, 45.3, 30.2, 22.4, 18.2; IR (ATR): ~ = 2930, 2102, 1702, 1425, 1243, 1089, 900, 820, 682; MS (EI): m/z (%) = 257 ([M+H] +, 14), 256 ([M] +, 76), 214 (18), 213 (100), 211 (27), 168 (16), 167 (10); HRMS (ESI +, m/z): calculated for C 17 H 20 O 2 Na [M+Na] + : ; found: Reaction of phenyl 6-(pivaloyloxy)-2-naphthoate O O OPh OPh PivO Me + 3a 9 ZnBr Ni(cod) 2 /dcype THF/iPr 2 O Temp, 18 h Me Me Me Entry Temp ( C) 10 Yield (%) 11 Yield (%) a Reaction conditions: 9 (87 mg, 0.25 mmol), [Ni(cod) 2 ] (3.4 mg, mmol), dcype (5.3 mg, mmol), ipr 2 O (0.7 ml), n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)], 18 h. a Reaction was performed with [Ni(cod) 2 ] (6.8 mg, mmol), dcype (10.6 mg, mmol), n-pentylzinc bromide [0.75 mmol in THF (1.0 ml)]. S22

23 An oven-dried tube with a teflon sealed screwcap was charged with a magnetic stir bar, catalyst [Ni(cod) 2 ] (3.4 mg, mmol), dcype (5.3 mg, mmol), 9 (87 mg, 0.25 mmol) and ipr 2 O (0.7 ml) in a glovebox filled with argon. The reaction mixture was stirred at room temperature for 5 min, then n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was added slowly. The tube was sealed, removed from the glovebox, and the mixture stirred at the indicated temperature for 18 h. After cooling to room temperature, the mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2,6-dipentylnaphthalene and starting material 9. Me 1 H NMR (600 MHz, Chloroform-d) δ 7.71 (d, J = Me 8.3 Hz, 2H), 7.59 (s, 2H), 7.32 (d, J = 8.3 Hz, 2H), 2.77 (t, J = 7.7 Hz, 4H), (m, 4H), (m, 8H), 0.92 (t, J = 7.0 Hz, 6H); 13 C NMR (151 MHz, Chloroform-d) δ 139.5, 132.0, 127.4, 127.2, 126.0, 36.0, 31.5, 31.1, 22.6, 14.1; IR (ATR): ~ = 2926, 2327, 2105, 1606, 1456, 1096, 883, 810, 733; MS (EI): m/z (%) = 269 ([M+H] +, 16), 268 ([M] +, 68), 212 (30), 211 (100), 155 (17), 154 (28), 153(14), 142 (13), 141 (36). The physical data were identical in all respects to those previously reported. 20 Reaction of 6-(4-Chlorophenyl)naphthalen-2-yl pivalate OPiv Me Cl Me 12 3a + ZnBr Ni(cod) 2 /dcype THF/iPr 2 O Temp, 18 h Me 82% An oven-dried tube with a teflon sealed screwcap was charged with a magnetic stir bar, catalyst [Ni(cod) 2 ] (3.4 mg, mmol), dcype (5.3 mg, mmol), 12 (85 mg, 0.25 mmol) and ipr 2 O (0.7 ml) in a glovebox filled with argon. The reaction mixture was stirred at room temperature for 5 min, then n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was S23

24 added slowly. The tube was sealed, removed from the glovebox, and the mixture was stirred at 70 C for 18 h. After cooling to room temperature, the mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2-pentyl-6-(4-pentylphenyl)naphthalene as a white solid (71 mg, mmol, 82% yield). M.p o C. 1 H NMR (600 MHz, Chloroform-d) δ 8.00 (s, 1H), 7.84 (d, J = 8.5 Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.72 (dd, J = 8.5, 1.9 Hz, 1H), (m, 3H), 7.36 (dd, J = 8.3, 1.7 Hz, 1H), 7.30 (d, J = 8.1 Hz, 2H), 2.79 (t, J = 7.7 Hz, 2H), 2.68 (t, J = 7.8 Hz, 2H), (m, 4H), (m, 8H), (m, 6H); 13 C NMR (151 MHz, Chloroform-d) δ 142.0, 140.4, 138.5, 137.6, 132.6, 132.1, 128.9, 127.9, 127.8, 127.8, 127.1, 126.0, 125.5, 125.2, 36.1, 35.6, 31.5, 31.5, 31.2, 31.0, 22.6, 14.1; IR (ATR): ~ = 3023, 2924, 2323, 1914, 1602, 1501, 1459, 1374, 1230, 962, 888, 810, 665; MS (EI): m/z (%) = 345 ([M+H] +, 29), 344 ([M] +, 100), 288 (23), 287 (85), 231 (15), 230 (43). Procedures for the decarbonylative alkylation of phenyl esters with NiCl 2 as catalyst: An oven-dried tube with a teflon sealed screwcap was charged with a magnetic stir bar, 1a (62 mg, 0.25 mmol) and [NiCl 2 ] (3.2 mg, mmol). The tube was transferred to a glovebox filled with argon and charged with dcype (10.6 mg, mmol), and ipr 2 O (0.7 ml). The reaction mixture was stirred at room temperature for 5 min, then n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was added slowly. The tube was sealed, removed from the glovebox, and the mixture stirred at 150 C for 18 h. After cooling to room temperature, the mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous S24

25 magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2-pentylnaphthalene as a colorless oil (35 mg, mmol, 71% yield). An oven-dried Schlenk tube with a teflon sealed screwcap was charged with a magnetic stir bar, 1a (62 mg, 0.25 mmol), [NiCl 2 ] (3.2 mg, mmol) and dcype 2HBF 4 (15 mg, mmol), and then the tube was evacuated and refilled with argon for three times. Next ipr 2 O (0.7 ml) was added and the reaction mixture was stirred at room temperature for 5 min. Subsequently n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was added slowly. The tube was sealed, and the mixture was stirred at 150 C for 18 h. After cooling to room temperature, the mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2-pentylnaphthalene as a colorless oil (14mg, mmol, 28% yield). S25

26 Procedure for the alkylation of pivaloyl esters with NiCl 2 as catalyst: An oven-dried tube with a teflon sealed screwcap was charged with a magnetic stir bar, 2a (57 mg, 0.25 mmol) and [NiCl 2 ] (1.6 mg, mmol), after that the tube was transferred to a glovebox filled with argon and charged with dcype (5.3 mg, mmol), and ipr 2 O (0.7 ml). The reaction mixture was stirred at room temperature for 5 min, then n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was added slowly. The tube was sealed, removed from the glovebox, and the mixture stirred at 70 C for 18 h. After cooling to room temperature, the mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2-pentylnaphthalene as a colorless oil (46 mg, mmol, 93% yield). An oven-dried schlenk tube with a teflon sealed screwcap was charged with a magnetic stir bar, 2a (57 mg, 0.25 mmol), [NiCl 2 ] (1.6 mg, mmol) and dcype 2HBF 4 (7.5 mg, mmol), and then the mixture was pumped and refilled with argon for three times. After ipr 2 O (0.7 ml) was added, the reaction mixture was stirred at room temperature for 5 min, then n-pentylzinc bromide [0.5 mmol in THF (1.0 ml)] was added slowly. The tube was sealed, and the mixture stirred at 70 C for 18 h. After cooling to room temperature, the S26

27 mixture was quenched with aqueous HCl (2 M, 5 ml) and extracted with EtOAc (20*3 ml). The combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated followed by purification on silica gel (eluent: hexane) to afford 2-pentylnaphthalene as a colorless oil (43 mg, mmol, 87% yield). S27

28 References: 1. Krasovskiy, A.; Knochel, P., Synthesis 2006, Wegner, H.; Schweighauser, L.; Bodoky, I.; Kessler, S.; Häussinger, D., Synthesis 2012, 44, Ebden, M. R.; Simpkins, N. S.; Fox, D. N. A. Tetrahedron 1998, 54, Tanimoro, K.; Ueno, M.; Takeda, K.; Kirihata, M.; Tanimori, S., J. Org. Chem. 2012, 77, Bhuniaa, S.; Md. Abu Sohela, S.; Yanga, C.-C.; Lushb, S.-F.; Shenc, F.-M.; Liua, R.-S., J. Organomet. Chem. 2009, 694, Trost, B. M.; Dogra, K. Org. Lett. 2007, 9, Katritzky, A. R.; Lang, H.; Lan, X., Tetrahedron 1993, 49, Wang, Y. ; Chen, C.; Peng, J.; Li, M., Angew. Chem., Int. Ed. 2013, 52, Liu, X.; Hsiao, C.-C.; Kalvet, I.; Leiendecker, M.; Guo, L.; Schoenebeck, F.; Rueping, M., Angew. Chem., Int. Ed. 2016, 55, Giannerini, M.; Fananas-Mastral, M.; Feringa, B. L. Nat. Chem. 2013, 5, Gatti, M.; Wu, L.; Drinkel, E.; Gaggia, F.; Blumentritt, S.; Linden, A.; Dorta, R., ARKIVOC 2011, 6, Shu, C.; Li, L.; Chen, C.-B.; Shen, H.-C.; Ye, L.-W., Chem. Asian J. 2014, 9, Satoh, T.; Kondo, A.; Musashi, J., Tetrahedron 2004, 60, Jiang, Q.; Zhao, A.; Xu, B.; Jia, J.; Liu, X.; Guo, C., J. Org. Chem. 2014, 79, Horn, J.; Marsden, S. P.; Nelson, A.; House, D.; Weingarten, G. G., Org. Lett. 2008, 10, Guan, B.-T.; Xiang, S.-K.; Wang, B.-Q.; Sun, Z.-P.; Wang, Y.; Zhao, K.-Q.; Shi, Z.-J., J. Am. Chem. Soc. 2008, 130, Lee, J.-Y.; Fu, G. C., J. Am. Chem. Soc. 2003, 125, Yonehara, F.; Kido, Y.; Sugimoto, H.; Morita, S.; Yamaguchi, M. J. Org. Chem. 2003, 68, Gandon, V.; Bertus, P.; Szymoniak, J., Eur. J. Org. Chem. 2000, Tobisu, M.; Takahira, T.; Morioka, T.; Chatani, N. J. Am. Chem. Soc. 2016, 138, S28