化学合成。
化学合成
合成路线 1(1. 合成:87630-35-1)
产率:98%
合成条件:Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.50 h; Inert atmosphere Stage #2: at -78℃; for 5 h; Inert atmosphere
实验步骤:在-78℃下,将n-BuLi(1.57M,在正己烷中,17.3mL,27.1mmol)滴加到吡咯(19,1.52g,22.6mmol)的THF(36mL)溶液中,并且整个混合物 在-78℃下搅拌30分钟。 向混合物中加入TIPSCl(5.3mL,24.9mmol),并将全部混合物在-78℃下搅拌5小时。星期六 NH4Cl aq。 在0℃下向混合物中加入,并用AcOEt萃取整个混合物。 在减压下从AcOEt萃取物中除去溶剂,得到粗产物,将其通过SiO 2柱(正己烷/ AcOEt = 10:1)纯化,得到1-三异丙基硅烷基-1H-吡咯(4.94g,98%),为 无色油。
参考文献:
- [1] Journal of Natural Products, 2004, vol. 67, # 11, p. 1929 - 1931 [2] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 13, p. 4358 - 4361 [3] Chemistry - A European Journal, 2016, vol. 22, # 16, p. 5504 - 5508 [4] Chemistry - An Asian Journal, 2016, vol. 11, # 7, p. 986 - 990 [5] Tetrahedron, 2008, vol. 64, # 49, p. 11180 - 11184 [6] Organic Letters, 2014, vol. 16, # 24, p. 6334 - 6337 [7] Tetrahedron, 2011, vol. 67, # 35, p. 6673 - 6678 [8] Synthesis, 2010, # 19, p. 3346 - 3352 [9] Organic Letters, 2014, vol. 16, # 19, p. 5212 - 5215 [10] Tetrahedron, 2005, vol. 61, # 32, p. 7661 - 7668 [11] Patent: WO2014/210159, 2014, A1. Location in patent: Page/Page column 89 [12] European Journal of Medicinal Chemistry, 2012, vol. 57, p. 391 - 397 [13] Organic Letters, 2017, vol. 19, # 7, p. 1500 - 1503 [14] Tetrahedron Letters, 1983, vol. 24, # 33, p. 3455 - 3456 [15] Organometallics, 2014, vol. 33, # 1, p. 145 - 157 [16] Patent: WO2013/90210, 2013, A1. Location in patent: Page/Page column 74-75 [17] Patent: WO2008/82725, 2008, A1. Location in patent: Page/Page column 97-98 [18] Journal of the Chemical Society, Faraday Transactions, 1991, vol. 87, # 11, p. 1765 - 1770 [19] Molecular Crystals and Liquid Crystals (1969-1991), 1988, vol. 160, p. 79 - 88 [20] Journal of Organic Chemistry, 1990, vol. 55, # 26, p. 6317 - 6328 [21] Chemische Berichte, 1989, vol. 122, p. 169 - 174 [22] Bioorganic and Medicinal Chemistry Letters, 1999, vol. 9, # 14, p. 1969 - 1972 [23] Angewandte Chemie - International Edition, 2006, vol. 45, # 21, p. 3484 - 3488 [24] Patent: US5817652, 1998, A [25] Journal of the American Chemical Society, 2009, vol. 131, # 33, p. 11640 - 11641 [26] Patent: WO2011/130628, 2011, A1. Location in patent: Page/Page column 234 [27] Patent: US2013/102595, 2013, A1. Location in patent: Paragraph 0605; 0606 [28] Chemistry - A European Journal, 2015, vol. 21, # 3, p. 975 - 979 [29] Patent: JP2015/187145, 2015, A. Location in patent: Paragraph 0514