Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C H Bonds by Silver-Mediated C H Activation: A Synthetic and Mechanistic Investigation

Transcription

1 Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C H Bonds by Silver-Mediated C H Activation: A Synthetic and Mechanistic Investigation Sarah Yunmi Lee and John F. Hartwig* Department of Chemistry, University of California, Berkeley, CA 94720, United States Supporting Information Table of Contents I. General Information S1 II. Synthesis of di-tert-butylarylphosphines S2 III. Synthesis of Allylic Pivalates S4 IV. Direct Allylations of Arenes with Allylic Pivalates S7 V. H/D Exchange Experiments of 1-Fluoronaphthalene S16 VI. Preparation of Palladium Complexes (PdL2, 6, and 12) S17 VII. Preparation of Silver Complexes (7 and 8) S23 VIII. Reactivity and Mechanistic Studies IX. NMR Spectra of Isolated Compounds S38 S29 I. General Information All reactions were assembled under an atmosphere of nitrogen using oven-dried glassware. Tetrahydrofuran (THF), diethyl ether, toluene, dichloromethane, and pentane were degassed by purging with nitrogen and then dried with a solvent purification system containing activated alumina. Pd(OAc)2 and Pd(OPiv)2 were purchased from Strem or Aldrich and used as received. All arene substrates were purchased from commercial suppliers and degassed with nitrogen for 30 min prior to use. Silver pivalate was prepared by the reaction of silver nitrate and pivalic acid. 1 All other reagents were purchased from commercial suppliers and used as received. NMR spectra were acquired on 400, 500, and 600 MHz Bruker S-3 instruments at the University of California, Berkeley NMR facility. Chemical shifts were reported relative to residual solvent peaks (CDCl3 = 7.26 ppm for 1 H and 77.2 ppm for 13 C; CD2Cl2 = 5.32 ppm for 1 H and 53.8 ppm for 13 C; C6D6 = 7.16 ppm for 1 H and for 13 C). S1

2 II. Synthesis of di-tert-butylarylphosphines Synthesis of di-tert-butyl(2-methoxyphenyl)phosphine (Pt-Bu2(2-OMeC6H4; L). This procedure is modified from a published procedure. 2 Preparation of (2-methoxyphenyl)lithium. To a solution of 2-bromoanisole [ ] (5.61 g, 30.0 mmol) in pentane (18 ml) at 0 C was added n-buthyllithium (12 ml, 30 mmol; 2.5 M in hexanes) dropwise over 3 min. The resulting mixture was stirred for 1 h at room temperature, and white precipitates were collected by filtration (washed with 10 ml of pentane). (2- Methoxyphenyl)lithium was isolated as a white powder (3.41 g, >99%). Di-tert-butylchlorophosphine (4.06 g, 22.5 mmol) and diethyl ether (25 ml) were placed in a 100-mL round-bottom flask equipped with a stir bar. To this vial was added (2- methoxyphenyl)lithium (3.08 g, 27.0 mmol) in diethyl ether (20 ml). The resulting mixture was stirred at room temperature for 12 h and then filtered through a pad of silica (eluted with 10 ml of tetrahydrofuran). The filtrate was concentrated under reduced pressure. The yellow residue was dissolved in 10 ml of 5% diethyl ether in pentanes and filtered through a pad of silica (eluted with 30 ml of 5% diethyl ether in pentanes). The filtrate was concentrated under reduced pressure. The title compound was isolated as a colorless oil (4.70 g, 83%). (Note: all manipulations including purification were conducted in the nitrogen-filled glovebox). Spectral data matched those of a previous report. 2 Note: The title compound exists as a ~1:1 mixture of two conformers due to the restricted rotation around P C(aryl) bond. 1 H NMR (400 MHz, C6D6) δ 7.93 (dd, J = 14.2 Hz, J = 7.4 Hz, 0.5H), 7.72 (d, J = 7.5 Hz, 0.5H), 7.14 (dd, J = 13.6 Hz, J = 6.8 Hz, 1H), 6.85 (dt, J = 14.3 Hz, J = 7.3 Hz, 1H), 6.59 (dd, J = 8.3 Hz, J = 4.9 Hz, 0.5H), 6.47 (d, J = 8.1 Hz, 0.5H), 3.37 (s, 1.5H), 3.21 (s, 1.5H), (m, 18H). 31 P NMR (162 MHz, C6D6) δ 55.0, Synthesis of di-tert-butyl(4-methoxyphenyl)phosphine [ ]. Di-tertbutylchlorophosphine (900 mg, 5.00 mmol), CuCl (25 mg, 0.25 mmol), and THF (5.0 ml) were placed in a 50-mL round-bottom flask equipped with a stir bar. To this solution was added (4- methoxyphenyl)magnesium bromide (15 ml of 0.50 M in THF, 7.5 mmol) dropwise over 45 min. The resulting mixture was refluxed for 12 h and then cooled to room temperature. Aqueous S2

3 sulfuric acid (3.0 ml of a 5% aqueous solution), water (5.0 ml), and THF (3.0 ml) were added to the reaction mixture. The layers were separated, and the aqueous layer was washed with diethyl ether (3 ml x 2). The combined organic layers were washed with water (5.0 ml), dried over MgSO4, filtered, and concentrated. The residue was purified by column chromatography (10% diethyl ether in pentane; run in the nitrogen-filled glovebox), which furnished the product as a colorless oil (yield was not determined). 1 H NMR (400 MHz, CD2Cl2) δ 7.58 (dd, J = 8.7 Hz, J = 6.9 Hz, 2H), 6.87 (d, J = 8.7 Hz, 2H), 3.80 (s, 3H), 1.16 (d, J = 11.6 Hz, 18H). 13 C NMR (101 MHz, CD2Cl2) δ 160.8, (d, J = 21.4 Hz), (d, J = 20.9 Hz), (d, J = 9.0 Hz), 55.5, 32.1 (d, J = 21.2 Hz), 30.6 (d, J = 14.6 Hz). 31 P NMR (243 MHz, C6D6) δ MS (EI) m/z (M+) calcd for [C15H25OP]: 252, found: 252. Synthesis of di-tert-butyl(4-methoxyphenyl)phosphine [ ]. Di-tertbutylchlorophosphine (900 mg, 5.00 mmol), CuCl (25 mg, 0.25 mmol), and THF (5.0 ml) were placed in a 50-mL round-bottom flask equipped with a stir bar. To this solution was added (2- trifluoromethylphenyl)magnesium bromide (15 ml of 0.50 M in 2-MeTHF, 7.5 mmol) dropwise over 45 min. The resulting mixture was refluxed for 12 h and then cooled to room temperature. Aqueous sulfuric acid (3.0 ml of a 5% aqueous solution), water (5.0 ml), and THF (3.0 ml) were added to the reaction mixture. The layers were separated, and the aqueous layer was washed with diethyl ether (3 ml x 2). The combined organic layers were washed with water (5.0 ml), dried over MgSO4, filtered, and concentrated. The residue was purified by column chromatography (10% diethyl ether in pentane; run in the nitrogen-filled glovebox), which furnished the product as a colorless oil (yield was not determined). 1 H NMR (500 MHz, C6D6) δ 7.79 (d, J = 7.6 Hz, 1H), 7.58 (dt, J = 8.1, J = 1.9 Hz, 1H), 7.00 (t, J = 7.5 Hz, 1H), 6.91 (t, J = 7.7 Hz, 1H), 1.12 (d, J = 11.8 Hz, 18H). 31 P NMR (162 MHz, C6D6) δ F NMR (376 MHz, C6D6) δ (d, J = 59.0 Hz). MS (EI) m/z (M+) calcd for [C15H22F3P]: 290, found: 290. S3

4 III. Synthesis of Allylic Pivalates General Procedure 1. This procedure is modified from a published procedure for the acylation of allylic alcohols. 3 To a solution of an allylic alcohol and 4-dimethylaminopyridine (DMAP) in CH2Cl2 was added pivalic anhydride. The mixture was cooled to 0 C. To this solution was added pyridine in CH2Cl2 dropwise over 5 min. Next, the reaction mixture was stirred at room temperature. After 12 h, HCl (2M) was added, and the aqueous layer was extracted with CH2Cl2. The combined organic layers were washed with the saturated solution of NaHCO3 (aq), dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was then purified by column chromatography (10% EtOAC in hexanes; KMnO4 stain). (E)-3-(p-tolyl)allyl pivalate (2b): The title compound was prepared according to the General Procedure 1, using (E)-3-(p-tolyl)prop-2-en-1-ol [ ] (860 mg, 5.80 mmol), Piv2O (1.08 g, 5.80 mmol), DMAP (70.9 mg, mmol), pyridine (0.470 ml, 5.80 mmol), and dichloromethane (1.2 ml). After purification by flash chromatography, the title compound was isolated as a white solid (1.18 g, 87% yield). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), 6.61 (d, J = 15.6 Hz, 1H), (m, 1H), 4.71 (d, J = 6.5 Hz, 2H), 2.34 (s, 3H), 1.23 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.5, 138.0, 133.8, 133.7, 129.4, 126.6, 122.7, 65.2, 39.0, 27.4, MS (EI) m/z (M + ) calcd for [C15H20O2]: 232, found: 232. (E)-3-(4-(trifluoromethyl)phenyl)allyl pivalate (2c): The title compound was prepared according to the General Procedure 1, using (E)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-ol [ ] (905 mg, 4.48 mmol), Piv2O (834 mg, 4.48 mmol), DMAP (54.7 mg, mmol), pyridine (0.360 ml, 4.48 mmol), and dichloromethane (0.93 ml). After purification by flash chromatography, the title compound was isolated as a white solid (0.88 g, 69% yield). 1 H NMR (400 MHz, CDCl3) δ 7.58(d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 6.66 (d, J = 16.1 Hz, 1H), (m, 1H), 4.75 (d, J = 6.1 Hz, 2H), 1.24 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.4, 140.0, 131.9, (d, J = 32.4 Hz), 126.9, 126.5, (q, J = 3.8 Hz), 122.9, 64.6, 39.0, F NMR (376 MHz, CDCl3) δ MS (EI) m/z (M + ) calcd for [C15H17F3O2]: 286, found: 286. S4

5 (E)-3-(4-chlorophenyl)allyl pivalate (2d): The title compound was prepared according to the General Procedure 1, using (E)-3-(4- chlorophenyl)prop-2-en-1-ol [ ] (1.26 g, 7.50 mmol), Piv2O (1.40 g, 7.50 mmol), DMAP (91.6 mg, mmol), pyridine (0.600 ml, 7.50 mmol), and dichloromethane (1.5 ml). After purification by flash chromatography, the title compound was isolated as a colorless oil (1.22 g, 64% yield). 1 H NMR (400 MHz, CDCl3) δ (m, 4H), 6.59 (d, J = 16.0, 1H), 6.25 (dt, J = 16.3 Hz, 6.2 Hz, 1H), 4.71 (d, J = 6.2 Hz, 2H), 1.23 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.3, 134.9, 133.7, 132.3, 128.8, 127.9, 124.4, 64.8, 38.9, MS (EI) m/z (M + ) calcd for [C14H17ClO2]: 252, found: 252. Methyl (E)-4-(3-(pivaloyloxy)prop-1-en-1-yl)benzoate (2e): The title compound was prepared according to the General Procedure 1, using methyl (E)-4-(3-hydroxyprop-1-en-1-yl)benzoate [ ] (76.9 mg, mmol), Piv2O (74.5 mg, mmol), DMAP (4.89 mg, mmol), pyridine ( ml, mmol), and dichloromethane (0.10 ml). After purification by flash chromatography, the title compound was isolated as a white solid (90.0 mg, 85% yield). 1 H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.3 Hz, 2H), 7.44 (d, J = 8.3 Hz, 2H), 6.67 (d, J = 16.0 Hz, 1H), 6.39 (dt, J = 16.0 Hz, J = 6.0 Hz 1H), 4.75 (dd, J = 6.0 Hz, J = 1.6 Hz, 2H), 3.91 (s, 3H), 1.24 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.0, 166.6, 140.7, 132.1, 129.9, 129.3, , , 64.4, 52.0, 38.8, MS (EI) m/z (M + ) calcd for [C16H20O4]: 276, found: 276. (E)-3-(2-methoxyphenyl)allyl pivalate (2f): The title compound was prepared according to the General Procedure 1, using 3-(2- methoxyphenyl)prop-2-en-1-ol [ ] (821 mg, 5.00 mmol), Piv2O (931 mg, 5.00 mmol), DMAP (61.1 mg, mmol), pyridine (0.400 ml, 5.00 mmol), and dichloromethane (1.0 ml). After purification by flash chromatography, the title compound was isolated as a colorless oil (870 mg, 70% yield; contained 11% of (Z)-isomer). 1 H NMR (400 MHz, CDCl3) δ 7.44 (dd, J = 7.6 Hz, J =1.7 Hz, 1H), (m, 1H), (m, 3H), 6.30 (dt, J = 16.0 Hz, J = 6.3 Hz, 1H), 4.73 (dd, J = 6.3, J = 1.4 Hz, 2H), 3.85 (s, 3H), 1.23 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.5, 157.0, 129.2, 128.6, 127.2, 125.5, 124.3, 120.8, 111.0, 65.6, 55.6, 39.0, MS (EI) m/z (M + ) calcd for [C15H20O3]: 248, found: 248. S5

6 (E)-3-(3-methoxyphenyl)allyl pivalate (2g): The title compound was prepared according to the General Procedure 1, using (E)-3-(3- methoxyphenyl)prop-2-en-1-ol [ ] (1.22 mg, 7.43 mmol), Piv2O (1.38 g, 7.43 mmol), DMAP (90.8 mg, mmol), pyridine (0.600 ml, 7.43 mmol), and dichloromethane (1.5 ml). After purification by flash chromatography, the title compound was isolated as a colorless oil (1.65 g, 89% yield). 1 H NMR (400 MHz, CDCl3) δ (m, 1H), 6.99 (d, J = 7.8 Hz, 1H), 6.93 (t, J = 2.1 Hz, 1H), 6.82 (dd, J = 8.3 Hz, J = 2.6 Hz, 1H), 6.61 (d, J = 15.8 Hz, 1H), 6.28 (dt, J = 15.8 Hz, J = 6.2 Hz, 1H), 4.72 (dd, J = 6.2 Hz, J = 1.4 Hz, 2H), 3.82 (s, 3H), 1.23 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.4, 159.9, 137.9, 133.6, 129.7, 124.0, 119.4, 113.8, 112.0, 64.9, 55.3, 38.9, MS (EI) m/z (M + ) calcd for [C15H20O3]: 248, found: 248. (E)-3-(naphthalen-2-yl)allyl pivalate (2h): The title compound was prepared according to the General Procedure 1, using (E)-3-(naphthalen- 2-yl)prop-2-en-1-ol [ ] (1.00 g, 5.43 mmol), Piv2O (1.01 g, 5.43 mmol), DMAP (66.3 mg, mmol), pyridine (0.440 ml, 5.43 mmol), and dichloromethane (1.2 ml). After purification by flash chromatography, the title compound was isolated as a white solid (1.12 g, 77% yield). 1 H NMR (400 MHz, CDCl3) δ (m, 3H), 7.75 (d, J = 1.7 Hz, 1H), 7.60 (dd, J = 8.6 Hz, J = 1.8 Hz, 1H), (m, 2H), 6.81 (d, J = 15.9 Hz, 1H), 6.41 (dt, J = 15.9 Hz, J = 6.2 Hz, 1H), 4.78 (dd, J = 6.3 Hz, J = 1.4 Hz, 2H), 1.25 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.5, 133.9, 133.8, 133.7, 133.3, 128.4, 128.2, 127.8, 126.9, 126.5, 126.2, 124.1, 123.7, 65.1, 39.0, MS (EI) m/z (M + ) calcd for [C18H20O2]: 268, found: 268. (E)-2-methyl-3-phenylallyl pivalate (2j): The title compound was prepared according to the General Procedure 1, using (E)-2-methyl-3-phenylprop-2-en- 1-ol [ ] (1.11 g, 7.50 mmol), Piv2O (1.40 g, 7.50 mmol), DMAP (91.6 mg, mmol), pyridine (0.600 ml, 7.50 mmol), and dichloromethane (1.5 ml). After purification by flash chromatography, the title compound was isolated as a colorless oil (1.20 g, 69% yield). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 3H), 6.51 (s, 1H), 4.62 (s, 2H), 1.88 (s, 3H), 1.24 (s, 9H). 13 C NMR (101 MHz, CDCl3) δ 178.2, 137.2, 133.1, 129.0, 128.2, 127.6, 126.7, 69.8, 39.0, 27.3, MS (EI) m/z (M + ) calcd for [C15H20O2]: 232, found: 232. S6

7 IV. Direct Allylations of Arenes with Allylic Pivalates General Procedure 2. Pd(OAc)2 (7.68 mg, mmol), Cs2CO3 (274 mg, mmol), AgOPiv (73.1 mg, mmol), arene (1.40 ml) were added to a 20-mL vial equipped with a stir bar. To this vial was added Pt-Bu2(2-OMeC6H4) (17.7 mg, mmol) and allylic pivalate (0.350 mmol). This vial was sealed with a Teflon-lined cap and electrical tape. The reaction mixture was heated at 120 C with stirring in an aluminum block. After 17 h, the reaction mixture was cooled to room temperature, filtered through a pad of Celite (eluted with dichloromethane 20 ml), and then concentrated under reduced pressure. The residue was purified by column chromatography (5% Et2O in hexanes 20% Et2O in hexanes; KMnO4 stain). 1-Cinnamyl-2-fluorobenzene (Table 2, entry 1) [ ]. Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (60.6 mg, 82%). Spectral data matched those of a previous report. 4 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 3H), (m, 2H), (m, 2H), 6.46 (d, J = 15.8 Hz, 1H), 6.34 (dt, J = 15.8 Hz, J = 6.7 Hz, 1H), 3.58 (d, J = 6.7 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 137.5, 131.6, (d, J = 4.8 Hz), 128.6, (d, J = 8.0 Hz), 127.7, , , 126.3, (d, J = 3.6 Hz), (d, J = 22.0 Hz), 32.3 (d, J = 3.1 Hz). 19 F NMR (376 MHz, CDCl3) δ (m). MS (EI) m/z (M + ) calcd for [C15H13F]: 212, found: 212. (E)-1-fluoro-2-(3-(p-tolyl)allyl)benzene (Table 2, entry 2). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with (E)-3-(p-tolyl)allyl pivalate (81.3 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (60.3 mg, 76%). 1 H NMR (400 MHz, CDCl3) δ (m, 4H), (m, 4H), 6.44 (d, J = 15.9 Hz, 1H), 6.29 (dt, J = 15.5 Hz, J = 6.6 Hz, 1H), 3.57 (d, J = 6.9 Hz, 2H), 2.33 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 137.0, 134.7, 131.4, (d, J = 4.7 Hz), 129.3, (d, J = 8.0 Hz), (d, J = 15.5 Hz), 126.6, 126.2, (d, J = 3.5 Hz), (d, J = 21.9 Hz), 32.3 (d, J = 2.9 Hz), F NMR (376 MHz, CDCl3) δ (m). MS (EI) m/z (M + ) calcd for [C16H15F]: 226, found: 226. S7

8 (E)-1-fluoro-2-(3-(4-(trifluoromethyl)phenyl)allyl)benzene (Table 2, entry 3). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with (E)-3-(4- (trifluoromethyl)phenyl)allyl pivalate (100 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (56.8 mg, 58%). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 141.0, (d, J = 4.8 Hz), 130.6, 130.3, (m), (d, J = 8.1 Hz), (d, J = 15.9 Hz), 126.4, (m), (d, J = 3.6 Hz), 123.0, (d, J = 22.0 Hz), 32.5 (d, J = 3.0 Hz). 19 F NMR (376 MHz, CDCl3) δ -61.6, (m). MS (EI) m/z (M + ) calcd for [C16H12F4]: 280, found: 280. (E)-1-fluoro-2-(3-(4-chlorophenyl)allyl)benzene (Table 2, entry 4). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with (E)-3-(4-chlorophenyl)allyl pivalate (88.5 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (53.8 mg, 62%). 1 H NMR (400 MHz, CDCl3) δ (m, 6H), (m, 2H), 6.40 (d, J = 15.9 Hz, 1H), (m, 1H), 3.56 (d, J = 6.4 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ161.1 (d, J = Hz), 136.0, 132.9, (d, J = 4.6 Hz), 130.3, 128.8, 128.5, (d, J = 8.1 Hz), 127.5, (d, J = 16.0 Hz), (d, J = 3.7 Hz), (d, J = 21.9 Hz), 32.4 (d, J = 3.0 Hz). 19 F NMR (376 MHz, CDCl3) δ (m). MS (EI) m/z (M + ) calcd for [C15H12ClF]: 246, found: 246. Methyl (E)-4-(3-(2-fluorophenyl)prop-1-en-1yl)benzoate (Table 2, entry 5). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with methyl (E)-4-(3-(pivaloyloxy)prop-1-en-1-yl)benzoate (96.7 mg, mmol). After purification by column chromatography, the title compound was isolated as a white solid (50.9 mg, 54%). 1 H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), (m, 2H), (m, 2H), 6.47 (s, 2H), 3.90 (s, 3H), 3.60 (s, 2H). 13 C NMR (101 MHz, CDCl3) δ 167.0, (d, J = Hz), 142.0, (d, J = 4.6 Hz), 130.7, , , 128.8, (d, J = 8.0 Hz), (d, J = 15.9 Hz), 126.1, (d, J = 3.6 Hz), (d, J = 22.0 Hz), 52.1, 32.5 (d, J = 3.1 Hz). 19 F NMR (376 MHz, CDCl3) δ (m). S8

9 MS (EI) m/z (M + ) calcd for [C17H15FO2]: 270, found: 270. (E)-1-fluoro-2-(3-(2-methoxyphenyl)allyl)benzene (Table 2, entry 6). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with (E)-3-(2-methoxyphenyl)allyl pivalate (86.9 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (73.8 mg, 87%). 1H NMR (400 MHz, CDCl3) δ 7.47 (dd, J = 7.6 Hz, J = 1.8 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 3H), 6.39 (dt, J = 15.9 Hz, J = 7.0 Hz, 1H), 3.89 (s, 3H), 3.64 (d, J = 7.0 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 156.6, (d, J = 4.8 Hz), , , (d, J = 8.0 Hz), (d, J = 16.0 Hz), 126.8, 126.5, 126.4, (d, J = 3.5 Hz), 120.8, (d, J = 22.1 Hz), 111.0, 55.6, 32.8 (d, J = 3.2 Hz). 19 F NMR (376 MHz, CDCl3) δ MS (EI) m/z (M + ) calcd for [C16H15FO]: 242, found: 242. (E)-1-fluoro-2-(3-(3-methoxyphenyl)allyl)benzene (Table 2, entry 7). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with (E)-3-(3- methoxyphenyl)allyl pivalate (86.9 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (70.9 mg, 84%). 1 H NMR (400 MHz, CDCl3) δ (m, 3H), (m, 2H), 6.95 (d, J = 7.7 Hz, 1H), 6.89 (s, 1H), 6.76 (d, J = 8.3 Hz, 1H), 6.43 (d, J = 15.8 Hz, 1H), 6.33 (dt, J = 15.8 Hz, J = 6.6 Hz, 1H), 3.80 (s, 3H), 3.57 (d, J = 6.5 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 159.9, 138.9, 131.5, (d, J =4.7 Hz), 129.6, 128.1, 128.0, (d, J = 15.9 Hz), (d, J = 3.6 Hz), 119.0, (d, J = 22.0 Hz), 113.1, 111.6, 55.3, 32.3 (d, J = 3.0 Hz). 19 F NMR (376 MHz, CDCl3) δ (m). MS (EI) m/z (M + ) calcd for [C16H15FO]: 242, found: 242. (E)-2-(3-(2-fluorophenyl)prop-1-en-1-yl)naphthalene (Table 2, entry 8). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with (E)-3-(naphthalen-2- yl)allyl pivalate (93.9 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (71.3 mg, 78%). S9

10 1 H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 7.5 Hz, 3H), 7.70 (s, 1H), 7.58 (d, J = 8.5 Hz, 1H), (m, 2H), (m, 2H), 7.08 (dt, J = 18.1 Hz, J = 8.4 Hz, 2H), 6.62 (d, J = 15.6 Hz, 1H), (m, 1H), 3.63 (d, J = 7.0 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 134.9, 133.8, 132.9, 131.6, (d, J = 4.8 Hz), , , 128.1, 128.0, 127.8, (d, J = 16.0 Hz), 126.3, 125.9, 125.8, (d, J = 3.6 Hz), 123.7, (d, J = 22.0 Hz), 32.5 (d, J = 3.0 Hz). 19 F NMR (376 MHz, CDCl3) δ (m). MS (EI) m/z (M + ) calcd for [C19H15F]: 262, found: Fluoro-2-(2-methylallyl)benzene (Table 2, entry 9) [ ]. Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with 3-chloro-2-methylprop-1-ene (31.7 mg, mmol). The yield of 3i (74%) was determined by GC analysis with dodecane as an internal standard. After purification by column chromatography (pentane), the title compound was isolated as a colorless oil (22.8 mg, 43%). 1 H NMR (400 MHz, CD2Cl2) δ (m, 2H), (m, 2H), 4.81 (s, 1H), 4.66 (s, 1H), 3.35 (s, 2H), 1.72 (s, 3H). 13 C NMR (101 MHz, CD2Cl2) δ (d, J = Hz), 144.5, 31.6 (d, J = 4.7 Hz), (d, J = 8.1 Hz), (d, J = 15.8 Hz), (d, J = 3.6 Hz), (d, J = 22.4 Hz), 111.9, 37.3 (d, J = 3.0 Hz), F NMR (376 MHz, CD2Cl2) δ (m). MS (EI) m/z (M + ) calcd for [C10H11F]: 150, found: 150. (E)-1-Fluoro-2-(2-methyl-3-phenylallyl)benzene (Table 2, entry 10). Following General Procedure 2, the title compound was prepared by the reaction of fluorobenzene (1.40 ml) with (E)-2-methyl-3-phenylallyl pivalate (81.3 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (59.6 mg, 75%; a 3:1 mixture of E and Z isomers by 1 H and 19 F NMR spectroscopy). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 5H), (m, 2H), 6.55 (s, 1H of Z), 6.34 (s, 1H of E), 3.62 (s, 2H of Z), 3.52 (s, 2H of E), (m, 3H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 138.3, 136.9, (d, J = 4.7 Hz), 129.0, (d, J = 16.4 Hz), 128.2, 128.1, 127.0, 126.2, (d, J = 3.6 Hz), (d, J = 22.3 Hz), 39.4 (d, J = 2.7 Hz), F NMR (376 MHz, CDCl3) δ (m; Z), (m; E). Note: The (E) (major) and (Z) (minor) isomers were assigned by NOESY spectroscopy. S10

11 S11

12 2-cinnamyl-1-fluoronaphthalene (Table 3, entry 1). Following procedure 2, the title compound was prepared by the reaction of 1- fluoronaphthalene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a yellow solid (62.6 mg, 64%). 1 H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 8.1 Hz, 1H), 7.83 (d, J = 7.9 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 1H), 6.5 (d, J = 15.9 Hz, 1H), 6.40 (dt, J = 15.9 Hz, J = 6.5 Hz, 1H), 3.75 (d, J = 6.8 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ (d, J =251.0 Hz), 137.5, (d, J = 4.8 Hz), 131.5, 128.6, (d, J = 5.2 Hz), 127.9, (d, J = 3.0 Hz), 127.3, , , , (d, J = 17.6 Hz), (d, J = 4.4 Hz), (d, J = 15.0 Hz), (d, J =5.7 Hz), 32.2 (d, J = 3.6 Hz). 19 F NMR (376 MHz, CDCl3) δ MS (EI) m/z (M + ) calcd for [C19H15F]: 262, found: cinnamyl-2-fluoro-3-methylbenzene (Table 3, entry 2). Following procedure 2, the title compound was prepared by the reaction of 1-fluoro- 2-methylbenzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (37.7 mg, 48%). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), 6.46 (d, J = 15.8 Hz, 1H), 6.34 (dt, J = 15.8 Hz, J = 6.7 Hz, 1H), 3.55 (d, J = 6.7 Hz, 2H), 2.28 (d, J = 2.2 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 137.6, 131.4, (d, J = 5.1 Hz), 128.6, (d, J = 4.6 Hz), 128.0, 127.3, (d, J = 16.9 Hz), 126.3, (d, J = 17.6 Hz), (d, J = 4.3 Hz), 32.5 (d, J = 3.5 Hz), 14.8 (d, J = 4.4 Hz). 19 F NMR (376 MHz, CDCl3) δ (m). MS (EI) m/z (M + ) calcd for [C16H15F]: 226, found: cinnamyl-1-fluoro-4-methylbenzene (Table 3, entry 3). Following procedure 2, the title compound was prepared by the reaction of 1-fluoro-4- methylbenzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a colorless oil (58.8 mg, 74%). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), 6.46 (d, J = 15.8 Hz, 1H), 6.33 (dt, J = 15.8 Hz, J = 6.7 Hz, 1H), 3.53 (d, J = 6.7 Hz, 2H), 2.29 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 137.5, (d, J = 3.6 Hz), 131.4, (d, J =4.5 Hz), 128.6, (d, J = 7.8 Hz), 127.9, 127.3, (d, J = 16.0 Hz), 126.3, (d, J = 22.1 Hz), 32.4 (d, J = 2.9 Hz), F NMR (376 MHz, CDCl3) δ (m). MS (EI) m/z (M + ) calcd for [C16H15F]: 226, found: 226. S12

13 2-cinnamyl-1-fluoro-4-methoxybenzene (Table 3, entry 4). Following procedure 2, the title compound was prepared by the reaction of 1-fluoro-4-methoxybenzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a yellow oil (70.6 mg, 83%; an isomeric mixture of 3:1 by 19 F NMR spectroscopy). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 6.47 (d, J = 15.8 Hz, 1H), (m, 1H), 3.77 (s, 3H), 3.53 (d, J = 6.8 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 155.8, (d, J = Hz), 137.4, 131.7, 128.6, 127.5, 127.3, 126.3, 126.2, 115.9, (d, J = 17.8 Hz), (d, J = 7.9 Hz), 55.8, 32.6 (d, J = 2.9 Hz). 19 F NMR (376 MHz, CDCl3) δ (m; minor isomer), (m; major isomer). MS (EI) m/z (M + ) calcd for [C16H15FO]: 242, found: Cinnamyl-1-fluoro-4-(trifluoromethyl)benzene (Table 3, entry 5). Following procedure 2, the title compound was prepared by the reaction of 1- fluoro-4-(trifluoromethyl)benzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). The yield of 5e (87%) was determined by 1 H NMR spectroscopy with 1,1,2,2-tetrachloroethane as an internal standard. After column chromatography, the title compound was isolated as a colorless oil (91.2 mg, 93%; contained the biaryl side product, 2,2'-difluoro-5,5'-bis(trifluoromethyl)-1,1'-biphenyl; 6:1 ratio of the tile compound and the biaryl). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 2H), (m, 1H), 7.16 (t, J = 8.9 Hz, 1H), 6.51 (d, J = 16.0 Hz, 1H), 6.32 (dt, J = 15.8 Hz, J = 6.8 Hz, 1H), 3.62 (d, J = 6.8 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ (d, J = Hz), 137.1, 132.5, 128.7, 128.5, 128.3, (m), 127.6, 126.4, 126.3, (m), 122.6, (d, J = 23.6 Hz), 32.3 (d, J = 2.8 Hz). 19 F NMR (376 MHz, CDCl3) δ -61.0, MS (EI) m/z (M + ) calcd for [C16H12F4]: 280, found: 280. The biaryl side product, 2,2'-difluoro-5,5'-bis(trifluoromethyl)-1,1'-biphenyl, was prepared from the reaction of 1-fluoro-4-(trifluoromethyl)benzene under standard allylation conditions in the absence of allylic pivalate. This compound was isolated as a colorless oil by preparative TLC (eluted with 10% EtOAc in hexanes). 1 H NMR (400 MHz, CDCl3) δ (m, 4H), (m, 2H). S13

14 19 F NMR (376 MHz, CDCl3) δ -61.2, MS (EI) m/z (M + ) calcd for [C14H6F8]: 326, found: cinnamylbenzo[d][1,3]dioxole (Table 3, entry 6). Following procedure 2, the title compound was prepared by the reaction of benzo[d][1,3]dioxole (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a yellow oil (55.3 mg, 66%). 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 2H), 6.47 (d, J = 15.8 Hz, 1H), 6.35 (dt, J = 15.7 Hz, J = 6.7 Hz, 1H), 5.96 (s, 2H), 3.51 (dd, J = 6.7 Hz, J = 1.2 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 147.3, 145.6, 137.5, 131.4, 128.6, 127.6, 127.3, 126.3, 122.7, 121.7, 121.7, 106.9, 100.8, MS (EI) m/z (M + ) calcd for [C16H14O2]: 238, found: chloro-2-cinnamyl-3-methoxybenzene (Table 3, entry 7). Following procedure 2, the title compound was prepared by the reaction of 1-chloro-3-methoxybenzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a light yellow oil (71.5 mg, 79%; a 6:1 mixture of isomers). 1 H NMR (400 MHz, CDCl3) δ (m, 4H), (m, 2H), (m, 1H), 6.79 (d, J = 8.2 Hz, 1H), 6.43 (d, J = 15.7 Hz, 1H), 6.30 (dt, J = 15.8 Hz, J = 6.4 Hz, 1H), 3.85 (s, 3H), 3.71 (d, J = 6.4 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 158.6, 137.9, 135.2, 130.7, , 127.7, 127.1, 127.0, 126.9, 126.2, 121.9, 109.1, 56.1, MS (EI) m/z (M + ) calcd for [C16H15ClO]: 258, found: Chloro-2-cinnamyl-4-(trifluoromethyl)benzene (Table 3, entry 8) [ ]. Following procedure 2, the title compound was prepared by the reaction of 1-chloro-4-(trifluoromethyl)benzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). The yield of 5h (36%) was determined by 1 H NMR spectroscopy with 1,1,2,2-tetrachloroethane as an internal standard. After column chromatography, the title compound was isolated as a colorless oil (co-eluted with the biaryl side products (2 isomers) from the arylation of arene with aryl chloride; determined by GC/MS). Spectral data of 5h matched those of a previous report. 5 S14

15 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 2H), 6.49 (d, J = 15.8 Hz, 1H), (m, 1H), 3.71 (d, J = 6.8 Hz, 2H). 2-Cinnamyl-1-methoxy-4-(trifluoromethyl)benzene (Table 3, entry 9). Following procedure 2, the title compound was prepared by the reaction of 1- methoxy-4-(trifluoromethyl)benzene (1.40 ml) with cinnamyl pivalate (76.4 mg, mmol). After purification by column chromatography, the title compound was isolated as a light yellow oil (29.6 mg, 29%; a 16:1 mixture of isomers by 1 H and 19 F NMR spectroscopy). 1 H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.5 Hz, 1H), 7.43 (s, 1H), (m, 2H), 7.29 (t, J = 7.7 Hz, 2H), (m, 1H), 6.92 (d, J = 8.6 Hz, 1H), 6.45 (d, J = 15.9 Hz, 1H), 6.34 (dt, J = 15.8 Hz, J = 6.7 Hz, 1H), 3.90 (s, 3H), 3.55 (d, J = 6.7 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 159.9, 137.6, 131.6, 129.6, 128.6, 128.3, 127.7, 127.3, (q, J = 3.6 Hz), 126.3, (m), 122.3, 110.1, 55.8, F NMR (376 MHz, CDCl3) δ MS (EI) m/z (M + ) calcd for [C17H15F3O]: 292, found: 292. Eq 1. Pd(OAc)2 (1.12 mg, mmol), Cs2CO3 (39.1 mg, mmol), AgOPiv (10.4 mg, mmol), fluorobenzene (0.20 ml) were added to a 4-mL vial equipped with a stir bar. To this vial was added Pt-Bu2(2-OMeC6H4) (2.52 mg, mmol) and 1-phenylallyl pivalate [ ] (10.9 mg, mmol). This vial was sealed with a Teflon-lined cap and electrical tape. The reaction mixture was heated at 120 C with stirring in an aluminum block. After 17 h, the reaction mixture was cooled to room temperature, filtered through a pad of silica (eluted with ethyl acetate 2.0 ml). The yield was determined by GC analysis with dodecane as an internal standard. S15

16 V. H/D Exchange Experiments of 1-Fluoronaphthalene General Procedure 3. Pd(OAc)2 (4.49 mg, mmol), Cs2CO3 (78.2 mg, mmol), and AgOPiv (20.9 mg, mmol) were placed in a 4-mL vial equipped with a stir bar. Pt-Bu2(2- OMeC6H4) (10.1 mg, mmol), 1-fluoronaphthalene (14.6 mg, mmol), D2O (20.0 mg, 1.00 mmol), and 1,4-dioxane (0.10 ml) were added to this vial. This vial was sealed with a Teflon-lined cap and electrical tape. The reaction mixture was heated at 120 C with stirring in an aluminum block. After 17 h, the reaction mixture was cooled to room temperature, filtered through a pad of Celite (eluted with CH2Cl2), and then concentrated under reduced pressure. The amount of the deuteration was determined by 1 H and 19 F NMR spectroscopy. Note: With 1,1,2,2-tetrachloroethane as an internal standard for the 1 H NMR spectroscopy, we determined that the combined yield of 1-fluoronaphthane (starting material) and the deuterated product is generally over 95% for the experiments listed in Table S1; the loss of <5% can be explained by their volatility. The yield of the deuteration was determined assuming the combined yield of 1-fluoronaphthalene (1b) and [D]-1b is 100%. Table S1. S16

17 VI. Preparation of Palladium Complexes (PdL2, 6, and 12) Pd[Pt-Bu2(2-OMeC6H4)]2 (PdL2). This procedure is based on a published procedure. 6 Pd(COD)Br2 [ ] (93.6 mg, mmol) and toluene (0.40 ml) were placed in a 20 ml-vial equipped with a stir. To this vial was added NaOH (20.0 mg, mmol) in methanol (0.13 ml) at 0 C. The resulting mixture was stirred at 0 C for 20 min. Next, Pt-Bu2(2-OMeC6H4) (126 mg, mmol) in toluene (0.20 ml) was added. After stirring for 10 min at room temperature, Pt-Bu2(2- OMeC6H4) was fully consumed as judged by 31 P NMR spectroscopy. Methanol (0.50 ml) was added to this solution to precipitate the product, which was then filtered, washed with methanol (2.0 ml). The filter solid (a light-green solid) was dissolved in diethyl ether, filtered through a pad of Celite (eluted with diethyl ether 5.0 ml), and concentrated under reduced pressure to give the title compound as a light yellow solid (110 mg, 72%). 1 H NMR (400 MHz, C6D6) δ 9.85 (qd, J = 7.5 Hz, J = 1.9 Hz, 2H), (m, 2H), 7.01 (t, J = 7.4 Hz, 2H), 6.46 (d, J = 8.1 Hz, 2H), 3.21 (s, 6H), (m, 36H). 13 C NMR (101 MHz, C6D6) δ 160.6, (t, J = 22.0 Hz), 131.4, (m), (t, J = 8.3 Hz), 110.3, 53.5, 35.7 (t, J = 2.9 Hz), 31.7 (t, J = 6.7 Hz). 31 P NMR (162 MHz, C6D6) δ Analysis calcd for C30H50O2P2Pd: C 58.96, H 8.25; found C 58.80, H Crystals suitable for X-ray crystallography were grown from the saturated solution of toluene at -20 C. A yellow prism x x mm in size was mounted on a Cryoloop with Paratone oil. Data were collected in a nitrogen gas stream at 100(2) K using and scans. Crystal-to-detector distance was 40 mm and exposure time was 10 seconds per frame using a scan width of 2.0. Data collection was 100.0% complete to in. A total of reflections were collected covering the indices, -9<=h<=9, -29<=k<=29, -10<=l<= reflections were found to be symmetry independent, with an Rint of Indexing and unit cell refinement indicated a primitive, monoclinic lattice. The space group was found to be P 21/c (No. 14). The data were integrated using the Bruker SAINT software program and scaled using the SADABS software program. Solution by iterative methods (SHELXT-2014) produced a complete heavy-atom S17

18 phasing model consistent with the proposed structure. All non-hydrogen atoms were refined anisotropically by full-matrix least-squares (SHELXL-2014). All hydrogen atoms were placed using a riding model. Their positions were constrained relative to their parent atom using the appropriate HFIX command in SHELXL Table S2. Crystal data and structure refinement for Pd[Pt-Bu2(2-OMeC6H4)]2 (PdL2). Empirical formula Formula weight Temperature Wavelength Crystal system C30 H50 O2 P2 Pd 100(2) K Å Monoclinic Space group P 21/c Unit cell dimensions a = (3) Å = 90. b = (9) Å = (2). c = (3) Å = 90. Volume (10) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 644 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=9, -29<=k<=29, -10<=l<=10 Independent reflections 2753 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2753 / 0 / 167 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 S18

19 Cinnamylpalladium pivalate 6. Palladium(π-cinnamyl) chloride dimer [ ] (77.7 mg, mmol) was placed in a 20 ml-vial equipped with a stir bar. Pt-Bu2(2-OMeC6H4) (75.7 mg, mmol) in toluene (1.0 ml) was added to this vial, and the resulting mixture was stirred at room temperature. After 30 min, this mixture was transferred to an another 20 ml-vial containing AgOPiv (62.7 mg, mmol) and THF (1.0 ml) equipped with a stir bar. This reaction mixture was stirred at room temperature with vigorous stirring. After 17 h, the reaction mixture was filtered through a pad of Celite (eluted with toluene), and concentrated under reduced pressure to give a yellow-brown solid. The title compound was obtained as a yellow crystalline solid (133 mg, 77%) after recrystallizations from the saturated solution of toluene at - 20 C. 1 H NMR (500 MHz, toluene-d8 at 343K) δ 8.10 (br s, 1H), 7.49 (d, J = 7.5 Hz, 2H), 7.12 (t, J = 7.4 Hz, 2H), (m, 2H), 6.81 (t, J = 7.6 Hz, 1H), (m, 1H), 5.76 (t, J = 11.1 Hz, 1H), 5.52 (dt, J = 12.2 Hz, J = 8.8 Hz, 1H), 3.34 (s, 3H), 2.59 (d, J = 9.1 Hz, 2H), 1.33 (d, J = 14.1 Hz, 18H), 1.02 (s, 9H). 31 P NMR (162 MHz, C6D6) δ 87.6 (br). Analysis calcd for C29H43O3PPd: C 60.36, H 7.51; found C 60.48, H Crystals suitable for X-ray crystallography were obtained by cooling the saturated solution in toluene to -20 C. A yellow block x x mm in size was mounted on a Cryoloop with Paratone oil. Data were collected in a nitrogen gas stream at 100(2) K using and scans. Crystal-to-detector distance was 40 mm and exposure time was 10 seconds per frame using a scan width of 2.0. Data collection was 100.0% complete to in. A total of reflections were collected covering the indices, -15<=h<=15, -22<=k<=22, -15<=l<= reflections were found to be symmetry independent, with an Rint of Indexing and unit cell refinement indicated a primitive, monoclinic lattice. The space group was found to be P 21/c (No. 14). The data were S19

20 integrated using the Bruker SAINT software program and scaled using the SADABS software program. Solution by iterative methods (SHELXT-2014) produced a complete heavy-atom phasing model consistent with the proposed structure. All non-hydrogen atoms were refined anisotropically by full-matrix least-squares (SHELXL-2014). All hydrogen atoms were placed using a riding model. Their positions were constrained relative to their parent atom using the appropriate HFIX command in SHELXL Table S3. Crystal data and structure refinement for cinnamylpalladium pivalate 6. Empirical formula Formula weight Temperature Wavelength Crystal system C29 H43 O3 P Pd 100(2) K Å Monoclinic Space group P 21/c Unit cell dimensions a = (9) Å = 90. b = (13) Å = (3). c = (9) Å = 90. Volume (3) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1208 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=15, -22<=k<=22, -15<=l<=15 Independent reflections 5222 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5222 / 0 / 325 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient Largest diff. peak and hole n/a and e.å S20

21 Palladacycle (12) (Eq 9). Pd(OPiv)2 (123 mg, mmol) was placed in a 20-mL vial equipped with a stir bar. To this vial was added Pt-Bu(2-OMeC6H4) (101 mg, mmol) in toluene (3.0 ml). This reaction mixture was stirred for 10 min at room temperature. The 31 P NMR spectrum of the mixture contained one singlet at ppm. The yield of the title compound was 98% by 1 H NMR spectroscopy with an internal standard. The reaction mixture was concentrated under reduced pressure. The residue was purified by recrystallzations from a saturated solution of pentane at -20 C, which afforded the title compound as a white solid (124 mg, 63%; contained ~0.7 equivalent of pentane). 1 H NMR (600 MHz, C6D6) δ 7.51 (t, J = 6.9 Hz, 2H), (m, 2H), 6.22 (dd, J = 8.3 Hz, J = 3.7 Hz, 2H), 3.11 (s, 6H), 1.49 (s, 18H), 1.45 (d, J = 15.3 Hz, 18H), 1.37 (d, J = 15.6 Hz, 18H). 13 C NMR (151 MHz, C6D6) δ 187.3, 156.3, 136.4, 136.2, 129.7, (d, J = 3.1 Hz), (d, J = 5.1 Hz), 54.2, 40.9 (d, J = 3.4 Hz), 35.8 (d, J = 17.1 Hz), 34.5 (d, J = 14.3 Hz), 30.7 (d, J = 5.1 Hz), 30.4 (d, J = 5.3 Hz), P NMR (162 MHz, C6D6) δ Crystals suitable for X-ray crystallography were grown from the saturated solution of pentane at -20 C. Pentane molecule was included. A colorless prism x x mm in size was mounted on a Cryoloop with Paratone oil. Data were collected in a nitrogen gas stream at 100(2) K using and scans. Crystal-to-detector distance was 40 mm and exposure time was 5 seconds per frame using a scan width of 2.0. Data collection was 99.7% complete to in. A total of reflections were collected covering the indices, -13<=h<=13, -26<=k<=29, -21<=l<= reflections were found to be symmetry independent, with an Rint of Indexing and unit cell refinement indicated a S21

22 primitive, monoclinic lattice. The space group was found to be P 21/n (No. 14). The data were integrated using the Bruker SAINT software program and scaled using the SADABS software program. Solution by iterative methods (SHELXT-2014) produced a complete heavy-atom phasing model consistent with the proposed structure. All non-hydrogen atoms were refined anisotropically by full-matrix least-squares (SHELXL-2014). All hydrogen atoms were placed using a riding model. Their positions were constrained relative to their parent atom using the appropriate HFIX command in SHELXL Table S4. Crystal data and structure refinement for palladacycle 12 Empirical formula Formula weight Temperature Wavelength Crystal system C45 H78 O6 P2 Pd2 100(2) K Å Monoclinic Space group P 21/n Unit cell dimensions a = (14) Å = 90. b = (3) Å = (5). c = (2) Å = 90. Volume (10) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 2072 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=13, -26<=k<=29, -21<=l<=21 Independent reflections 9119 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 9119 / 0 / 518 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 S22

23 VII. Preparation of Silver Complexes (7 and 8) Silver pivalate ligated by Pt-Bu(2-OMeC6H4). AgOPiv (20.9 mg, mmol) was placed in a 20-mL vial equipped with a stir bar. To this vial was added Pt-Bu(2-OMeC6H4) (25.2 mg, mmol) in benzene (0.50 ml). This reaction mixture was stirred for 10 min at room temperature and then concentrated under reduced pressure to afford the title compound as an off-white solid. 1 H NMR (400 MHz, CD2Cl2) δ 7.98 (dd, J = 17.8 Hz, J = 7.5 Hz, 1H of 7a, 37%), 7.66 (t, J = 7.1 Hz, 1H of 7b, 63%), 7.49 (t, J = 7.2 Hz, 1H), (m, 2H), 3.89 (s, 3H of 7b, 63%), 3.84 (s, 3H of 7a, 37%), 1.34 (d, J = 15.4 Hz, 18H), 1.18 (s, 9H). 31 P NMR (162 MHz, C6D6) δ 84.5 (dd, J = Hz, J = 49.3 Hz; 7a, 37%), 29.6 (dd, J = Hz, J = 49.7 Hz; 7b, 63%). 31 P NMR (162 MHz, CD2Cl2) δ 88.1 (app. d, J = Hz; 7a, 37%), 327 (app. d, J = Hz; 7b, 63%). *Note: The configuration of 7a and 7b was assigned by NOESY spectroscopy at 0 C (CD2Cl2). S23

24 S24

25 Crystals suitable for X-ray diffraction were grown from the saturated solution of diethyl ether at -20 C. A colorless prism x x mm in size was mounted on a Cryoloop with Paratone oil. Data were collected in a nitrogen gas stream at 100(2) K using and scans. Crystal-to-detector distance was 40 mm and exposure time was 10 seconds per frame using a scan width of 1.0. Data collection was 100.0% complete to in. A total of reflections were collected covering the indices, -21<=h<=19, -11<=k<=12, -29<=l<= reflections were found to be symmetry independent, with an Rint of Indexing and unit cell refinement indicated a primitive, monoclinic lattice. The space group was found to be P 21/n (No. 14). The data were integrated using the Bruker SAINT software program and scaled using the SADABS software program. Solution by iterative methods (SHELXT-2014) produced a complete heavy-atom phasing model consistent with the proposed structure. All non-hydrogen atoms were refined anisotropically by full-matrix least-squares (SHELXL-2014). All hydrogen atoms were placed using a riding model. Their positions were constrained relative to their parent atom using the appropriate HFIX command in SHELXL Table S5. Crystal data and structure refinement for Silver pivalate ligated by Pt-Bu(2-OMeC6H4) Empirical formula Formula weight Temperature Wavelength Crystal system C20 H34 Ag O3 P 100(2) K Å Monoclinic Space group P 21/n Unit cell dimensions a = (5) Å = 90. b = (3) Å = (2). c = (8) Å = 90. Volume (2) Å 3 S25

26 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1920 Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected <=h<=19, -11<=k<=12, -29<=l<=27 Independent reflections 7905 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7905 / 6 / 491 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 (5-Fluoro-2-methoxyphenyl)lithium (9). 2-bromo-4-fluoro-1-methoxybenzene [ ] (1.02 g, 5.00 mmol) and pentane (3.0 ml) were placed in a 20-mL vial equipped with a stir. To this vial was added n-buli (2.0 ml of 2.5 M in hexanes, 5.0 mmol) dropwise over 3 min at 0 C. The reaction mixture was stirred at room temperature for 1 h, and then white precipitates were collected by filtration (washed with 5.0 ml of pentane). This compound was used in the next step without further purification. AgAr ligated by Pt-Bu(2-OMeC6H4) (8a; eq 6). A 20-mL vial was charged with AgBr (56.3 mg, mmol), (5-fluoro-2-methoxyphenyl)lithium (39.6 mg, mmol), diethyl ether (3.0 ml), and a stir bar. After stirring for 1 h at room temperature, Pt-Bu(2-OMeC6H4) (75.7 mg, mmol) was added to this solution. The resulting mixture was stirred at room temperature for 30 S26

27 min, filtered through a pad of Celite (eluted with diethyl ether), and concentrated under reduced pressure. The residue was then dissolved in dichloromethane, filtered through a pad of Celite (eluted with dichloromethane), and concentrated under reduced pressure to afford a title compound as an off-white, sticky solid (127 mg, 87%). This compound was stored under a nitrogen atmosphere, in the dark at -20 C. *Note: The configuration of 8a-a and 8a-b was assigned by analogy to L-AgOPiv (7a and 7b). 1 H NMR (400 MHz, CD2Cl2) δ 8.18 (dd, J = 17.1, J = 7.5 Hz, 1H of 8a-a, 46%), 7.69 (t, J = 6.4 Hz, 1H of 8a-b, 54%), 7.50 (q, J = 7.1 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), 3.91 (s, 3H of 8a-b, 54%), 3.85 (s, 3H of 8a-a, 46%), 3.72 (s, 3H), 1.38 (d, J = 14.9 Hz, 18H). 31 P NMR (162 MHz, CD2Cl2) δ 75.3 (br d, J = Hz; 8a-a, 46%), 27.8 (br d, J = Hz; 8a-b, 54%). 19 F NMR (376 MHz, CD2Cl2) δ (m). AgAr ligated by P(2-OMeC6H4)3. A 20-mL vial was charged with AgBr (37.6 mg, mmol), (5-fluoro-2-methoxyphenyl)lithium (26.4 mg, mmol), diethyl ether (2.0 ml), and a stir bar. After stirring for 1 h at room temperature, P(2-OMeC6H4)3 (70.5 mg, 0.20 mmol) was added to this solution. The resulting mixture was stirred at room temperature for 30 min (the product was insoluble in diethyl ether). Tetrahydrofuran (1.0 ml) and dichloromethane (2.0 ml) were added to this solution. The resulting mixture was filtered through a pad of Celite (eluted with dichloromethane) and concentrated under reduced pressure to furnish the title compound as an off-white solid (82.0 mg, 70%). This compound was stored under a nitrogen atmosphere, dark at -20 C. 1 H NMR (400 MHz, CD2Cl2) δ (m, 3H), 7.21 (dd, J = 7.4 Hz, J = 2.8 Hz, 1H), 7.01 (dd, J = 8.3 Hz, J = 5.6 Hz, 3H), 6.93 (td, J = 7.5 Hz, J = 1.3 Hz, 3H), 6.82 (t, J = 8.3 Hz, 3H), (m, 2H), 3.80 (s, 9H), 3.69 (s, 3H). 31 P NMR (162 MHz, CD2Cl2) δ (br m). 19 F NMR (376 MHz, CD2Cl2) δ (m). Analysis calcd for C28H27AgFO4P: C 57.45, H 4.65; found C 56.96, H S27