Supporting Information. Activation

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1 Supporting Information Nickel-Catalyzed C sp2 -C sp3 Cross Coupling via C-O Bond Activation Lin Guo, Chien Chi Hsiao, Huifeng Yue, Xiangqian Liu, and Magnus Rueping* Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, Aachen, Germany Magnus.rueping@rwth-aachen.de I II III IV V VI VII VIII IX General Information Optimization Studies Synthesis of Starting Materials Preparation of B-Alkyl-9-BBN Typical Procedure for the Catalytic Reactions Gram Scale Experiment Spectroscopic Data of Products Synthetic Application Copies of 1 H and 13 C NMR Spectra S1

2 I. General Information Unless otherwise noted, all commercially available compounds were used as provided without further purification. Solvents for chromatography were technical grade and freshly distilled prior to use. Diisopropyl ether used in reactions was analytical grade and distilled from benzophenone/na. Analytical thin-layer chromatography (TLC) was performed on Merck silica gel aluminium plates with F-254 indicator, visualised by irradiation with UV light. Column chromatography was performed using silica gel (Macherey Nagel, particle size mm). Solvent mixtures are understood as volume/volume. 1 H-NMR and 13 C-NMR were recorded on a Varian AV300, AV400 or AV600 spectrometer in CDCl 3 and are reported relative to the solvents residual 1 H-signal (CHCl 3, δ(h) 7.26). Data are reported in the following order: chemical shift (δ) in ppm; multiplicities are indicated s (singlet), bs (broad singlet), d (doublet), t (triplet), m (multiplet); coupling constants (J) are in Hertz (Hz). Melting points were measured using open glass capillaries in a Buchi SMP-20 apparatus. IR spectra were recorded on a Perkin Elmer-100 spectrometer and are reported in terms of frequency of absorption (cm -1 ). Mass spectra (EI-MS, 70 ev) were conducted on a Finnigan SSQ 7000 spectrometer. HRMS were recorded on a Thermo Scientific LTQ Orbitrap XL spectrometer. S2

3 II. Optimization Studies Table S1. Effect of solvent a Entry [Ni] Solvent T ( C) Yield of 3a (%) b 1 Ni(COD) 2 THF Ni(COD) 2 DME Ni(COD) 2 1,4-dioxane Ni(COD) 2 Toluene Ni(COD) 2 i Pr 2 O a Reaction conditions: 1a (0.20 mmol), 2a (0.32 mmol), Ni catalyst (8 mol%), ligand (16 mol%), base (1.2 equiv.), i BuOH (2 equiv.), solvent (0.1 M) at the corresponding temperature for 12 h. b NMR yields using 1,3,5- () 3 C 6 H 3 as an internal standard. Table S2. Effect of nickel catalyst utilized a Entry [Ni] Solvent T ( C) Yield of 3a (%) b 1 NiBr 2 i Pr 2 O NiCl 2 glyme i Pr 2 O Ni(acac) 2 i Pr 2 O c Ni(IMes) 2 i Pr 2 O Ni(COD) 2 i Pr 2 O a Reaction conditions: 1a (0.20 mmol), 2a (0.32 mmol), Ni catalyst (8 mol%), ligand (16 mol%), base (1.5 equiv.), solvent (0.1 M) at 100 for 12 h. b NMR yields. c Without ligand. S3

4 Table S3. Effect of the supporting ligand a Entry [Ni] Ligand (x) T ( C) Yield of 3a (%) b 1 Ni(COD) 2 None Ni(COD) 2 P t Bu 3 (16) Ni(COD) 2 PPh 3 (16) Ni(COD) 2 PCy 3 (16) Ni(COD) 2 dppe (8) 100 < 5 6 Ni(COD) 2 dppf (8) Ni(COD) 2 dcype (8) Ni(COD) 2 dcypf (8) Ni(COD) 2 SIPr HCl (16) Ni(COD) 2 IPr HCl (16) Ni(COD) 2 ICy HCl (16) Ni(COD) 2 IMes HCl (16) c Ni(COD) 2 IPr HCl (10) a Reaction conditions: 1a (0.20 mmol), 2a (0.32 mmol), Ni catalyst (8 mol%), ligand (x mol%), base (1.5 equiv.), solvent (0.1 M) at 100 for 12 h. b NMR yields. c Ni catalyst (5 mol%). S4

5 Table S4. Effect of temperature a Entry Solvent T ( C) Yield of 3a (%) b 1 i Pr 2 O 40 trace 2 i Pr 2 O 60 < 5 3 i Pr 2 O i Pr 2 O i Pr 2 O i Pr 2 O i Pr 2 O a Reaction conditions: 1a (0.20 mmol), 2a (0.32 mmol), Ni catalyst (8 mol%), ligand (16 mol%), base (1.5 equiv.), solvent (0.1 M) at the corresponding temperature for 12 h. b NMR yields. Table S5. Effect of base a Entry Base Solvent T ( C) Yield of 3a (%) b 1 Li 2 CO 3 i Pr 2 O Na 2 CO 3 i Pr 2 O K 2 CO 3 i Pr 2 O 100 < 5 4 Na 2 HCO 3 i Pr 2 O K 3 PO 4 i Pr 2 O CsF i Pr 2 O NaO t Bu i Pr 2 O none i Pr 2 O a Reaction conditions: 1a (0.20 mmol), 2a (0.32 mmol), Ni catalyst (8 mol%), ligand (x mol%), base (1.5 equiv), solvent (0.1 M) at 100 for 12 h. b NMR yields. S5

6 Table S6. Effect for protecting groups of phenol derivatives a Entry R Yield of 3a (%) b 1 Ts 98 2 Ms 89 3 SO 2 NEt CONEt Boc 75 6 Piv 93 7 Bn 0 8 i Pr 0 9 Et 0 10 Me 0 a Reaction conditions: 1 (0.20 mmol), 2a (0.32 mmol), Ni catalyst (8 mol%), ligand (16 mol%), base (1.5 equiv), solvent (0.1 M) at 110 for 12 h. b NMR yields. S6

7 Table S7. Effect of alkylboron nuclephile a Entry Alkylboron Ligand (x mol%) Yield of 3 (%) b 1 9 PCy 3 (16) dcype (8) IPr HCl (16) PCy 3 (16) dcype (8) IPr HCl (16) 0 a Reaction conditions: 1a (0.20 mmol), 9 or 10 (0.40 mmol), Ni catalyst (8 mol%), ligand (8 or 16 mol%), base (1.5 equiv.), solvent (0.1 M) at the corresponding temperature for 12 h. b NMR yields. S7

8 III.Synthesis of Starting Materials Aryl pivalates have been prepared via the classical reaction of the free alcohol in the presence of Et 3 N (1.20 equiv), PivCl (1.20 equiv) in dichloromethane at room temperature. 1 Naphthalen-2-yl pivalate (1a) 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 2H), 7.80 (dd, J = 8.0, 1.4 Hz, 1H), 7.54 (d, J = 2.3 Hz, 1H), (m, 2H), 7.20 (dd, J = 8.8, 2.3 Hz, 1H), 1.41 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.4, 148.9, 133.9, 131.5, 129.4, 127.9, 127.7, 126.6, 125.7, 121.3, 118.5, 39.3, Data in accordance with the literature. 1 Naphthalen-1-yl pivalate (1b) 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 2H), 7.75 (d, J = 8.3 Hz, 1H), (m, 2H), 7.48 (t, J = 7.9 Hz, 1H), 7.24 (d, J = 7.5 Hz, 1H), 1.53 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 176.1, 146.9, 134.7, 128.1, 127.1, , , 125.8, 125.5, 121.1, 118.0, 39.6, Data in accordance with the literature. 1 Phenanthren-9-yl pivalate (1c) 1 H NMR (600 MHz, CDCl 3 ): δ = 8.72 (d, J = 8.3 Hz, 1H), 8.67 (d, J = 8.3 Hz, 1H), 7.96 (dd, J = 8.1, 0.6 Hz, 1H), 7.85 (dd, J = 8.1, 0.6 Hz, 1H), (m, 1H), (m, 3H), 7.51 (s, 1H), 1.54 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.1, 145.3, 131.7, 131.6, 128.9, 128.5, 127.2, 127.1, , , 126.4, 123.1, 122.7, 121.8, 117.6, 39.7, Data in accordance with the literature. 2 [1,1'-Biphenyl]-4-yl pivalate (1d) 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 4H), (m, 2H), 7.34 (tt, J = 7.2, 1.2 Hz, 1H), 7.13 (d, J = 8.8 Hz, 2H), 1.38 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.1, 150.5, 140.4, 138.7, 128.8, 128.1, 127.3, 127.1, 121.8, 39.1, Data in accordance with the literature. 3 [1,1'-Biphenyl]-3-yl pivalate (1e) 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 2H), (m, 4H), (m, 1H), (m, 1H), (m, 1H), 1.38 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ): S8

9 δ = 177.1, 151.6, 142.9, 140.3, 129.7, 128.8, 127.7, 127.3, 124.4, 120.3, 39.2, Data in accordance with the literature. 4 [1,1'-Biphenyl]-2-yl pivalate (1f) 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 8H), 7.12 (dd, J = 8.0, 1.2 Hz, 1H), 1.16 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 176.8, 148.2, 137.6, 135.3, 130.9, 129.3, 128.5, 128.1, 127.4, 126.1, 122.7, 38.9, Data in accordance with the literature. 5 4-Methoxynaphthalen-1-yl pivalate (1g) 1 H NMR (600 MHz, CDCl 3 ): δ = 8.27 (d, J = 8.2, 1H), 7.77(d, J = 7.5, 1H), (m, 2H), 7.10 (d, J = 8.2, 1H), 6.77 (d, J = 8.2, 1H), 4.00 (s, 3H), 1.49 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.5, 153.3, 140.3, 127.7, 127.0, 126.3, 125.7, 122.5, 120.8, 117.6, 103.0, 55.8, 39.5, Data in accordance with the literature. 1 7-Methoxynaphthalen-2-yl pivalate (1h) 1 H NMR (400 MHz, CDCl 3 ): δ = 7.75 (dd, J = 15.0, 8.8 Hz, 2H), 7.45 (d, J = 2.1 Hz, 1H), (m, 3H), 3.90 (s, 3H), 1.43 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ): δ = 177.3, 158.3, 149.6, 135.3, 129.3, 129.1, 127.0, 118.8, 118.5, 117.5, 105.7, 55.4, 39.3, Data in accordance with the literature. 5 Methyl 6-(pivaloyloxy)-2-naphthoate (1i) 1 H NMR (600 MHz, CDCl 3 ): δ = 8.61 (d, J = 0.6 Hz, 1H), 8.07 (dd, J = 8.6, 1.6 Hz, 1H), 7.96 (d, J = 8.8 Hz, 1H), 7.83 (d, J = 8.8 Hz, 1H), 7.58 (d, J = 2.1 Hz, 1H), 7.27 (dd, J = 9.1, 2.1 Hz, 1H), 3.98 (s, 3H), 1.41 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.1, 167.2, , , 127.9, 127.3, 126.0, 122.2, 118.5, , Data in accordance with the literature. 6 6-(Trimethylsilyl)naphthalen-2-yl pivalate (1j) White solid (Mp: C). 1 H NMR (600 MHz, CDCl 3 ): δ = 8.00 (s, 1H), 7.85 (d, J = 8.8 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.60 (dd, J = 8.1, 1.0 Hz, 1H), 7.50 (d, J = 2.2 Hz, 1H), 7.19 (dd, J = 8.8, 2.2 Hz, 1H), 1.41 (s, 9H), 0.35 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.3, 149.1, 137.7, 134.1, 133.6, 130.9, 130.6, 129.5, 126.7, 121.3, 118.3, 39.2, 27.3, IR (ATR): ~ = 2958, 1746, 1606, 1470, 1373, 1218, 1126, 831, 757 cm -1. MS S9

10 (EI): m/z (%) = (M +, 100), (74), (94), 57.1 (73). HRMS (ESI) for C 18 H 24 O 2 Si: calculated for [M+Na] , found Acetylphenyl pivalate (1k) 1 H NMR (600 MHz, CDCl 3 ): δ = 7.99 (d, J = 8.6 Hz, 2H), 7.16 (d, J = 8.6 Hz, 2H), 2.60 (s, 3H), 1.37 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 197.0, 176.6, 155.0, 134.6, 130.0, 121.8, 39.3, 27.2, Data in accordance with the literature. 6 6-(4-Fluorophenyl)naphthalen-2-yl pivalate (1l) White solid (Mp: C). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.98 (s, 1H), (m, 2H), (m, 3H), 7.55 (s, 1H), (m, 3H), 1.42 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.3, (d, J C-F = Hz), 149.0, 137.4, (d, J C-F = 2.7 Hz), 132.9, 131.6, 129.6, (d, J = 8.0 Hz), 128.3, 126.2, 125.6, 121.8, 118.3, (d, J = 21.4 Hz), 39.3, F NMR (564 MHz, CDCl 3 ): δ = IR (ATR): ~ = 2967, 1746, 1594, 1486, 1370, 1222, 1116, 1018, 898, 813 cm -1. MS (EI): m/z (%) = (M +, 15), (33), (32), (60), (59), (50), (51), 84.9 (31), 57.1 (100). HRMS (ESI) for C 21 H 19 FO 2 : calculated for [M+Na] , found Methylquinolin-4-yl pivalate (1m) 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 1H), 7.86 (dd, J = 8.4, 1.3 Hz, 1H), 7.71 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H), 7.51 (ddd, J = 8.2, 6.8, 1.3 Hz, 1H), 7.26 (s, 1H), 2.75 (s, 3H), 1.49 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 176.0, 160.0, 154.6, 149.6, 130.1, 128.9, 126.1, 121.1, 121.0, 113.7, 39.9, 27.4, Data in accordance with the literature. 5 3,4-Dihydronaphthalen-1-yl pivalate (1n) 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), (m, 1H), 5.67 (t, J = 4.7, 1H), 2.87 (t, J = 8.1, 2H), (m, 2H), 1.38 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 177.0, 145.9, 136.6, 130.9, 128.0, 127.7, 126.5, 120.7, 115.2, 39.4, 27.7, 27.5, Data in accordance with the literature. 1 S10

11 3,4-Dihydronaphthalen-2-yl pivalate (1o) 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.01 (d, J = 7.1 Hz, 1H), 6.20 (s, 1H), 3.00 (t, J = 8.3 Hz, 2H), 2.49 (t, J = 8.3 Hz, 2H), 1.31 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 176.8, 151.3, 133.4, 133.3, 127.3, 126.7, 126.6, 126.2, 114.5, 39.0, 28.6, 27.2, Data in accordance with the literature. 7 2,2-Diphenylvinyl pivalate (1p) 1 H NMR (600 MHz, CDCl 3 ): δ = 7.62 (s, 1H), (m, 10H), 1.21 (s, 9H). 13 C NMR (150 MHz, CDCl 3 ): δ = 175.5, 139.1, 136.8, 132.8, 130.1, , , 128.0, 127.6, 127.5, 127.4, 38.9, Data in accordance with the literature. 8 S11

12 IV. Preparation of B-Alkyl-9-BBNs The B-alkyl-9-BBN could be generated in situ from the corresponding alkenes with 9-BBN dimer. As mentioned in Fu s paper, 9 in a nitrogen-filled glovebox the corresponding olefin (0.32 mmol) was added to 9-BBN dimer (39.0 mg, 0.16 mmol) in a 10-mL vial equipped with a stirring bar. Diisopropyl ether (1.0 ml) was added and then the vial was capped and removed from the glovebox. The reaction mixture was stirred at 60 C for 1.5 h, and allowed to cool to room temperature. The vial was then taken back into the glovebox and could be directly used in the catalytic reactions. V. Typical Procedure for the Catalytic Reactions In a nitrogen-filled glovebox, an oven-dried sealed tube containing a stirring bar was charged with aryl pivalate substrate (0.20 mmol), yellow Ni(COD) 2 (4.4 mg, 8 mol%), IPr. HCl ligand (13.6 mg, 16 mol%), cesium carbonate (97.7 mg, 0.30 mmol) and freshly distilled diisopropyl ether (1.0 ml). Subsequently, the B-alkyl-9-BBN solution was added via syringe, and the reaction mixture was stirred at 110 C for 12 h. Upon purification via column chromatography the pure product was obtained after solvent removal. S12

13 VI. Gram Scale Experiment In a nitrogen-filled glovebox, 1-allyl-4-methoxybenzene (1.08 ml, 7.01 mmol) was added to 9-BBN dimer (854.1 mg, 3.50 mmol) in a 100-mL sealed tube equipped with a stirring bar. Distilled diisopropyl ether (21.9 ml) was added and then the tube was capped and removed from the glovebox. The reaction mixture was stirred at 60 C for 1.5 h, allowed to cool to room temperature, and then taken back into the glovebox. Another 100-mL oven-dried sealed tube containing a stirring bar was charged with naphthalen-2-yl pivalate (1a, 1.00 g, 4.38 mmol), yellow Ni(COD) 2 (24.0 mg, 2 mol%), IPr. HCl ligand (74.4 mg, 4 mol%), cesium carbonate (2.14 g, 6.57 mmol) in the glovebox. Subsequently, the prepared B-alkyl-9-BBN solution was added via syringe, and the reaction mixture was stirred at 110 C for 68 h. After it was cooled down to room temperature, the reaction mixture was extracted three times with ethyl acetate. The combined organic layer was washed with brine, dried over Na 2 SO 4, and then filtrated. The filtrate was concentrated in vacuo and the residue was purified by flash column chromatography (eluent: pure hexane to 50:1 hexane:etoac) to afford the corresponding product 3a as a white solid in 46% yield. S13

14 VII. Spectroscopic Data of Products 2-(3-(4-Methoxyphenyl)propyl)naphthalene (3a) As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (50:1 hexane:etoac), 51.3 mg (93%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.63 (s, 1H), (m, 2H), 7.35 (d, J = 8.4 Hz, 1H), 7.14 (d, J = 8.3 Hz, 2H), 6.86 (d, J = 8.3 Hz, 2H), 3.81 (s, 3H), 2.82 (t, J = 7.7 Hz, 2H), 2.65 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.8, 139.9, 134.4, 133.7, 132.0, 129.4, 127.9, 127.7, , , 126.5, 125.9, 125.1, 113.8, 55.3, 35.6, 34.6, 33.2; IR (ATR): ~ = 2931, 2852, 1696, 1607, 1509, 1452, 1244, 1181, 1027, 813, 743 cm -1 ; MS (EI): m/z (%) = (M +, 77), (100), (34), (47); HRMS (EI) for C 20 H 20 O: calculated for [M] , found (3-(4-Methoxyphenyl)propyl)naphthalene (3b) As for general procedure, starting from naphthalen-1-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (50:1 hexane:etoac), 50.2 mg (91%). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 1H), (m, 1H), 7.72 (d, J = 8.1 Hz, 1H), (m, 2H), 7.41 (t, J = 7.6 Hz, 1H), 7.34 (d, J = 6.9 Hz, 1H), 7.16 (d, J = 8.5 Hz, 2H), 6.86 (d, J = 8.5 Hz, 2H), 3.81 (s, 3H), 3.11 (t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 157.8, 138.6, 134.3, 134.0, 132.0, 129.4, 128.8, 126.6, 126.0, 125.8, 125.6, 125.5, 123.9, 113.8, 55.4, 35.0, 32.6; IR (ATR): ~ = 2933, 2858, 1609, 1510, 1459, 1243, 1176, 1034, 779, 731 cm -1 ; MS (EI): m/z (%) = (M +, 100), (43), (47), (45); HRMS (EI) for C 20 H 20 O: calculated for [M] , found S14

15 9-(3-(4-Methoxyphenyl)propyl)phenanthrene (3c) As for general procedure, starting from phenanthren-9-yl pivalate (55.6 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (50:1 hexane:etoac), 51.5 mg (79%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = 8.75 (dd, J = 8.1, 0.6 Hz, 1H), 8.67 (dd, J = 8.1, 0.6 Hz, 1H), 8.05 (dd, J = 7.7, 1.2 Hz, 1H), 7.84 (dd, J = 7.7, 1.2 Hz, 1H), (m, 5H), 7.18 (d, J = 8.6 Hz, 2H), 6.88 (d, J = 8.6 Hz, 2H), 3.82 (s, 3H), 3.15 (t, J = 7.6 Hz, 2H), 2.77 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.8, 136.5, 134.3, 132.0, 131.3, 130.8, 129.7, 129.5, 128.1, 126.7, 126.5, 126.2, 126.1, 126.0, 124.5, 123.3, 122.5, 113.8, 55.3, 35.1, 32.9, 32.0; IR (ATR): ~ = 3347, 2944, 2719, 1676, 1598, 1466, 1256, 1142, 1028, 806, 748 cm -1 ; MS (EI): m/z (%) = (M +, 54), (100), (79); HRMS (EI) for C 24 H 22 O: calculated for [M] , found (3-(4-Methoxyphenyl)propyl)-1,1'-biphenyl (3d) As for general procedure, starting from [1,1'-biphenyl]-4-yl Ph pivalate (50.8 mg, 0.20 mmol), the product was isolated as colorless solid after flash chromatography on silica gel (50:1 hexane:etoac), 45.3 mg (75%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 2H), (m, 2H), (m, 2H), (m, 1H), (m, 2H), 7.13 (d, J = 8.6 Hz, 2H), (m, 2H), 3.80 (s, 3H), 2.69 (t, J = 7.7 Hz, 2H), 2.64 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.8, 141.6, 141.2, 138.7, 134.4, 129.4, 128.9, 128.8, , , 113.8, 55.4, 35.1, 34.6, 33.2; IR (ATR): ~ = 2929, 2855, 1606, 1504, 1241, 1176, 1114, 1032, 824, 756, 700 cm -1 ; MS (EI): m/z (%) = (M +, 9), (28), (100); HRMS (EI) for C 22 H 22 O: calculated for [M] , found (3-(4-Methoxyphenyl)propyl)-1,1'-biphenyl (3e) As for general procedure, starting from [1,1'-biphenyl]-3-yl pivalate Ph (50.8 mg, 0.20 mmol), the product was isolated as colorless oil after S15

16 flash chromatography on silica gel (50:1 hexane:etoac), 42.9 mg (71%). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.61 (d, J = 7.6 Hz, 2H), (m, 4H), (m, 2H), 7.19 (d, J = 7.5 Hz, 1H), 7.13 (d, J = 8.6 Hz, 2H), 6.85 (d, J = 8.6 Hz, 2H), 3.81 (s, 3H), 2.72 (t, J = 7.7 Hz, 2H), 2.65 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.8, 142.9, 141.5, 141.3, 134.4, 129.4, 128.8, 127.5, 127.4, 127.3, 127.2, 124.7, 113.8, 55.3, 35.6, 34.6, 33.3; IR (ATR): ~ = 3029, 2930, 2855, 2111, 1743, 1607, 1510, 1456, 1244, 1175, 1106, 1033, 802, 754, 698 cm -1 ; MS (EI): m/z (%) = (M +, 2), (100); HRMS (ESI) for C 22 H 22 ONa: calculated for [M+Na] , found (3-(4-Methoxyphenyl)propyl)-1,1'-biphenyl (3f) As for general procedure, starting from [1,1'-biphenyl]-2-yl pivalate Ph (50.8 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (50:1 hexane:etoac), 32.0 mg (53%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), (m, 6H), 6.96 (d, J = 8.6 Hz, 2H), 6.78 (d, J = 8.6 Hz, 2H), 3.79 (s, 3H), 2.63 (t, J = 7.7 Hz, 2H), 2.46 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.7, 142.0, 141.9, 139.9, 134.3, 130.1, , , 129.2, 128.1, 127.4, 126.8, 125.7, 113.7, 55.3, 34.8, 33.1, 32.7; IR (ATR): ~ = 3058, 3023, 2930, 2857, 2318, 2085, 1737, 1609, 1510, 1457, 1243, 1176, 1035, 826, 750, 701 cm -1 ; MS (EI): m/z (%) = (M +, 21), (100); HRMS (ESI) for C 22 H 22 ONa: calculated for [M+Na] , found Methoxy-4-(3-(4-methoxyphenyl)propyl)naphthalene (3g) As for general procedure, starting from 4-methoxynaphthalen-1-yl pivalate (51.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (40:1 hexane:etoac), 35.5 mg (58%). 1 H NMR (600 MHz, CDCl 3 ): δ = 8.31 (d, J = 8.5 Hz, 1H), 7.91 (d, J = 8.2 Hz, 1H), (m, 2H), 7.22 (d, J = 7.8 Hz, 1H), 7.14 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H), 6.75 (d, J = 7.8 Hz, 1H), 3.99 (s, 3H), 3.80 (s, 3H), 3.02 (t, J = 7.6 Hz, 2H), 2.70 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.8, 154.1, 134.5, 132.7, 130.4, 129.4, 126.3, 126.0, 125.6, 124.8, 123.7, 122.6, 113.8, S16

17 103.4, 55.5, 55.3, 35.0, 32.6, 32.1; IR (ATR): ~ = 2930, 1601, 1507, 1259, 1182, 1043, 826, 603 cm -1 ; MS (EI): m/z (%) = (M +, 100), (77), (20), (20); HRMS (ESI) for C 21 H 22 O 2 : calculated for [M+Na] , found Mthoxy-7-(3-(4-methoxyphenyl)propyl)naphthalene (3h) MeO As for general procedure, starting from 7-methoxynaphthalen-2-yl pivalate (51.7 mg, 0.20 mmol), the product was isolated as light yellow solid after flash chromatography on silica gel (50:1 hexane:etoac), 53.8 mg (88%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = 7.71 (dd, J = 8.3, 4.9 Hz, 2H), 7.54 (s, 1H), 7.20 (d, J = 8.3 Hz, 1H), 7.13 (d, J = 8.4 Hz, 2H), (m, 2H), 6.86 (d, J = 8.4 Hz, 2H), 3.93 (s, 3H), 3.81 (s, 3H), 2.80 (t, J = 7.6 Hz, 2H), 2.65 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = , , 140.5, 134.8, 134.4, 129.4, 129.2, 127.6, 127.5, 125.5, 125.2, 117.9, 113.8, 105.5, 55.3, 35.6, 34.6, 33.2; IR (ATR): ~ = 3005, 2930, 2851, 1608, 1509, 1458, 1247, 1212, 1174, 1027, 834, 740 cm -1 ; MS (EI): m/z (%) = (M +, 49), (100); HRMS (ESI) for C 21 H 22 O 2 : calculated for [M+Na] , found Methyl 6-(3-(4-methoxyphenyl)propyl)-2-naphthoate (3i) As for general procedure, starting from methyl MeO O 6-(pivaloyloxy)-2-naphthoate (57.2 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (30:1 hexane:etoac), 47.4 mg (71%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = 8.57 (s, 1H), 8.03 (dd, J = 8.5, 1.5 Hz, 1H), 7.87 (d, J = 8.5 Hz, 1H), 7.80 (d, J = 8.5 Hz, 1H), 7.65 (s, 1H), 7.39 (dd, J = 8.5, 1.5 Hz, 1H), 7.12 (d, J = 8.6 Hz, 2H), 6.84 (d, J = 8.6 Hz, 2H), 3.98 (s, 3H), 3.79 (s, 3H), 2.82 (t, J = 7.6 Hz, 2H), 2.64 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 167.5, 157.9, 142.9, 135.9, 134.2, 131.1, 130.9, , , 128.3, 127.7, 126.7, 126.4, 125.4, 113.8, 55.4, 52.3, 35.7, 34.6, 33.0; IR (ATR): ~ = 2931, 2853, 1712, 1619, 1506, 1281, 1185, 1028, 904, 823, 588 cm -1 ; MS (EI): m/z (%) = (M +, 100), (44), (86), (89); HRMS (EI) for C 22 H 22 O 3 : calculated for [M] , found S17

18 (6-(3-(4-Methoxyphenyl)propyl)naphthalen-2-yl)trimethylsilane (3j) As for general procedure, starting from Me 3 Si 6-(trimethylsilyl)naphthalen-2-yl pivalate (60.1 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (pure hexane), 48.7mg (70%). H NMR (600 MHz, CDCl 3 ): δ = 7.98 (s, 1H), 7.77 (t, J = 7.8 Hz, 2H), (m, 2H), 7.34 (d, J = 8.3 Hz, 1H), 7.12 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H), 3.80 (s, 3H), 2.81 (t, J = 7.6 Hz, 2H), 2.63 (t, J = 7.6 Hz, 2H), (m, 2H), 0.35 (s, 9H); 3 C NMR (150 MHz, CDCl 3 ): δ = 157.8, 140.4, 137.0, 134.4, 133.9, 133.6, 131.6, 129.9, 129.4, 128.0, 127.5, 126.6, 126.3, 113.8, 55.3, 35.6, 34.6, 33.2, -1.0; IR (ATR): ~ = 2937, 2311, 2093, 1739, 1611, 1509, 1457, 1245, 1087, 1036, 830, 753 cm -1 ; MS (EI): m/z (%) = (M +, 100), (50), (27); HRMS (ESI) for C 23 H 28 OSi: calculated for [M+Na] , found (4-(3-(4-Mthoxyphenyl)propyl)phenyl)ethanone (3k) As for general procedure, starting from 4-acetylphenyl Me O pivalate (44.1 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (16:1 hexane:etoac), 33.3 mg (62%). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.88 (d, J = 8.3 Hz, 2H), 7.27 (d, J = 8.3 Hz, 2H), 7.09 (d, J = 8.6 Hz, 2H), 6.84 (d, J = 8.5 Hz, 2H), 3.79 (s, 3H), 2.69 (t, J = 7.6 Hz, 2H), (m, 5H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 198.0, 157.9, 148.3, 135.1, 134.0, 129.4, 128.7, 128.6, 113.8, 55.3, 35.4, 34.5, 32.9, 26.7; IR (ATR): ~ = 2925, 1678, 1605, 1264, 1185, 1059, 825, 666 cm -1 ; MS (EI): m/z (%) = (M +, 43), (100); HRMS (ESI) for C 18 H 20 O 2 : calculated for [M+Na] , found (4-Fluorophenyl)-6-(3-(4-methoxyphenyl)propyl)naphthalene (3l) As for general procedure, starting from 6-(4-fluorophenyl)naphthalen-2-yl pivalate (64.5 mg, F S18

19 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (40:1 hexane:etoac), 46.6 mg (63%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = 7.95 (s, 1H), 7.83 (dd, J = 14.8, 8.4 Hz, 2H), (m, 4H), 7.37 (dd, J = 8.4, 1.5 Hz, 1H), 7.17 (t, J = 8.7 Hz, 2H), 7.13 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H), 3.80 (s, 3H), 2.82 (t, J = 7.6 Hz, 2H), 2.65 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = (d, J C-F = Hz), 157.8, 140.2, (d, J C-F = 2.9 Hz), 136.9, 134.4, 132.8, 132.2, 129.4, (d, J C-F = 7.9 Hz), , , , 126.3, (d, J C-F = 3.3 Hz), (d, J C-F = 21.4 Hz), 113.8, 55.3, 35.6, 34.6, 33.1; 19 F NMR (564 MHz, CDCl 3 ): δ = ; IR (ATR): ~ = 3002, 2928, 2852, 1751, 1602, 1508, 1457, 1238, 1036, 886, 815, 699 cm -1 ; MS (EI): m/z (%) = (M +, 93), (100), (65); HRMS (ESI) for C 26 H 23 FO: calculated for [M] , found (3-(4-Methoxyphenyl)propyl)-2-methylquinoline (3m) As for general procedure, starting from 2-methylquinolin-4-yl pivalate N Me (48.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (8:1 hexane:etoac), 48.9 mg (84%). 1 H NMR (600 MHz, CDCl 3 ): δ = 8.02 (d, J = 8.2 Hz, 1H), 7.89 (d, J = 8.2 Hz, 1H), (m, 1H), (m, 1H), 7.13 (d, J = 8.6 Hz, 2H), 7.12 (s, 1H), 6.85 (d, J = 8.6 Hz, 2H), 3.80 (s, 3H), 3.03 (t, J = 7.8 Hz, 2H), (m, 5H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 158.7, 157.9, 148.2, 148.1, 133.7, , , 129.1, 125.8, 125.5, 123.4, 121.7, 113.9, 55.3, 34.9, 31.8, 31.5, 25.4; IR (ATR): ~ = 2999, 2933, 2859, 1603, 1510, 1456, 1243, 1177, 1033, 830, 760 cm -1 ; MS (EI): m/z (%) = (M +, 100), (67), (79), (79); HRMS (ESI) for C 20 H 21 NO: calculated for [M+H] , found (3-(4-Methoxyphenyl)propyl)-1,2-dihydronaphthalene (3n) As for general procedure, starting from 3,4-dihydronaphthalen-1-yl pivalate (46.0 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (50:1 hexane:etoac), 28.4 mg (51%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 2H), (m, 4H), 6.83 (d, J = 8.5 Hz, 2H), 5.86 (t, J = 4.5 Hz, 1H), 3.79 (s, 3H), 2.74 (t, J = 7.7 Hz, S19

20 2H), 2.63 (t, J = 7.7 Hz, 2H), 2.47 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.7, 136.9, 136.3, 135.0, 134.6, 129.4, 127.6, 126.6, 126.3, 125.0, 122.7, 113.8, 55.4, 34.9, 32.2, 30.4, 28.6, 23.2; IR (ATR): ~ = 2929, 2859, 2834, 1727, 1510, 1455, 1244, 1036, 813, 739 cm -1 ; MS (EI): m/z (%) = (M +, 14), (100); HRMS (EI) for C 20 H 22 O: calculated for [M] , found (3-(4-Methoxyphenyl)propyl)-1,2-dihydronaphthalene (3o) As for general procedure, starting from 3,4-dihydronaphthalen-2-yl pivalate (46.0 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (50:1 hexane:etoac), 37.8 mg (68%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 5H), 7.00 (d, J = 7.4 Hz, 1H), (m, 2H), 6.25 (s, 1H), 3.81 (s, 3H), 2.82 (t, J = 8.2 Hz, 2H), 2.62 (t, J = 8.2 Hz, 2H), 2.26 (q, J = 7.4 Hz, 4H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 157.8, 142.0, 135.0, , , 129.4, 127.2, 126.5, 126.1, 125.4, 122.5, 113.8, 55.3, 37.0, 34.7, 29.6, 28.3, 27.4; IR (ATR): ~ = 2915, 2339, 2093, 1745, 1616, 1479, 1236, 1036, 763 cm -1 ; MS (EI): m/z (%) = (M +, 47), (100), (72); HRMS (ESI) for C 20 H 22 ONa: calculated for [M+Na] , found (5-(4-Methoxyphenyl)pent-1-ene-1,1-diyl)dibenzene (3p) As for general procedure, starting from 2,2-diphenylvinyl pivalate (56.1 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (50:1 hexane:etoac), 38.1 mg (58%). 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 10H), 7.05 (d, J = 8.6 Hz, 2H), 6.81 (d, J = 8.6 Hz, 2H), 6.11 (t, J = 7.5 Hz, 1H), 3.79 (s, 3H), 2.56 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 157.7, 142.9, 142.0, 140.3, 134.5, 130.0, 129.8, 129.3, 128.2, 128.1, 127.3, , , 113.8, 55.3, 34.6, 32.0, 29.4; IR (ATR): ~ = 3056, 3024, 2925, 2855, 2323, 2083, 1734, 1609, 1510, 1446, 1298, 1244, 1176, 1033, 909, 809, 762, 732, 698 cm -1 ; MS (EI): m/z (%) = (M +, 14), (100); HRMS (ESI) for C 24 H 24 ONa: calculated for [M+Na] , found S20

21 2-(3-Phenylpropyl)naphthalene (4a) As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (pure hexane), 39.8 mg (81%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.65 (s, 1H), (m, 2H), 7.37 (d, J = 8.2, 1H), 7.33 (t, J = 7.6 Hz, 2H), (m, 3H), 2.85 (t, J = 7.7 Hz, 2H), 2.73 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 142.3, 139.9, 133.7, 132.1, 128.5, 128.4, 127.9, 127.7, 127.5, 127.4, 126.5, 125.9, 125.8, 125.2, 35.7, 35.5, 32.9; IR (ATR): ~ = 3029, 2929, 2856, 2323, 2100, 1740, 1449, 1365, 1216, 813, 742, 700 cm -1 ; MS (EI): m/z (%) = (M +, 58), (100); Data in accordance with the literature (3-(p-Tolyl)propyl)naphthalene (4b) As for general procedure, starting from naphthalen-2-yl pivalate Me (45.7 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (pure hexane), 45.3 mg (87%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.64 (s, 1H), (m, 2H), 7.36 (d, J = 8.4 Hz, 1H), (m, 4H), 2.84 (t, J = 7.7 Hz, 2H), 2.68 (t, J = 7.7 Hz, 2H), 2.35 (s, 3H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 139.9, 139.2, 135.3, 133.7, 132.0, 129.1, 128.4, 127.9, 127.7, , , 126.5, 125.9, 125.1, 35.6, 35.1, 33.0, 21.1; IR (ATR): ~ = 3039, 2927, 2858, 1510, 1447, 808, 745 cm -1 ; MS (EI): m/z (%) = (M +, 68), (100); HRMS (EI) for C 20 H 20 : calculated for [M] , found (3-(3,4-Dimethoxyphenyl)propyl)naphthalene (4c) As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (16:1 hexane:etoac), 55.1 mg (90%). Mp: C; 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 3H), 7.63 (s, 1H), S21

22 (m, 2H), 7.35 (dd, J = 8.4, 1.4 Hz, 1H), 6.82 (d, J = 8.1 Hz, 1H), (m, 2H), 3.88 (s, 3H), 3.87 (s, 3H), 2.83 (t, J = 7.7 Hz, 2H), 2.65 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 148.9, 147.2, 139.9, 135.0, 133.7, 132.1, 127.9, 127.7, 127.4, 126.5, 126.0, 125.2, 120.3, 111.9, 111.3, 56.0, 55.9, 35.6, 35.1, 33.1; IR (ATR): ~ = 2931, 2852, 1725, 1594, 1510, 1454, 1247, 1141, 1027, 808, 750 cm -1 ; MS (EI): m/z (%) = (M +, 100), (42); HRMS (ESI) for C 21 H 22 O 2 : calculated for [M] , found (3-(4-Fluorophenyl)propyl)naphthalene (4d) As for general procedure, starting from naphthalen-2-yl pivalate F (45.7 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (50:1 hexane:etoac), 39.1 mg (74%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.62 (s, 1H), (m, 2H), 7.34 (d, J = 8.3 Hz, 1H), (m, 2H), 6.99 (t, J = 8.5 Hz, 2H), 2.82 (t, J = 7.7 Hz, 2H), 2.67 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = (d, J C-F = Hz), 139.7, (d, J C-F = 3.0 Hz), 133.7, 132.1, (d, J C-F = 7.7 Hz), 128.0, 127.7, 127.5, 127.4, 126.5, 126.0, 125.2, (d, J C-F = 21.0 Hz), 35.5, 34.7, 33.1; 19 F NMR (564 MHz, CDCl 3 ): δ = ; IR (ATR): ~ = 3050, 2926, 2855, 2105, 1600, 1507, 1456, 1220, 1155, 817, 744 cm -1 ; MS (EI): m/z (%) = (M +, 73), (100); HRMS (ESI) for C 19 H 17 F: calculated for [M] , found (3-(4-(Trifluoromethyl)phenyl)propyl)naphthalene (4e) As for general procedure, starting from naphthalen-2-yl pivalate CF 3 (45.7 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (pure hexane), 36.4 mg (58%). Mp: C; 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 3H), 7.63 (s, 1H), 7.56 (d, J = 8.0 Hz, 2H), (m, 2H), (m, 3H), 2.84 (t, J = 7.7 Hz, 2H), 2.75 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 146.4, 139.4, 133.7, 132.1, 128.8, (q, J C-F = 37.2 Hz), 128.1, 127.7, 127.5, 127.3, 126.6, 126.1, (q, J C-F = 3.8 Hz), , (q, J C-F = Hz), 35.5, 35.3, 32.6; 19 F NMR (376 MHz, CDCl 3 ): δ = (s, CF 3 ); IR (ATR): ~ = 3049, 2934, 2860, 1740, 1614, 1321, S22

23 1115, 820, 746 cm -1 ; MS (EI): m/z (%) = (M +, 88), (100), (62); HRMS (EI) for C 20 H 17 F 3 : calculatedfor [M] , found (3-(Naphthalen-2-yl)propyl)benzo[d][1,3]dioxole (4f) O O As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (50:1 hexane:etoac), 53.4 mg (92%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.62 (s, 1H), (m, 2H), 7.33 (d, J = 8.4 Hz, 1H), 6.74 (d, J = 7.9 Hz, 1H), 6.70 (s, 1H), (m, 1H), 5.93 (s, 2H), 2.80 (t, J = 7.7 Hz, 2H), 2.62 (t, J = 7.7 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 147.6, 145.6, 139.8, 136.2, 133.7, 132.0, 127.9, 127.7, 127.5, 127.4, 126.5, 126.0, 125.2, 121.2, 109.0, 108.2, 100.8, 35.5, 35.2, 33.2; IR (ATR): ~ = 2926, 2321, 2095, 1728, 1605, 1487, 1365, 1243, 1114, 1037, 933, 803, 745 cm -1 ; MS (EI): m/z (%) = (M +, 100), (43), (45); HRMS (EI) for C 20 H 18 O 2 : calculated for [M] , found (4-Phenylbutyl)naphthalene (4g) As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (pure hexane), 42.1 mg (81%). Mp: C; 1 H NMR (400 MHz, CDCl 3 ): δ = (m, 3H), 7.61 (s, 1H), (m, 2H), 7.34 (dd, J = 8.4, 1.5 Hz, 1H), (m, 2H), (m, 3H), 2.82 (t, J = 7.3 Hz, 2H), 2.67 (t, J = 7.3 Hz, 2H), (m, 4H); 13 C NMR (100 MHz, CDCl 3 ): δ = 142.6, 140.1, 133.7, 132.0, 128.5, 128.3, 127.9, 127.7, 127.5, 127.5, 126.4, 125.9, 125.7, 125.1, 36.0, 35.9, 31.2, 31.0; IR (ATR): ~ = 3030, 2927, 2853, 1596, 1492, 1458, 816, 737 cm -1 ; MS (EI): m/z (%) = (M +, 86), (100), 90.9 (71); HRMS (ESI) for C 20 H 20 : calculated for [M] , found S23

24 1-(3-(Naphthalen-2-yl)propyl)-1H-indole (4h) As for general procedure, starting from naphthalen-2-yl pivalate N (45.7 mg, 0.20 mmol), the product was isolated as yellow oil after flash chromatography on silica gel (40:1 hexane:etoac), 31.4 mg (56%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.68 (d, J = 7.9 Hz, 1H), 7.62 (s, 1H), (m, 2H), 7.33 (d, J = 8.3 Hz, 2H), 7.23 (t, J = 7.6 Hz, 1H), (m, 2H), 6.55 (d, J = 3.1 Hz, 1H), 4.19 (t, J = 7.6 Hz, 2H), 2.82 (t, J = 7.6 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 138.5, 136.0, 133.6, 132.2, 128.7, 128.2, 127.8, 127.7, 127.5, 127.1, 126.7, 126.1, 125.4, 121.5, 121.1, 119.3, 109.5, 101.2, 45.7, 33.2, 31.4; IR (ATR): ~ = 3049, 2926, 1306, 1189, 1042, 887, 616 cm -1 ; MS (EI): m/z (%) = (M +, 84), (37), (58), (100), (46); HRMS (ESI) for C 21 H 19 N: calculated for [M+H] , found (3-Phenoxypropyl)naphthalene (4i) As for general procedure, starting from naphthalen-2-yl pivalate O (45.7 mg, 0.20 mmol), the product was isolated as white solid after flash chromatography on silica gel (pure hexane), 35.1 mg (67%). Mp: C; 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.66 (s, 1H), (m, 2H), 7.38 (d, J = 8.1 Hz, 1H), 7.29 (t, J = 7.5 Hz, 2H), (m, 3H), 4.01 (t, J = 6.0 Hz, 2H), 3.00 (t, J = 7.4 Hz, 2H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 159.1, 139.1, 133.7, 132.1, 129.5, 128.1, 127.7, 127.5, 127.4, 126.6, 126.0, 125.3, 120.7, 114.6, 66.8, 32.4, 30.9; IR (ATR): ~ = 2957, 2921, 1727, 1596, 1473, 1243, 1035, 820, 746, 695 cm -1 ; MS (EI): m/z (%) = (M +, 100), (37), (66), (81); HRMS (EI) for C 19 H 18 O: calculated for [M] , found (2-Methyl-3-phenylpropyl)naphthalene (4j) Me As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (pure hexane), 24.4 mg (47%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.60 (s, 1H), (m, 2H), (m, 3H), (m, 3H), 2.86 (dd, J S24

25 = 13.4, 5.9 Hz, 1H), 2.74 (dd, J = 13.4, 5.9 Hz, 1H), 2.58 (dd, J = 13.5, 8.3 Hz, 1H), 2.47 (dd, J = 13.4, 8.3 Hz, 1H), (m, 1H), 0.87 (d, J = 6.6 Hz, 3H); 13 C NMR (150 MHz, CDCl 3 ): δ = 141.3, 138.9, 133.6, 132.1, 129.3, 128.3, 128.0, 127.8, 127.7, 127.5, 127.4, , , 125.2, 43.6, 43.5, 37.2, 19.3; IR (ATR): ~ = 3033, 2919, 2319, 2097, 1740, 1451, 1367, 1219, 810, 740, 700 cm -1 ; MS (EI): m/z (%) = (M +, 52), (100), (55), 90.9 (42); HRMS (EI) for C 20 H 20 : calculated for [M] , found (3-Cyclohexylpropyl)naphthalene (4k) As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (pure hexane), 39.8 mg (79%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.61 (s, 1H), (m, 2H), 7.33 (dd, J = 8.3, 1.6 Hz, 1H), 2.75 (t, J = 7.7 Hz, 2H), (m, 7H), (m, 8H); 13 C NMR (150 MHz, CDCl 3 ): δ = 140.6, 133.7, 132.0, 127.8, 127.7, , , 126.3, 125.9, 125.0, 37.7, 37.3, 36.5, 33.5, 28.8, 26.8, 26.5; IR (ATR): ~ = 2920, 2849, 2114, 1448, 1261, 811, 742 cm -1 ; MS (EI): m/z (%) = (M +, 75), (94), (100); HRMS (EI) for C 19 H 24 : calculated for [M] , found Otylnaphthalene (4l) As for general procedure, starting from naphthalen-2-yl pivalate (45.7 mg, 0.20 mmol), the product was isolated as colorless oil after flash chromatography on silica gel (pure hexane), 29.8 mg (62%). 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 3H), 7.61 (s, 1H), (m, 2H), 7.34 (dd, J = 8.4, 1.6 Hz, 1H), 2.77 (t, J = 7.7 Hz, 2H), (m, 2H), (m, 10H), 0.88 (t, J = 7.0 Hz, 3H); 13 C NMR (150 MHz, CDCl 3 ): δ = 140.6, 133.7, 132.0, 127.8, 127.7, , , 126.3, 125.9, 125.0, 36.2, 32.0, 31.5, 29.6, 29.5, 29.4, 22.8, 14.2; IR (ATR): ~ = 3048, 2923, 2855, 1740, 1455, 1367, 1217, 810, 741 cm -1 ; MS (EI): m/z (%) = (M +, 73), (91), (100); Data in accordance with the literature. 11 S25

26 VIII. Synthetic Application 9-BBN PivO OTs 5 PhB(OH) 2 (2.0 equiv) Pd(OAc) 2 (2.0 mol%) XPhos (5.0 mol%) K 3 PO 4 (3.0 equiv) t BuOH, 90 C, 12 h PivO 6, 88% Me (1.6 equiv) Ni(COD) 2 (8.0 mol%) IPr.HCl (16.0 mol%) Cs 2 CO 3 (1.5 equiv) i Pr 2 O, 120 C, 40 h Me LiCH 2 SiMe 3 (1.3 equiv) Ni(COD) 2 (5.0 mol%) Me Toluene, 80 C, 5 h SiMe 3 7, 56% 8, 86% 3-Methoxy-5-(tosyloxy)phenyl pivalate (5) was synthesized from 3,5-dihydroxyanisole according to the literature method. 12 Synthesis of 5-methoxy-[1,1'-biphenyl]-3-yl pivalate (6) An oven-dried Schlenk tube containing a stirring bar was charged with 5 (61.7 mg, 0.20 mmol), phenylboronic acid (48.8 mg, 0.40 mmol), Pd(OAc) 2 (0.9 mg, mmol), XPhos (4.8 mg, 0.01 mmol) and K 3 PO 4 (127 mg, 0.60 mmol). The tube was degassed three times. Then 2.0 ml of t BuOH was charged and the reaction was stirred at 90 C for 12 h. The mixture was cooled to room temperature, quenched with saturated aqueous NH 4 Cl and extracted with ethyl acetate. The organic layer was concentrated under vacuum and the product 6 was purified by flash column chromatography and obtained as a light yellow oil H NMR (600 MHz, CDCl 3 ): δ = (m, 2H), 7.43 (t, J = 7.7 Hz, 2H), 7.36 (t, J = 7.4 Hz, 1H), S26

27 (m, 1H), (m, 1H), (m, 1H), 3.86 (s, 3H), 1.39 (s, 9H); 13 C NMR (150 MHz, CDCl 3 ): δ = 177.1, 160.7, 152.4, 143.5, 140.4, 128.8, 127.8, 127.3, 112.9, 110.6, 106.2, 55.6, 39.2, 27.2; IR (ATR): ~ = 2962, 2316, 2100, 1747, 1595, 1462, 1247, 1120, 1052, 857, 759, 692 cm -1 ; MS (EI): m/z (%) = (83), (M +, 100); HRMS (ESI) for C 18 H 20 O 3 : calculated for [M+Na] , found Synthesis of 3-methoxy-5-(3-(p-tolyl)propyl)-1,1'-biphenyl (7) In a nitrogen-filled glovebox, an oven-dried sealed tube containing a stirring bar was charged with 6 (56.8 mg, 0.20 mmol), yellow Ni(COD) 2 (4.4 mg, 8 mol%), IPr. HCl ligand (13.6 mg, 16 mol%), cesium carbonate (97.7 mg, 0.30 mmol) and freshly distilled diisopropyl ether (1.0 ml). Subsequently, the B-alkyl-9-BBN solution was added via syringe, and the reaction mixture was stirred at 120 C for 40 h. Upon purification via column chromatography the pure product 7 was obtained as a light yellow oil after solvent removal. 1 H NMR (600 MHz, CDCl 3 ): δ = (m, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.35 (t, J = 7.4 Hz, 1H), (m, 4H), 7.02 (s, 1H), (m, 1H), 6.74 (s, 1H), 3.86 (s, 3H), (m, 4H), 2.33 (s, 3H), (m, 2H); 13 C NMR (150 MHz, CDCl 3 ): δ = 160.0, 144.4, 142.7, 141.4, 139.2, 135.3, 129.1, 128.8, 128.4, 127.4, 127.3, 120.1, 113.1, 110.2, 55.4, 35.7, 35.1, 33.0, 21.1; IR (ATR): ~ = 3006, 2929, 2857, 2326, 2087, 1894, 1722, 1592, 1509, 1455, 1336, 1213, 1154, 1058, 855, 760, 698 cm -1 ; MS (EI): m/z (%) = (M +, 81), (100); HRMS (EI) for C 23 H 24 O: calculated for [M] , found S27

28 Synthesis of trimethyl((5-(3-(p-tolyl)propyl)-[1,1'-biphenyl]-3-yl)methyl)silane (8) Me LiCH 2 SiMe 3 (1.3 equiv) Ni(COD) 2 (5.0 mol%) Me Toluene, 80 C, 5 h SiMe 3 7 8, 86% An oven-dried, argon-flushed Schlenk tube was charged with 7 (31.6 mg, 0.1 mmol) and yellow Ni(COD) 2 (1.4 mg, 5 mol%). The tube was immediately sealed and again flushed with argon. Subsequently, freshly distilled toluene (1.5 ml) and a LiCH 2 SiMe 3 solution in pentane (1.0 M) were added and the mixture was stirred for 5 h at 80 C. Upon purification via column chromatography the pure product 8 was obtained as colorless oil after solvent removal H NMR (600 MHz, CDCl 3 ): δ = (m, 2H), 7.42 (t, J = 7.6 Hz, 2H), 7.33 (t, J = 7.4 Hz, 1H), (m, 5H), 7.05 (s, 1H), 6.82 (s, 1H), (m, 4H), 2.33 (s, 3H), 2.13 (s, 2H), (m, 2H), 0.03 (s, 9H); 13 C NMR (150 MHz, CDCl 3 ): δ = 142.6, 141.8, 141.1, 140.9, 139.4, 135.2, 129.1, 128.7, 128.4, 127.4, 127.3, 127.0, 124.5, 123.3, 35.6, 35.2, 33.3, 27.2, 21.1, -1.7; IR (ATR): ~ = 2927, 2317, 2097, 1593, 1440, 1246, 1155, 845, 695 cm -1 ; MS (EI): m/z (%) = (M +, 64), (69), 72.9 (100); HRMS (ESI) for C 26 H 32 Si: calculated for [M+Na] , found S28

29 References: 1. Quasdorf, K. W.; Tian, X.; Garg, N. K. J. Am. Chem. Soc. 2008, 130, Shimasaki, T.; Tobisu, M.; Chatani, N. Angew. Chem., Int. Ed. 2010, 49, Takise, R.; Muto, K.; Yamaguchi, J.; Itami, K. Angew. Chem., Int. Ed. 2014, 53, Xiao, B.; Fu, Y.; Xu, J.; Gong, T.-J.; Dai, J.-J.; Yi, J.; Liu, L. J. Am. Chem. Soc. 2010, 132, Zarate, C.; Martin, R. J. Am. Chem. Soc. 2014, 136, Gogsig, T. M.; Kleimark, J.; Nilsson, L.; Sten, O.; Korsager, S.; Lindhardt, A. T.; Norrby, P.; Skrydstrup, T. J. Am. Chem. Soc. 2012, 134, Li, B.-J.; Xu, L.; Wu, Z.-H.; Guan, B.-T.; Sun, C.-L.; Wang, B.-Q.; Shi, Z.-J. J. Am. Chem. Soc. 2009, 131, Kinuta, H.; Hasegawa, J.; Tobisu, M.; Chatani, N. Chem. Lett. 2015, 44, Saito, B.; Fu, G. C. J. Am. Chem. Soc. 2007, 129, Sugimoto, A.; Sakamoto, S.; Suyama, K.; Yoneda, S. Bull. Chem. Soc. Jpn. 1986, 59, Britton, M.; Fawthrop, S.; Gillies, D.; Sutcliffe, L.; Wu, X.; Smirnov, A. Magn. Reson. Chem. 1997, 35, Zhao, F.; Zhang, Y.-F.; Wen, J.; Yu, D.-G.; Wei, J.-B.; Xi, Z.-F.; Shi, Z.-J. Org. Lett. 2013, 15, Nguyen, H. N.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc. 2003, 125, Leiendecker, M.; Hsiao, C.-C.; Guo, L.; Alandini, N.; Rueping, M. Angew. Chem., Int. Ed. 2014, 53, S29

30 IX. Copies of 1 H and 13 C NMR Spectra S30

31 S31

32 S32

33 3a 3a S33

34 3b 3b S34

35 3c 3c S35

36 Ph 3d Ph 3d S36

37 Ph 3e Ph 3e S37

38 Ph 3f Ph 3f S38

39 3g 3g S39

40 MeO 3h MeO 3h S40

41 MeO O 3i MeO O 3i S41

42 Me 3 Si 3j Me 3 Si 3j S42

43 Me O 3k Me O 3k S43

44 F 3l F 3l S44

45 F 3l S45

46 N Me 3m N Me 3m S46

47 3n 3n S47

48 3o 3o S48

49 3p 3p S49

50 4a 4a S50

51 4b Me 4b Me S51

52 4c 4c S52

53 4d F 4d F S53

54 4d F S54

55 4e CF 3 4e CF 3 S55

56 4e CF 3 S56

57 O O 4f O O 4f S57

58 Ph 4g Ph 4g S58

59 N 4h N 4h S59

60 OPh 4i OPh 4i S60

61 Me 4j Me 4j S61

62 4k 4k S62

63 4l 4l S63

64 Ph PivO 6 Ph PivO 6 S64

65 Me 7 Me 7 S65

66 Me SiMe 3 8 Me SiMe 3 8 S66