Supporting Information Suzuki-Miyaura Coupling of HC-Boranes: a ew Addition to the C-C Coupling Toolbox Julien Monot, a Malika Makhlouf Brahmi, a Shau-Hua Ueng, a Carine Robert, a Marine Desage-El Murr, a Dennis P. Curran,*,a,b Max Malacria,*,a Louis Fensterbank,*,a and Emmanuel Lacôte*,a. a Institut Parisien de chimie moléculaire (UMR CRS 71), C. 229, UPMC Univ Paris 06, 4 place Jussieu, 75005 Paris, France. b University of Pittsburgh, Department of Chemistry,Pittsburgh, PA 152, USA. General Remarks. Reactions were carried out under argon gas, with magnetic stirring and redistilled solvents when necessary. Thin layer chromatography (TLC) was performed on Merck F254 silica gel Merck Geduran SI A silica gel (35 70 mm) was used for column chromatography. The melting points reported were measured with a SMP3 Stuart Scientific melting point apparatus and were uncorrected. IR spectra were recorded with a Bruker Tensor 27 ATR diamant PIKE spectrometer. 1 H-, 13 C- and 11 B-MR spectra were recorded with Bruker Avance 0 spectrometer fitted with a BBF probe 13 C/ 11 B/ 1 H including z gradient. Chemical shifts are given in ppm. Unless otherwise noted, the MR spectra were recorded in CDCl 3. Chloroform (δ = 7.26 ppm) was used as internal standard in 1 H MR spectra, whereas CDCl 3 (δ = 77.2 ppm) was used as internal standard in 13 C MR spectra. 11 B chemical shifts are relative to Et 2 BF 3. Coupling constants (J) are given in Hertz (Hz). The terms m, s, d, t, q, quint. represent multiplet, singlet, doublet, triplet, quadruplet, quintuplet, respectively. The term br means that the signal is broad. In most of the cases, the carbenic carbon cannot be seen due to the coupling with the boron atom. HRMS were performed at the Institut de chimie moléculaire (FR 2769, UPMC). Pd(Ac) 2, RuPhos (2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl), Pd(dppf)Cl 2 and K 2 C 3 obtained from commercial sources were used as received. Microwave reactions were performed by using a Biotage Iniator Microwave Synthetizer 2.0. 1
General procedure for the preparation of imidazolylidene borane complexes. Sublimed potassium tert-butoxide (316.8 mg, 2.82 mmol) was added at 0 C to a suspension of imidazolylium chloride salt 1 (2.35 mmol) in THF ( ml). After min, the reaction mixture was filtrated through a celite pad and rinsed with EtAc. Solvents were removed in vacuo, and the residue was suspended in dry hexane (19 ml). The borane (1M solution in THF) was added to the carbene suspension at 0 C and the resulting solution was allowed to warm to room temperature overnight. The solvents were evaporated to deliver the expected complexes after appropriate purification. Imidazolylidene borane complex-bph 3 (1): BPh 3 This carbene-borane was obtained as a white solid after recristallyzation (DCM/Et 2 /Pentane: 1/3/5). (95% yield). Mp 175-177 C; IR (neat): ν = 56, 2965, 2929, 2871, 20, 1883, 18, 908 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 7. (t, J = 7.8 Hz, 2H, arom.), 7.39 7. (m, H, arom.), 6.96 6.88 (m, 8H, arom.), 6.82 6.74 (m, 3H, arom.), 2.23 (sept., J = 6.9 Hz, 4H, CHMe 2 ), 1.25 (d, J = 6.9 Hz, 12H, CHMeMe), 1.09 (d, J = 6.9 Hz, 12H, CHMeMe) ; 13 C MR (0 MHz, CDCl 3 ): δ 144.9 (C arom.), 133.5 (CH arom.), 132.3 (CH arom.), 129.8 (CH arom.), 126.6 (CH arom.), 126.0 (CH arom.), 124.8 (CH arom.), 122.6 (CH arom.), 289 (CHMe 2 ), 24.7 (CHMeMe), 23.7 (CHMeMe) ; 11 B MR (BF 3 Et 2, 133 MHz, CDCl 3 ): δ - 0.85 (br s). 1 Arduengo, III, A. J.; Krafczyk, R.; Schmutzler, R. Tetrahedron 1999, 55, 14523-14534 2
Imidazolylidene borane complex-bet 3 (2): BEt 3 This carbene-borane was obtained analytically pure and used without further purification. (87% yield). Mp 150-153 C; IR (neat): ν = 69, 2963, 2870, 1950, 18, 10, 1366 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 7. (t, J= 7.5 Hz, 2H, arom.), 7.19 (d, J = 7.5 Hz, 4H, arom.), 6. (s, 2H, =CH()), 3.06 (sept., J = 6.8 Hz, 4H, CHMe 2 ), 1.52 (d, J = 6.8 Hz, 12H, CHMeMe), 1.18 (t, J = 7.6 Hz, 9H, CH 2 Me), 1.07 (d, J = 7 Hz, 12H, CHMeMe), 0.56 (q, J = 7.6 Hz, 6H, CH 2 Me); 13 C MR (0 MHz, C 6 D 6 ): δ 146 (CiPr arom.), 137.0 (C arom.), 1.4 (CH arom.), 124.1 (=CH()), 123.8 (CH arom.), 29 (CHMe 2 ), 26.4 (CHMeMe), 22.5 (CHMeMe), 14.9 (br CH 2 Me), 12.4 (CH 2 Me); 11 B MR (BF 3 Et 2, 133 MHz, CDCl 3 ): δ - 13.2 (br s). 3
Procedure A: Coupling from iodides and triflates. To Pd(dppf)Cl 2 (4 mg, 6 mol%), the substrate (0.082 mmol) and the HC-borane (0.082 mmol), THF (4 ml) and water (150 µl) were added. The reaction mixture was stirred at C for 1h or at 1 C under micro-wave for 15 min. The solvent was then evaporated in vacuo and the residue was purified by flash chromtography (Si 2, Pentane to Pentane/Et 2 : 99/1). Procedure B : Coupling from bromides and triflates. An Ace pressure tube (15 ml) was charged with Pd(Ac) 2 (5.6 mg, 5%), XPhos (23.8 mg, %), the substrate (0.5 mmol) and the HC-Borane (0.5 mmol). The pressure tube was sealed with a septum, evacuated under vacuum, and purged with argon (three times). Toluene (2.5 ml) and water (250 µl) were added and the pressure tube was sealed with a teflon cap. The reaction mixture was stirred at C for 24 h or at 1 C under micro-wave for min. The reaction mixture was cooled at room temperature, filtered through a small pad of silica (Pentane/Ether: 95/5) and the solvent was evaporated in vacuo. The residue was purified by flash chromatography (Si 2, Pentane to Pentane/Et 2 : 99/1). Procedure C : Coupling from chlorides. An Ace pressure tube (15 ml) was charged with Pd(Ac) 2 (11.2 mg, %), RuPhos (46.7 mg, %), the substrate (0.5 mmol) and the HC-Borane (0.5 mmol). The pressure tube was sealed with a septum, evacuated under vacuum, and purged with argon (three times). Toluene (2.5 ml) and water (250 µl) were added and the pressure tube was sealed with a teflon cap. The reaction mixture was stirred at C for 24 h or at 1 C under micro-wave for min. The reaction mixture was cooled at room temperature, filtered through a small pad of silica (Pentane/Ether: 95/5) and the solvent was evaporated in vacuo. The residue was purified by flash chromatography (Si 2, Pentane to Pentane/Et 2 : 99/1). 4
1,1 -Biphenyl-4-carboxylic acid, cyclohexyl ester (3): The product was obtained as a white solid. Mp 96-99 C; IR (neat): ν = 2936, 2859, 17, 1112 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 8.12 (d, J= 8.1 Hz, 2H, arom.), 7.67 7.61 (m, 4H, arom.), 7.49 7. (m, 3H, arom.), 5.29 5.03 (m, 1H, CH), 1.98 1.95 (m, 2H, CH 2 ), 1.83 1.8 (m, 2H, CH 2 ), 1.64 1.58 (m, 3H, CH 2 ), 1.51 1.38 (m, 3H, CH 2 ); 13 C MR (0 MHz, CDCl 3 ): δ 165.8 (C=), 145.4 (C arom.), 1.1 (C arom.), 1 (CH arom.), 128.9 (CH arom.), 128 (CH arom.), 127.2 (CH arom.), 126.9 (CH arom.), 73 (CH), 31.6 (CH 2 ), 25.5 (CH 2 ), 23.6 (CH 2 ). 1-phenyl-2-(octyloxymethyl)benzene (4): The product was obtained as a colorless oil. IR (neat): ν =, 2924, 2853, 1951, 1895, 1812, 94 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 7.61 7.55 (m, 1H, arom.), 7.47 7.33 (m, 7H, arom.), 7.29 7.31 (m, 1H, arom.), 4.39 (s, 2H, ArCH 2 ), 3.42 (t, J = 6.6 Hz, 2H, CH 2 CH 2 ), 1.66 1.51 (m, 2H, CH 2 CH 2 ), 1.43 1.19 (m, H, CH 2 ), 0.91 (t, J = 6.8 Hz, 3H, Me); 13 C MR (0 MHz, CDCl 3 ): δ 141.8 (C arom.), 1.9 (C arom.), 135.8 (C arom.), 129.9 (CH arom.), 129.3 (CH arom.), 129.2 (CH arom.), 128.0 (CH arom.), 127.6 (CH arom.), 127.5 (CH arom.), 127.0 (CH arom.), 70.7 (ArCH 2 + CH 2 CH 2 ), 31.9 (CH 2 CH 2 ), 29.8 (CH 2 ), 29.5 (CH 2 ), 29.3 (CH 2 ), 26.3 (CH 2 ), 22.7 (CH 2 ), 14.1 (Me); HRMS calcd. For C 21 H 28 a ([M + a] + ): 319.32, found: 319.. 5
9-phenylphenanthrene (5): 19 18 17 15 16 9 14 8 13 1 2 6 3 5 7 4 11 12 The product was obtained as a white solid. Mp 6-9 C; IR (neat): ν = 57, 1951, 1491, 1450 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 8.87 (d, J= 8 Hz, 1H, H4), 8.82 (d, J= 8 Hz, 1H, H11), 8.06 (d, J= 8 Hz, 1H, H14), 7.99 (d, J= 8 Hz, 1H, H1), 7. 7.54 (m, H, arom.); 13 C MR (0 MHz, CDCl 3 ): δ 1.8 (C15), 138.7 (C9), 131.5 (C6), 131.1 (C7), 1.6 (C5), 1.0 (C19 + C17), 129.9 (C8), 128.6 (C18), 128.3 (C + C16), 127.5 (C1), 127.3 (C14), 126.9 (C2), 126.8 (C13), 126.5 (C3), 126.5 (C12), 126.4 (C), 122.9 (C4), 122.5 (C11) ; HRMS calcd. For C H + 14 ([M] + ): 254.90, found: 254.88. cyclohexyl 4-ethylbenzoate (6): The product was obtained as a colorless oil. IR (neat): ν = 2932, 2858, 1711, 15 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 7.96 (d, J = 7.8 Hz, 2H, arom.), 7.25 (d, J = 7.8 Hz, 2H, arom.), 5.05 4.99 (m, 1H, CH), 2.70 (q, J = 7.6 Hz, 2H, ArCH 2 ), 1.96-1.91 (m, 2H, CH 2 ), 1.82 1.77 (m, 2H, CH 2 ), 1.63-1.50 (m, 3H, CH 2 ), 1.49 1.27 (m, 3H, CH 2 ), 1.25 (t, J = 7.6 Hz, 3H, Me); 13 C MR (1 MHz, CDCl 3 ): δ 165.9 (C=), 149.3 (C arom.), 129.5 (CH arom.), 128.4 (C arom.), 127.7 (CH arom.), 72.6 (CH), 31.5 (CH 2 + ArCH 2 ), 28.8 (CH 2 ), 25.4 (CH 2 ), 23.6 (CH 2 ), 15.2 (Me) ; HRMS calcd. For C 15 H 2 a ([M + a] + ): 255.1355, found: 255.1355. 6
1-ethyl-2-(octyloxymethyl)benzene (7): The product was obtained as a colorless oil. IR (neat): ν = 21, 2957, 2925, 96 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 7.34 (d, J = 7.5 Hz, 1H, arom.), 7.26 7.16 (m, 3H, arom.), 4.52 (s, 2H, ArCH 2 ), 3.48 (t, J = 6.6, 2H, CH 2 CH 2 ), 2.70 (q, J = 7.5 Hz, 2H, ArCH 2 Me), 1.62 (quint., J= 6.6 Hz, 2H, CH 2 CH 2 ), 1.49 1.19 (m, 13H, CH 2 + ArCH 2 Me), 0.88 (t, J = 7.5 Hz, 3H, CH 2 CH 2 Me) ; 13 C MR (0 MHz, CDCl 3 ): δ 142.6 (C arom.), 135.8 (C arom.), 128.8 (CH arom.), 128.3 (CH arom.), 127.8 (CH arom.), 125.6 (CH arom.), 70.9 (CH 2 ), 70.6 (CH 2 ), 31.8 (CH 2 ), 29.8 (CH 2 ), 29.4 (CH 2 ), 29.3 (CH 2 ), 26.2 (CH 2 ), 25.2 (CH 2 ), 22.6 (CH 2 ), 15.1 (Me), 14.0 (Me) ; HRMS calcd. For C 17 H 28 a ([M + a] + ): 271.32, found: 271.33. 9-ethylphenanthrene (8): 1 4 2 8 5 3 11 9 7 12 6 The product was obtained as a white solid. Mp 65-66 C; IR (neat): ν = 76, 2965, 2933, 2874, 1948, 1917, 1900 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 8.74 (d, J= 9.2 Hz, 1H, H6), 8.67 (d, J = 7.6 Hz, 1H, H12), 8.13 (d, J = 9.2 Hz, 1H, H1), 7.84 (d, J= 7.6 Hz, 1H, H15), 7.74 7.52 (m, 5H, arom.), 3.17 (q, J = 7.5 Hz, 2H, CH 2 ), 1.46 (t, J= 7.5 Hz, 3H, Me) ; 13 C MR (0 MHz, CDCl 3 ) : δ 138.2 (C arom.), 132.0 (C arom.), 131.2 (C arom.), 1.6 (C arom.), 129.6 (C arom.), 128.0 (C15), 126.5 (CH arom.), 126.4 (CH arom.), 126.0 (CH arom.), 125.8 (CH arom.), 124.9 (CH arom.), 124.2 (CH arom.), 123.2 (CH arom.), 122.4 (CH arom.), 26 (CH 2 Me), 14.4 (CH 2 Me) ; HRMS calcd. For C 16 H 14 + ([M] + ): 6.90, found: 6.89. 16 15 14 13 7
1,1-diphenylbut-1-ene (9): The product is obtained as a colorless oil. IR (neat): ν = 55, 22, 29, 2926, 2852, 1946, 1886, 16, 1731, 1443, 1663 cm -1 ; 1 H MR (0 MHz, CDCl 3 ): δ 7.43 7.18 (m, H, arom.), 6.09 (t, J= 7.6 Hz, 1H, =CH), 2.15 (quint., J = 7.5 Hz, 2H, CH 2 Me), 1.07 (t, J = 7.5 Hz, 3H, Me); 13 C MR (0 MHz, CDCl 3 ): δ 142.8 (C arom.), 141.0 (C arom.), 1.2 (C arom.), 131.7 (CH arom.), 129.9 (CH arom.), 128.1 (CH arom.), 128.0 (CH arom.), 127.2 (CH arom.), 126.8 (CH arom.), 126.7 (CH arom.), 23.2 (CH 2 Me), 14.5 (CH 2 Me). 8
9 BPh 3 1 H MR 2.1195 9.81 7.2618 2.9711 4.0000 11.937 11.842 Integral 7.3499 7.3373 7.33 7.31 7.20 6.9433 6.9395 6.9252 6.9121 6.9061 6.7981 6.7948 6.7915 6.7767 6.7625 6.7587 6.7554 2.2450 2.22 2.21 2.16 1.2686 1.2516 1.09 1.0785 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 BPh 3 13 C MR 144.9008 133.4622 132.55 129.7692 126.5990 125.9649 124.8339 122.6490 77.4770 77.10 76.84 28.97 24.6793 23.6853 50 70 90 0 1 1 1 1 150 1 170 1 190 1 1
11B en 8 scans, avec D1 = 2s 11 B MR -0.0000-0.8511 BPh 3 1 35 25 15 5 0-5 - -15 - -25 - -35-1H routine : 8 scans Integral 2.0770 4.1714 1.8741 4.0000 11.8.482 12.364 6.0356 7.32 7.38 7.2847 7.1975 7.1784 6.25 3.0904 3.0734 3.0570 3.00 3.02 1.5250 1.5086 1.1968 1.1782 1.1590 1.0763 1.0587 0.5837 0.5651 0.5459 0.5267 1 H MR BEt 3 2 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
JM277-13C 146.06 137.0653 1.38 124.1357 123.7673 13 C MR 29.0021 26.59 22.4816 14.9587 12.37 BEt 3 2 1 150 1 1 1 1 0 90 70 50 0 11B en 8 scans, avec D1 = 2s -13.2432 11 B MR BEt 3 2 0 0 - - - - -0 11
12 2.0000 3.8902 1.6902 0.8875 1.0715 2.00 2.2161 3.4677 3.5336 Integral 8.1356 8.1153 7.6715 7.6507 7.68 7.6364 7.6183 7.4896 7.4715 7.4518 7.41 7.3948 7.20 5.2941 5.2925 5.0892 5.0771 5.0667 5.0569 5.0448 5.0355 1.9842 1.9623 1.9546 1.8351 1.8269 1.8116 1.34 1.6450 1.6368 1.6132 1.50 1.5897 1.58 1.5146 1.4987 1.4905 1.4817 1.4741 1.4658 1.4576 1.4417 1.43 1.89 1.3848 1.3782 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 1 H MR 165.8359 145.39 1.11 1.05 128.8724 128.0327 127.2444 126.9359 77.3170 77.0000 76.68 73.0243 31.6481 25.4789 23.6625 50 70 90 0 1 1 1 1 150 1 170 13 C MR 3 3
13 0.9758 7.1887 1.0042 2.0000 1.9782 2.3413.9 3.2314 Integral 7.3756 7.3619 7.3586 7.3159 7.3126 7.20 4.3933 3.4312 3.4148 3.3983 1.65 1.5952 1.5754 1.3426 1.3245 1.2943 0.9234 0.9070 0.8894 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 1H routine : 8 scans 1 H MR 141. 1.9235 135.7911 129.94 129.2706 129.2278 128.0368 127.5570 127.4798 127.00 77.3725 77.0555 76.7385 70.7321 31.8750 29.7929 29.4758 29.3131 26.2970 22.6983 14.1472 50 70 90 0 1 1 1 1 13 C MR 4 4
1H routine : 8 scans 8.84 8.82 8.8256 8.59 8.0684 8.0482 8.0005 7.9813 7.16 7.7813 7.77 7.7638 7.7611 7.7435 7.7397 7.7298 7.7265 7.7117 7.76 7.6975 7.6926 7.6893 7.6816 7.6778 7.68 7.6427 7. 7.6235 7.71 7.43 7.5863 7.5824 7.5715 7.56 7.5507 7.5474 1 H MR 5 Integral 2.0000 2.0274 5.2956 3.9257 11.0.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 13C routine : 32 scans 1.7737 138.7345 131.5285 131.87 1.5946 1.0291 129.9263 128.6153 128.26 127.4757 127.3129 126.8845 126.7903 126.5332 126.4561 126.47 122.86 122.4890 13 C MR 5 1 150 1 1 1 1 0 90 70 50 14
15 1.9084 3.6735 1.0000 1.9659 2.0653 2.0994 3.43 3.3123 3.05 Integral 7.9739 7.9537 7.2644 7.2627 7.20 7.2584 7.24 5.0503 5.04 5.0284 5.0185 5.0086 4.9966 4.9873 2.7299 2.77 2.6915 2.6729 1.9425 1.9223 1.9135 1.66 1.7973 1.7886 1.7814 1.7738 1.5973 1.5738 1.5650 1.5426 1.4637 1.4549 1.4390 1.42 1.2713 1.2527 1.2335 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 1 H MR 165.8874 149.3334 129.5493 128.4354 127.6557 72.5959 31.5539 28.8377 25.44 23.5597 15.1884 50 70 90 0 1 1 1 1 150 1 170 13C routine : 32 scans 13 C MR 6 6
1H routine : 8 scans Integral 7.3296 7.2485 7.23 7.2162 1.12 7.1975 7.1773 2.7639 7.1592 1 H MR 7 4.5226 1.98 3.5008 3.49 3.4843 3.4816 3.4679 3.4652 2.0728 2.74 2.7118 2.6932 2.6745 2.0000 1.6543 1.6390 1.6215 1.34 1.5869 1.3628 1.3459 1.2785 1.2571 1.2538 1.2379 1.2346 1.2193 1.21 0.9004 0.8867 0.88 0.8686 2.26 13.8 3.50 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 13C routine : 32 scans 142.6159 135.8384 128.8467 128.3497 127.8356 125.6336 70.8651 70.5909 31.89 29.7888 29.4118 29.24 26.2244 25.1876 22.6257 15.1370 14.03 13 C MR 7 150 1 1 1 1 0 90 70 50 16
1H routine : 8 scans 7.8778 7.8745 7.82 7.8564 7.7074 7.6948 7.6898 7.6811 7.6789 7.6706 7.6663 7.6635 7.6509 7.6487 7.6312 7.6164 7.6137 7.69 7.5967 7.5939 7.5797 3.2244 3.57 3.1871 3.1685 1.5067 1.4902 1.48 1.4716 1.4694 1 H MR 8 1.0000 0.9645 0.97 0.9841 4.8874 2.0445 3.0556 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 13C routine : 32 scans 138.1518 132.0341 131.2372 1.32 129.5578 128.0070 126.4989 126.4218 126.0363 125.7964 124.8624 124.2284 123.1573 122.3947 26.0701 14.3916 13 C MR 8 1 1 1 1 0 90 70 50 17
18 2.0566 9.65 1.0000 2.0481 3.1490 Integral 7.2533 7.2462 7.2429 7.23 7.2292 7.2259 7.2227 7.2166 7.2133 7.21 7.1964 7.1931 6.1175 6.0983 6.0797 2.1846 2.1819 2.16 2.1627 2.1468 2.1441 2.1370 2.1282 2.1254 2.96 2.68 1.06 1.0778 1.0707 1.0619 1.0592 1.0433 1.00 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 JM193-pub 1 H MR 142.8215 1.9965 1.2682 131.6913 129.89 128.0926 128.0327 127.15 126.81 126.73 23.1826 14.4944 50 70 90 0 1 1 1 1 JM193-pub 13 C MR 9 9