Diverse Functionalization of Corannulene: Easy Access to Pentagonal Superstructure

Transcription

1 Diverse Functionalization of Corannulene: Easy Access to Pentagonal Superstructure Doron Pappo, a Tom Mejuch, a fer Reany, a Ephrath Solel, a Mahender Gurram b and Ehud Keinan*,a,b a Schulich Faculty of Chemistry, Technion - Israel Institute of Technology, Technion City, Haifa 32000, Israel, and b Department of Molecular Biology and the Skaggs Institute for Chemical Biology, The Scripps Research Institute, orth Torrey Pines Road, La Jolla, California 92037, USA. keinan@tx.technion.ac.il Table of Contents General methods...page S2 Experimental procedures for syntheses of the compounds page S3 Selected 1 H-MR, 13 C-MR and IR spectra of compounds page S14 References...Page S31 S1

2 General Methods 1 H-MR, 13 C-MR spectra were recorded on a Bruker Ultrashield AV300 spectrometer, operating at 300 MHz ( 1 H), MHz ( 13 C) and AV500 operating at 500 MHz ( 1 H), MHz ( 13 C). Chemical shifts are reported as δ value in ppm and referenced to Me 4 Si (δ=0.0). CI-MS spectra were measured on a Finnigan TSQ-70 spectrometer and MALDI-TF spectra were measured on a MALDI Micromass spectrometer using α- cyano-4-hydroxycinnamic acid as a matrix. TLC was performed on glass sheets precoated with silica-gel (Merck, Kieselgel 60, F254, Art.5715). Column chromatographic separations were performed on silica-gel (Merck, Kieselgel 60, mesh, Art. 9385) under pressure (flash chromatography). Extra dry dioxane and DMF were purchased (sure-seal) from Aldrich. THF was distilled from a-benzophenone according to literature procedures. 1,3,5,7,9-pentachlorocorannulene was prepared according to literature procedure. 1 Except for 4-tert-butylthiophenylboronic acid which was prepared according to literature procedures, 2 all arylboronic acids used in this work were purchased from commercial sources. S2

3 Experimental Section R Cl R Cl Cl () 2 B R (8eq.) Pd(t-Bu 3 P) 2 (20%mol.) R Cl CsF(15eq) Cl dioxane 80 ο C R General procedure for the coupling of 1,3,5,7,9-pentachlorocorannulene with arylboronic acids: To an oven dried three neck flask connected to a Schlenk line were added 1,3,5,7,9-pentachlorocorannulene (42 mg, 0.1 mmol), 3 arylboronic acid (0.8 mmol), CsF (226 mg, 1.5 mmol) and Pd[P(t-Bu) 3 ] 2 (0.02 mmol, 10 mg). The flask was purged repeatedly with nitrogen before dry dioxane (8 ml) was added. The mixture was stirred for 15 min. at room temperature and kept at 80 ο C for hrs. The solvent was removed, water was added (10 ml) and extracted with tetrachloroethane (2 10 ml ). The combined organic solvents were washed with 1 a (10 ml), water (2 10 ml), and removed under reduced pressure (without drying and filtration), toluene (2 ml) was added to the yellow crude solid and the product was filtered and washed with toluene (2 2 ml), methanol (2 2 ml) and dichloromethane (2 2 ml) to furnish 1,3,5,7,9-penta-arylcorannulene as a pale yellow solid. R S3

4 C 2 CH 3 1,3,5,7,9-Penta-(4-methoxycarbonylphenyl)corannulene (2) H 3 C 2 C was prepared according to the general procedure: 1,3,5,7,9- C 2 CH 3 H 3 C 2 C C 2 CH 3 pentachlorocorannulene (168 mg, 0.4 mmol), Pd[P(t-Bu) 3 ] 2 (52 mg, 0.1 mmol), cesium fluoride (1.46 g, 9.6 mmol) and 4- methoxycarbonylphenylboronic acid (576 mg, 3.2 mmol) in dioxane (32 ml) were kept for 72 h at 80 ο C. Compound 2 (217 mg, 59%) was accepted as a pale yellow solid. 1 H- MR (500 MHz, CDCl 3 ): δ 8.16 (d, J = 8 Hz, 10H), 7.83 (s, 5H), 7.70 (d, J = 8 Hz, 10H), 3.97 (s, 15H). 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 167.0, 143.7, 141.6, 135.8, 130.3, 130.1, 129.7, 129.0, 126.6, 52.6; IR (KBr): 2951, 1728, 1607, 1436, 1286, 1160, 1110 cm -1 ; UV (C 2 H 2 Cl 4, nm): λ max 307; MS (MALDI) m/z: [(M+], calc.: C 2 H 1,3,5,7,9-Penta-(4-carboxyphenyl)corannulene (3): To a 2 C C 2 H stirred solution of compound 2 (20 mg, mmol) in dry THF (2 ml) was added potassium trimethylsilanolate (56 mg, C C 2 H mmol) and the reaction was kept at 80 ο C for 16 h. After cooling to room temperature the solution was acidified with 1 HCl (2 ml) and most of the THF was removed under reduced pressure leaving insoluble yellow solid. The solid was collected, washed with water (1 ml), methanol (1 ml) and dichloromethane (1 ml) to afford compound 3 (16 mg, 86%) as an insoluble yellow solid. 1 H-MR (500 MHz, DMS-d 6 ): δ (bs, 5H), 8.02 (bs, 10H), 7.8 (bs, 15H); Due to poor solubility of 3 in common deuterated solvents 13 C-MR couldn t be measured; IR (KBr): 3234, S4

5 2993, 1699, 1607, 1416, 1246, 1180 cm -1 ; MS (MALDI) m/z: (M-H+a, 100%), calc.: (100%). CH 2 1,3,5,7,9-Penta-(4-hydroxymethylphenyl)corannulene (4). To H 2 C CH 2 a stirred solution of compound 2 (21 mg, mmol) in dry THF at -78 ο C was added diisobutylaluminum hydride (1 ml, 1 H 2 C CH 2 M in toluene, large excess). The mixture allowed to warm to room teperature and stirred for 18 h before it was quenched with 1 HCl. The precipitate solid was collected, washed with water (2 2 ml), methanol (2 ml) and dichloromethane (2 2 ml) to afford compound 4 (12 mg, 65%) as yellow solid. 1 H- MR (500 MHz, DMS-d 6 ): δ (br m, 25H), 5.37 (br s, 5H, ), 4.64 (br s, 10H); Due to poor solubility of 4 in common deuterated solvents 13 C-MR couldn t be measured; MS (MALDI) m/z: (M+-1, 100%); calc.: (100%). CH 3 1,3,5,7,9-Penta-(4-methoxyphenyl)corannulene (5) was H 3 C prepared according to the general procedure: 1,3,5,7,9- CH 3 pentachlorocorannulene (82 mg, 0.2 mmol), 4- H 3 C CH 3 methoxyphenylboronic acid (244 mg, 1.6 mmol), cesium fluoride (452 mg, 3.2 mmol), Pd[P(t-Bu) 3 ] 2 (20 mg, 0.04 mmol) in Dry dioxane (16 ml) were kept for 48 h at 80 ο C. Compound 5 (128 mg, 82%) was obtained as a pale yellow solid. 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ 7.83 (s, 5H), 7.66 (d, J = 8 Hz, 10H), 7.06 (d, J = 8 Hz, 10H), 3.91 (s, 15H). 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 161.1, 143.6, 137.1, 134.0, 133.0, S5

6 131.2, 127.1, 116.1, 57.4; IR (KBr): 3000, 2952, 2834, 1606, 1513, 1436, 1280, 1252, 1177, 1036, 815 cm -1 ; UV (C 2 H 2 Cl 4, nm): λ max 274, 333 nm; MS (MALDI) m/z: (M+, 100%), (95%), (75%), calc.: (100%), (60%), (17%). 1,3,5,7,9-Penta-(4-hydroxyphenyl)corannulene (6) To an ice cold solution of compound 5 (83 mg, 0.1 mmol) in dry CH 2 Cl 2 (4 ml) was added BBr 3 (1 M solution in CH 2 Cl 2, 2.5 ml, 2.0 mmol) and the reaction was allowed to warm to room temperature. After 24 h water (3 ml) was added and the CH 2 Cl 2 was removed under reduce pressure. The insoluble yellow solid was collected and washed with water (2 2 ml), methanol (2 ml) and CH 2 Cl 2 (2 ml) to leave compound 6 (61 mg, 87%) as a pale yellow solid. 1 H and 13 C MR were not obtained due to poor solubility of 6 in common deuterated solvents; MS (MALDI) m/z: (M+, 100%), (80%), (50%), calc.: (100%), (54%), (17%). 1,3,5,7,9-Penta-(4-allyloxyphenyl)corannulene (7). ah (60% dispersion, 15 mg, 0.4 mmol) was added to a stirred solution of compound 6 (6 mg, mmol) in DMF (2 ml) at room temperature. The solution stirred for 30 min before allyl bromide (0.04 ml, 0.5 mmol) was added slowly. After 16 h the reaction was quenched with water (4 ml), extracted with CH 2 Cl 2 (2 X 4 ml), dried over as 4 and purified over silica gel preparative TLC (CHCl 3 -cyclohexane, 1:4) S6

7 to afford compound 7 (4 mg, 65%) as a yellow solid. 1 H-MR (500 MHz, CDCl 3 ): δ 7.82 (s, 5H), 7.63 (d, J = 8.7 Hz, 10H), 7.05 (d, J = 8.7 Hz, 10H), 6.13 (m, 5H), 5.48 (dd, J = 17.4, 1.5 Hz, 5H), 5.35 (dd, J = 10.5, 1.5 Hz, 5H), 4.64 (br d, J = 5.4 Hz, 10H); 13 C-MR (125 MHz, CDCl 3 ): δ 158.4, 142.3, 135.6, 133.8, 132.4, 131.2, 129.9, 125.4, 118.1, 115.1, 65.0; MS (MALDI) m/z: (M+, 100%), (75%), (36%), calc.: (100%), (70%), (24%). St-Bu 1,3,5,7,9-Penta-(4-tert-buthylthiophenyl)corannulene (8) was t-bus St-Bu prepared according to the general procedure: 1,3,5,7,9- t-bus St-Bu pentachlorocorannulene (42 mg, 0.1 mmol), 4-tertbuthylthiophenylboronic acid (168 mg, 0.8 mmol), cesium fluoride (226 mg, 1.5 mmol) and Pd[P(t-Bu) 3 ] 2 (10 mg, 0.02 mmol) in dry dioxane (8 ml) were kept for 24 h at 80 ο C. Compound 8 (60 mg, 59%) was collected as a pale yellow solid. 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ 7.92 (s, 5H), 7.69 (m, 20H), 1.38 (s, 45H); 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 141.7, 139.7, 137.7, 135.5, 132.6, 130.1, 126.2, 124.2, 46.6, 31.2; IR (KBr): 2968, 2919, 1491, 1456, 1363, 1165, 838 cm -1 ; UV (C 2 H 2 Cl 4, nm): λ max 277, 293, 328; MS (MALDI) m/z: (100%) and (70%) [M+ - isopropene], calcd.: (100%) and (75%). SH 1,3,5,7,9-Penta-(4-thiophenyl)lcorannulene (9). Compound 8 (15 HS HS SH mg, mmol) was dissolved in a freshly prepared mixture of Tf (0.3 ml), TFA (0.3 ml) and toluene (2 ml). The reaction SH S7

8 was heated to 80 ο C for 16 h, cooled and diluted with toluene (8 ml). The insoluble yellow solid was collected and washed with toluene (2 3 ml) methanol (2 ml) and dichloromethane (2 ml) to afford compound 9 (10 mg, 86%) as a yellow solid. 1 H and 13 C MR were not obtained due to poor solubility of 9 in common deuterated solvents; MS (MALDI) m/z: (100%) and (60%) [M+- H], calc.: (100%) and (54%). S S 1,3,5,7,9-Penta-(4-allylthiophenyl)corannulene (10). ah (60% dispersion, 13 mg, 0.3 mmol) was added to a stirred S solution of compound 9 (3 mg, mmol) in DMF (2 ml) S at room temperature. The solution stirred for 30 min before S allyl bromide (0.04 ml, 0.5 mmol) was added slowly. After 16 h water was added and the product was collected and washed with water (2 2 ml), methanol (2 ml) and CH 2 Cl 2 (2 ml) to afford compound 10 (3.1 mg, 82%) as a yellow solid. 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ 7.84 (s, 5H), 7.65 (d, J = 7.2 Hz, 10H), 7.43 (d, J = 7.2 Hz, 10H), 5.96 (m, 5H), 5.27 (d, J = 16.8, 5H), 5.17 (d, J = 9.3 Hz, 5H), 3.65 (d, J = 6.9 Hz, 5H); Due to poor solubility of 10 in common deuterated solvents 13 C-MR couldn t be measured; MS (MALDI) m/z: (M+-(ally) 5, 100%), calc.: (100%) S8

9 1,3,5,7,9-Penta-4-(1,3-dioxanyl)-phenylcorannulene (11) was prepared according to the general procedure: 1,3,5,7,9- pentachlorocorannulene (42 mg, 0.1 mmol), 4-[1,3-dioxan-2- yl)phenylboronic acid (166 mg, 0.8 mmol), cesium fluoride (226 mg, 1.6 mmol), Pd[P(t-Bu) 3 ] 2 (10 mg, 0.02 mmol) were kept for 24 h at 80 ο C. Compound 11 (65 mg, 61%) was collected as a pale yellow solid. 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ 7.92 (s, 5H), 7.75 (d, J = 8 Hz, 10H), 7.62 (d, J = 8 Hz, 10H), 5.58 (s, 5H), 4.3 (m, 10H), 4.02 (m, 10H), 2.25 (m, 5H), 1.48 (m, 5H); 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 139.9, 138.3, 135.6, 130.0, 129.2, 127.2, 126.9, 126.3, 101.5, 67.5, 25.9; IR (KBr): 2964, 2850, 1379, 1278, 1238, 1150, 1108, 1016, 990, 834 cm - 1; UV (C 2 H 2 Cl 4, nm): λ max 270, 289, 324; MS (MALDI) m/z: (M+, 100%), and (65%), calc.: (100%) and (75%). C 1,3,5,7,9-Penta-(4-formylphenyl)corannulene(12). TFA (0.5 C C ml) was added to a mixture of 11 (21 mg, 0.02 mmol) in CH 2 Cl 2 - H 2 (1:1, 2 ml) at room temperature. After 2 h the C C dichloromethane was removed under reduce pressure and the product was collected and washed with water (2 ml), methanol (2 ml) and CH 2 Cl 2 (2 ml) to afford compound 12 (13 mg, 85%) as a yellow solid. 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ (s, 5H), 8.03 (d, J = 10 Hz, 10H), 7.89 (d, J = 10 Hz, 10 H), 7.88 (s, 5H); 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 194.0, 147.0, 143.4, 137.7, 137.5, 132.4, 132.2, 130.7, 128.6; IR (KBr): 2821, 1704, 1602, 1212, 1172, 835, 803 cm -1 ; UV (C 2 H 2 Cl 4, nm): S9

10 λ max 278, 323; MS (MALDI) m/z: (M+, 100%), (64%), (20%), calc.: (100%), (60%), (14%). Me 1,3,5,7,9-penta-(6-methoxy-3-pyridinyl)corannulene (13). To Me Me an oven dried three neck flask connected to a Schlenk line were added 1,3,5,7,9-pentachlorocorannulene (42 mg, 0.1 mmol), (6- Me Me methoxy-3-pyridyl)boronic acid (122 mg, 0.8 mmol) and Pd[P(t- Bu) 3 ] 2 (0.02 mmol, 10 mg). The flask was purged repeatedly with nitrogen before dry dioxane (8 ml) was added follow by aqueous solution of K 3 P 4 (1.5 ml, 0.8 M). The mixture was stirred for 15 min. at room temperature, kept at 100 ο C for 72 hrs and cooled down to room temperature. Most of the solvent was removed; water was added (10 ml) and has been extracted with tetrachloroethane (2 X 10 ml). The combined organic solvents were removed under reduce pressure, toluene (2 ml) was added and the insoluble product was collected and washed with toluene (2 2 ml), methanol (2 2 ml) and dichloromethane (2 2 ml) affording compound 13 (40 mg, 51%) a pale yellow solid; 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ 8.43 (s, 5H), 7.97 (d, J = 10 Hz, 5H), 7.76 (s, 5H), 6.91 (d, J = 10 Hz, 5H), 3.99 (s, 15H); 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 165.8, 149.2, 141.9, 140.9, 137.4, 131.3, 130.1, 127.3, 112.8, 55.8; IR (KBr): 1601, 1498, 1262, 1127, 1027, 999, 956, 869, 833 cm -1 ; UV (C 2 H 2 Cl 4, nm): λ max 270, 303, 325; MS (MALDI) m/z: (M+, 100%), (M+H, 95%) calc.: (100%). S10

11 1,3,5,7,9-Penta-(4-pyridinyl)corannulene (14). To an oven dried three neck flask connected to a schlenk line were added 1,3,5,7,9- pentachlorocorannulene (42 mg, 0.1 mmol), 4-pyridinylboronic acid (100 mg, 0.8 mmol) and Pd[P(t-Bu) 3 ] 2 (20 mg, 0.04 mmol). The flask was purged repeatedly with nitrogen before dry DMF (3 ml) was added follow by aqueous solution of potassium phosphate (1 ml, 1.2 M).The resulting mixture was stirred at 100 C for 72 h, cooled down to room temperature and diluted with toluene (50 ml). The organic phase together with emulsion was extracted with water (2 20 ml) and washed with 10% a aqueous solution (2 20 ml) and water (2 30 ml). The combined organic solvents were removed under reduce pressure, toluene (2 ml) was added and the insoluble product was collected and washed with toluene (2 2 ml), methanol (2 2 ml) and dichloromethane (2 2 ml) to afford compound 14 (15 mg, 24%) as yellow solid. 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ 8.79 (d, J = 5.5 Hz, 10H), 7.93 (s, 5H), 7.66 (d, J = 5.5 Hz, 10H); 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 150.5, 146.4, 140.3, 136.1, 128.7, 126.7, 124.6; IR (KBr): 1590, 1438, 1414, 1252, 828, 653 cm -1 ; UV (C 2 H 2 Cl 4, nm): λ max 287, 316; MS (MALDI) m/z: [M+,100%], calc.:635.2 (100%). Fréchet-type dendrimer, F-G#1-(Acet) 10 (15). A mixture of compound 6 (10 mg, mmol), 1- (bromomethyl)-3,5-bis(2-propynyloxy)benzene (18) 4 (27 mg, 0.11 mmol) and K 2 C 3 (23 mg, 0.17 mmol) in DMF (1.5 ml) was heated to 50 ο C for 16 h, cooled down and poured into water (4 ml). The precipitate was collected, washed with water (2 ml), methanol (2 2 ml) and hexane (2 ml) affording compound S11

12 15 (23 mg, 96%) as a yellow solid. 1 H-MR (500 MHz, C 2 D 2 Cl 4 ): δ 7.85 (s, 5H), 7.68 (d, J = 7.8 Hz, 10H), 7.11 (d, J = 7.8 Hz, 10H), 6.74 (br s, 10H), 6.59 (br s, 5H), 5.08 (s, 10H), 4.71 (br d, J = 2.1 Hz, 20H), 2.59 (br s, 10H); 13 C-MR (125 MHz, C 2 D 2 Cl 4 ): δ 160.6, 160.2, 143.5, 141.4, 137.1, 134.4, 133.0, 131.2, 127.1, 116.7, 108.9, 103.5, 80.3, 78.1, 71.6, 57.9; MS (MALDI) m/z: [M+], calc.: Fréchet-type dendrimer, F-G#2-() 20 (16). To a stirred solution of compound 15 (20 mg, mmol), 5-(azidomethyl)benzene-1,3-diol (19) 4b (23 mg, 0.17 mmol) and sodium ascorbate (4 mg, mmol) in THF (4 ml) under argon atmosphere, was added CuS 4 (1.8 mg, mmol in 0.8 ml of H 2 ). The reaction was kept at 45 o C for 48 h and water was added (4 ml). The precipitate product was collected, washed with water (2 2 ml), ether (2 2 ml) and acetone (2 ml) to afford compound 16 (33 mg, 84%) as a brown solid, which was reacted directly in the next step. 1 H-MR (500 MHz, DMS-d 6 ): δ 9.34 (s, 20H, ), 8.20 (s, 10H), 7.78 (br s, 5H), 7.67 (br d, J = 7.8 Hz, 10H) 7.18 (br d, J = 7.8 Hz, 10H), 6.74 (br s, 10H), 6.71 (br s, 5H), 6.10 (br s, 30H), 5.37 (s, 20H), 5.11 (br s, 30H); 13 C-MR (125 MHz, DMS-d 6 ): δ 160.3, 159.6, 159.4, 143.7, 142.7, 140.3, 138.8, 135.6, 132.3, 131.8, 130.0, 125.9, 125.7, 116.3, 107.5, 106.6, 103.0, 101.7, 70.2, 67.9, S12

13 S13 Fréchet-type dendrimer, F-G#3-(Acet) 40 (17). A mixture of compound 16 (10 mg, mmol), compound 18 (24 mg, mmol) and K 2 C 3 (20 mg, 0.14 mmol) in DMF (1.5 ml) was heated to 50 ο C for 16 h, cooled down and poured into water (4 ml). The precipitate was collected, washed with water (2 ml), methanol (2 2 ml) and ether (2 2 ml) affording compound 17 (20 mg, 92%) as a yellow solid. 1 H-MR (300 MHz, CDCl 3 ): δ 7.79 (br s, 5H), 7.59 (br s, 10H), 7.52 (s, 10H), 7.03 (br s, 10H), (m, 105H), 5.29 (br s, 20H), 5.11 (br s, 20H), 5.02 (s, 5H), 4.86 (s, 40H), 4.60 (s, 80H), 2.47 (s, 40H); 13 C-MR (125 MHz, CDCl 3 ): δ 160.5, 159.9, 159.1, 158.8, 144.6, 142.2, 139.9, 139.4, 137.1, 135.8, 132.9, 131.4, 129.8, 125.6, 123.3, 115.5, 107.5, 107.1, 106.9, 103.4, 102.6, 101.8, 78.6, 76.2, 70.1 (2XC), 62.3, 56.2, 54.4; MS (MALDI) m/z: [M+], calc.:

14 1 H MR of compound 2 (CDCl 3, 500 MHz) C 2CH 3 H 3C 2C C 2CH 3 H 3C 2C C 2CH ppm 13 C MR of compound 2 (C 2 D 2 Cl 4, 125 MHz) C 2CH 3 H 3C 2C C 2CH 3 H 3C 2C C 2CH ppm S14

15 IR of compound 2 (KBr) Wavelength / cm -1 S15

16 1 H MR of compound 3 (DMS-d 6, 300 MHz). C 2H 2C C 2H 2C C 2H ppm IR of compound 3 (KBr) Wavelength / cm -1 S16

17 1 H MR of compound 4 (DMS-d 6, 500 MHz). CH 2 H 2C CH 2 H 2C CH ppm S17

18 1 H MR of compound 5 (C 2 D 2 Cl 4, 500 MHz) CH 3 H 3C CH 3 H 3C CH ppm C MR of compound 5 (C 2 D 2 Cl 4, 125 MHz) CH 3 H 3C CH 3 H 3C CH ppm S18

19 IR of compound 5 (KBr) Wavelength / cm -1 S19

20 1 H MR of compound 7 (C 2 D 2 Cl 4, 500 MHz) DCM ether ether ppm S20

21 1 H MR of compound 8 (C 2 D 2 Cl 4, 500 MHz) St-Bu t-bus St-Bu t-bus St-Bu DCM ppm C MR of compound 8 (C 2 D 2 Cl 4, 125 MHz) St-Bu t-bus St-Bu t-bus St-Bu ppm S21

22 1 H MR of compound 10 (C 2 D 2 Cl 4, 300 MHz). S S S S S ppm S22

23 1 H MR of compound 11 (C 2 D 2 Cl 4, 500 MHz) ppm IR of compound 11 (KBr) Wavelength / cm -1 S23

24 1 H MR of compound 12 (C 2 D 2 Cl 4, 500 MHz) C C C C C ppm 13 C MR of compound 12 (C 2 D 2 Cl 4, 125 MHz) C C C C C ppm S24

25 IR of compound 12 (KBr) Wavelength / cm -1 S25

26 1 H MR of compound 13 (C 2 D 2 Cl 4, 500 MHz) Me Me Me Me Me ppm 13 C MR of compound 13 (C 2 D 2 Cl 4, 125 MHz). Me Me Me Me Me ppm S26

27 1 H MR of compound 14 (C 2 D 2 Cl 4, 500 MHz) ppm C MR of compound 14 (C 2 D 2 Cl 4, 125 MHz). i ppm S27

28 1 H MR of compound 15 (C 2 D 2 Cl 4, 300 MHz) ppm C MR (coupled experiment) of compound 15 (C 2 D 2 Cl 4, 125 MHz) ppm S28

29 1 H MR of compound 16 (DMS-d 6, 500 MHz) Ether THF THF ppm C MR of compound 16 (DMS-d 6, 125 MHz). 16 THF ether acetone ether THF ppm S29

30 1 H MR of compound 17 (CDCl 3, 500 MHz) DMF 17 DMF ppm C MR of compound 17 (CDCl 3, 125 MHz). 17 acetone ether ether DMF DMF DMF ppm S30

31 References: (1) Mizyed, S.; Georghiou, P.; Bancu, M.; Cuadra, B.; Rai, A. K.; Cheng, P.; Scott, L. T. Journal of the American Chemical Society 2001, 123(51), (2) Bolletta, F.; Garelli, A.; Montalti, M.; Prodi, L.; Romeno, S.; Zaccheroni,.; Canovese, L.; Chessa, G.; Santo, C.; Visentin, F. Inorganica Chimica Acta, 2004, 357, (3) (a)barth, W. E.; Lawton, R. G. J. Am. Chem. Soc. 1966, 88, ; (b) Seiders, T. J.; Elliott, E.; Grube, G.; Siegel, J. S. J. Am. Chem. Soc. 1999, 121, ; (c) Sygula, A.; Rabideau, P. W. J. Am. Chem. Soc. 2000, 122, ; (d) Cheng, P. Ph.D. Dissertation, Boston College, Boston, MA, 1996; pp 212; (e) Scott, L. T. Pure Appl. Chem. 1996, 68, (4) (a) Kanamathareddy, S.; Gustch, C. D.; J. rg. Chem. 1996, 61, (b) Antoni, P.; ystrom, D.; Hawker, C. J.; Hult, A.; Malkoch, M. Chem. Commun. 2007, S31