Synlett, Table of Contents Synlett 2023; 34(18): 2193-2196DOI: 10.1055/a-2158-9726 cluster Modern Boron Chemistry: 60 Years of the Matteson Reaction Addition of a Phosphinoboronate Ester to Borole and Borafluorene Authors Author Affiliations Manjur O. Akram a Baylor University, Department of Chemistry and Biochemistry, One Bear Place #97348, Waco, TX 76798, USA Christopher M. Vogels b Mount Allison University, Department of Chemistry and Biochemistry, Sackville, NB E4L 1E4, Canada Webster L. Santos c Virginia Tech, Department of Chemistry, Blacksburg, VA 24060, USA Stephen A. Westcott b Mount Allison University, Department of Chemistry and Biochemistry, Sackville, NB E4L 1E4, Canada Caleb D. Martin∗ a Baylor University, Department of Chemistry and Biochemistry, One Bear Place #97348, Waco, TX 76798, USA Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Dedicated to Professor Donald Matteson and in memory of the late Professor Stephen Westcott in recognition of their contributions to organoboron chemistry. Abstract The additions of the phosphinoboronate ester Ph2PBpin to an antiaromatic borole and a borafluorene is reported. The Lewis acid/base adducts are obtained in excellent yields and represent the first P-donor adducts of Ph2PBpin. Key words Key wordspinacol diphenylphosphinoboronate - boroles - borafluorenes - antiaromaticity - Lewis acid Full Text References References and Notes 1 Paine RT, Noeth H. Chem. Rev. 1995; 95: 343 2 Gaumont AC, Carboni B. In Science of Synthesis, Vol. 6, Chap. 6.1.16. Kaufmann DE. Thieme; Stuttgart: 2005: 485 3 Bailey JA, Pringle PG. Coord. Chem. Rev. 2015; 297: 77 4 Power PP. 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The solvent was then removed in vacuo and the residue was washed with cold pentane (2 × 5 mL) and dried in vacuo. 1 Pale-yellow powder; yield: 319 mg (84%,); mp 216–219 °C. FTIR (neat): (ranked intensity) 1593 (11), 1483 (8), 1438 (9), 1340 (12), 1245 (5), 1129 (2), 1028 (13), 958 (14), 841 (4), 792 (6), 741 (7), 693 (1), 542 (10), 505 (3), 460 (15) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 6.9 Hz, 2 H), 7.43–7.38 (m, 6 H), 7.33–7.27 (m, 3 H), 7.24–7.22 (m, 4 H), 6.90–6.85 (m, 6 H), 6.82–6.78 (m, 6 H), 6.75–6.74 (m, 4 H), 6.59 (d, J = 7.0 Hz, 4 H), 1.01 (s, 12 H). 13C{1H} NMR (101 MHz, CDCl3): δ = 154.5, 153.5, 153.4, 143.5, 140.5, 135.4 (d, J = 8.5 Hz), 135.2 (d, J = 12.8 Hz), 130.4 (d, J = 2.6 Hz), 130.3 (d, J = 2.6 Hz), 129.7, 127.7, 127.6, 127.3, 126.9, 126.8, 125.9, 125.4, 125.2, 125.0, 124.3, 86.5, 86.5, 24.6. 31P NMR (162 MHz, CDCl3): δ = –34.2. 11B NMR (128 MHz, CDCl3): δ = 30.8, –5.2. HRMS (ESI): the adduct peak was not observed in the HRMS. Anal. Calcd for C52H47B2O2P: C, 82.56; H, 6.26. Found: C 82.36, H 6.32. Single crystals of 1 for X-ray diffraction studies were grown from a CH2Cl2 solution by vapor diffusion into toluene. 2 White powder; yield: 256 mg (93%,); mp 189–191 °C. FTIR (neat): (ranked intensity) 1483 (14), 1435 (8), 1373 (12), 1348 (10), 1244 (6), 1128 (4), 1103 (13), 961 (11), 836 (5), 734 (1), 696 (3), 647 (9), 616 (15), 506 (2), 427 (7) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 7.7 Hz, 4 H), 7.55 (d, J = 7.2 Hz, 2 H), 7.41 (td, J = 7.2, 1.6 Hz, 2 H), 7.30–7.15 (m, 13 H), 7.12 (t, J = 7.2 Hz, 2 H), 1.15 (s, 12 H). 13C{1H} NMR (101 MHz, CDCl3): δ = 153.0, 149.4, 134.6 (d, J = 7.5 Hz), 134.2, 132.9, 130.5 (d, J = 2.6 Hz), 128.3 (d, J = 9.5 Hz), 127.5, 126.5, 126.2, 125.8, 125.6, 125.6, 86.6, 86.6, 24.7. 31P NMR (162 MHz, CDCl3): δ = –35.2. 11B NMR (128 MHz, CDCl3): δ = 30.9, –9.3. HRMS (ESI): m/z [M + H] calcd for C36H36B2O2P: 553.2634; found: 553.2610. Anal. Calcd for C36H35B2O2P: C, 78.29; H, 6.39. Found: C, 78.54; H, 6.55. Single crystals for X-ray diffraction studies were grown from a CH2Cl2 solution of 2 by vapor diffusion into toluene. Supplementary Material Supplementary Material Supporting Information (PDF)
