Anes (five mL) and with water (5 mL). The aqueous layer was extracted
Anes (5 mL) and with water (5 mL). The aqueous layer was extracted 3 occasions with ethyl acetate (20 mL), plus the combined organic layers have been washed with brine (10 mL) and dried more than anhydrous Na2SO4. Solvent evaporation under reduced pressure ALK4 custom synthesis afforded compound eight as a brown oil (0.114 g, 0.241 mmol, 90 ), which was used directly in the subsequent step with no additional purification.dx.doi.org10.1021ic5008439 | Inorg. Chem. 2014, 53, 7518-ArticleEXPERIMENTAL SECTIONInorganic Chemistry(Note that as a way to receive the preferred compound in higher yields and no cost of side products, this Glycopeptide list reaction could not be carried out on far more than 0.150 g of 7.) 1H NMR (500 MHz, CDCl3, ): eight.79 (s, 1H), 7.82 (s, 1H), 7.40-7.32 (m, 3H), 7.24-7.20 (m, 2H), 6.87 (dd, J = 3.7, two.five Hz, 1H), 6.11 (dd, J = three.six, 2.7 Hz, 1H), six.01 (ddd, J = 3.six, two.7, 0.7 Hz, 1H), five.88 (ddd, J = three.7, 2.5, 0.9 Hz, 1H), 5.44 (s, 1H), 4.31 (q, J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H). 13C NMR (125 MHz, CDCl3, ): 161.71, 140.36, 137.84, 132.19, 128.65, 128.14, 127.34, 122.29, 116.01, 110.47, 109.97, 109.45, 97.54, 60.47, 44.21, 14.35. LRMS-ESI mz (relative intensity): 372.1 (33 ), 327.0 (100 ). (Z)-Ethyl 5-[(5-Bromo-2H-pyrrol-2-ylidene)(phenyl)methyl]1H-pyrrole-2-carboxylate (9). Compound 8 (0.114 g, 0.241 mmol) was dissolved in THF (six.7 mL) at 0 . two,3-Dichloro-5,6dicyano-1,4-benzoquinone (DDQ, 55 mg, 0.241 mmol) was dissolved in THF (1.four mL) and added dropwise. 1,5-Diazabicyclo(four.3.0)non-5ene (DBN, 30 L, 0.241 mmol) was added, and also the mixture was stirred at room temperature for 7 h. The reaction mixture was quenched by adding saturated aqueous NaHCO3 (ten mL), as well as the aqueous layer was extracted 3 instances with CH2Cl2 (10 mL). The combined organic layers had been washed with brine (ten mL) and dried more than anhydrous Na2SO4. Solvent evaporation below lowered pressure resulted in a brown oil. The crude solution was redissolved in 1:1 mixture of ethyl acetatehexanes and filtered by way of a silica pad in order to give compound 9 (75 mg, 0.202 mmol, 84 ) as a yellow oil. 1 H NMR (500 MHz, CDCl3, ): 7.55-7.45 (m, 5H), six.87 (dd, J = 4.1, two.4 Hz, 1H), 6.76 (d, J = four.5 Hz, 1H), six.52 (d, J = four.five Hz, 1H), six.33 (dd, J = 4.1, two.four Hz, 1H), 4.43 (q, J = 7.1 Hz, 2H), 1.46 (t, J = 7.1 Hz, 3H). 13C NMR (125 MHz, CDCl3, ): 160.54, 150.17, 149.00, 139.47, 137.00, 135.65, 134.87, 130.65, 129.57, 128.39, 127.99, 121.63, 115.54, 60.76, 14.26. LRMS-ESI mz (relative intensity): 370.9 (19 ), 325.1 (one hundred ). (Z)-Ethyl 5-[1H,5H(2,2-Bipyrrol]-5-ylidene(phenyl)methyl]1H-pyrrole-2-carboxylate (H2PD1). Compound 9 (75 mg, 0.202 mmol), LiCl (30 mg, 0.707 mmol), pyrrole-2-boronic acid (64 mg, 0.303 mmol), and Pd(PPh3)four (23 mg, ten mol , 20.two mol) have been dissolved in 1,2-dimethoxyethane (6.1 mL), along with the remedy was degassed for 2 h. A degassed solution of aqueous Na2CO3 (two M, 0.five mL) was added dropwise, and also the mixture was refluxed for 2 h. The reaction mixture was cooled to room temperature and diluted with water (ten mL). The aqueous layer was extracted 3 instances with CH2Cl2 (ten mL). The combined organic layers have been washed with brine (10 mL) and dried more than anhydrous Na2SO4. Solvent evaporation beneath reduced stress afforded the crude item, which was dissolved in CH2Cl2 (ten mL). The resolution was cooled to 0 , and trifluoroacetic acid (0.eight mL) was added dropwise. The mixture was stirred at space temperature for 8 h, cooled to 0 , and very carefully quenched with saturated aqueous NaHCO3 (20 mL). The mixture was extracted three times with CH.