TY - JOUR A1 - Silla, Josué M. A1 - Cormanich, Rodrigo A. A1 - Rittner, Roberto A1 - Freitas, Matheus P. T1 - Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids JF - Beilstein Journal of Organic Chemistry PY - 2013/// VL - 9 SP - 1127 EP - 1134 SN - 1860-5397 DO - 10.3762/bjoc.9.125 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.9.125 KW - conformational analysis KW - hydrogen bond KW - interactions with boron KW - monosubstituted phenylboranes KW - phenylboronic acids N2 - A 1TSJF,H(O) coupling pathway, dictated by a hydrogen bond, in some 2-fluorobenzoic acids has been observed, while such an interaction does not occur in 2-fluorophenol. Thus, this work reports the conformational analysis of 2-fluorophenylboronic acid (1), in order to evaluate a possible intramolecular OH∙∙∙F hydrogen bond in comparison to an nF→pB interaction, which mimics the quantum nF→σ*OH hydrogen bond that would be expected in 2-fluorophenol. 2-Fluorophenylborane (3), which does not experience hydrogen bonding, was used to verify whether nF→pB interaction governs the conformational equilibrium in 1 due to a predominant OH∙∙∙F hydrogen bond or to other effects. A series of 2-X-phenylboranes (X = Cl, Br, NH2, PH2, OH and SH) were further computationally analyzed to search for electron donors to boron, capable of influencing the conformational equilibrium. Overall, the intramolecular OH∙∙∙F hydrogen bond in 1 is quite stabilizing and dictates the 1hJF,H(O) coupling constant. Moreover, electron donation to the empty p orbital of boron (for noncoplanar BH2 moiety relative to the phenyl ring) is also significantly stabilizing for the NH2 and PH2 derivatives, but not enough to make the corresponding conformers appreciably populated, because of steric effects and the loss of πCC→pB resonance. Thus, the results found earlier for 2-fluorophenol about the lack of intramolecular hydrogen bonding are now corroborated. ER - TY - JOUR AU - Yang, W. AU - Gao, X. AU - Wang, B. JF - Med. Res. Rev. PY - 2003/// VL - 23 SP - 346 EP - 368 DO - 10.1002/med.10043 ER - TY - JOUR AU - Chen, X. AU - Liang, G. AU - Whitmire, D. AU - Bowen, J. P. JF - J. Phys. Org. Chem. PY - 1998/// VL - 11 SP - 378 EP - 386 DO - 10.1002/(SICI)1099-1395(199806)11:6<378::AID-POC987>3.0.CO;2-5 ER - TY - JOUR AU - Schinazi, R. F. AU - Laster, B. H. AU - Fairchild, R. G. AU - Prusoff, W. H. JF - Antimicrob. Agents PY - 1985/// VL - 24 SP - 260 EP - 265 ER - TY - JOUR AU - Schinazi, R. F. AU - Prusoff, W. H. JF - J. Org. Chem. PY - 1985/// VL - 50 SP - 841 EP - 847 DO - 10.1021/jo00206a024 ER - TY - JOUR AU - Lauer, M. AU - Wulff, G. JF - J. Organomet. Chem. PY - 1983/// VL - 256 SP - 1 EP - 9 DO - 10.1016/S0022-328X(00)99290-8 ER - TY - JOUR AU - Wulff, G. JF - Pure Appl. Chem. PY - 1982/// VL - 54 SP - 2093 EP - 2102 DO - 10.1351/pac198254112093 ER - TY - JOUR AU - Bhat, K. L. AU - Howard, N. J. AU - Rostami, H. AU - Lai, J. H. AU - Bock, C. W. JF - THEOCHEM PY - 2005/// VL - 723 SP - 147 EP - 157 DO - 10.1016/j.theochem.2005.01.033 ER - TY - JOUR AU - Niedenzu, K. JF - J. Organomet. Chem. PY - 1976/// VL - 119 SP - 57 EP - 130 DO - 10.1016/S0022-328X(00)82867-3 ER - TY - JOUR AU - Alkorta, I. AU - Elguero, J. AU - Denisov, G. S. JF - Magn. Reson. Chem. PY - 2008/// VL - 46 SP - 599 EP - 624 DO - 10.1002/mrc.2209 ER - TY - JOUR AU - Cormanich, R. A. AU - Moreira, M. A. AU - Freitas, M. P. AU - Ramalho, T. C. AU - Anconi, C. P. A. AU - Rittner, R. AU - Contreras, R. H. AU - Tormena, C. F. JF - Magn. Reson. Chem. PY - 2011/// VL - 49 SP - 763 EP - 767 DO - 10.1002/mrc.2838 ER - TY - JOUR AU - Moreira, M. A. AU - Cormanich, R. A. AU - de Rezende, F. M. P. AU - Silla, J. M. AU - Tormena, C. F. AU - Rittner, R. AU - Ramalho, T. C. AU - Freitas, M. P. JF - J. Mol. Struct. PY - 2012/// VL - 1009 SP - 11 EP - 15 DO - 10.1016/j.molstruc.2011.05.012 ER - TY - JOUR AU - Silvi, B. AU - Kryachko, E. S. AU - Tishchenko, O. AU - Fuster, F. AU - Nguyen, M. T. JF - Mol. Phys. PY - 2002/// VL - 100 SP - 1659 EP - 1675 DO - 10.1080/00268970210123315 ER - TY - JOUR AU - Dunitz, J. D. AU - Taylor, R. JF - Chem.–Eur. J. PY - 1997/// VL - 3 SP - 89 EP - 98 DO - 10.1002/chem.19970030115 ER - TY - JOUR AU - Takemura, H. AU - Ueda, R. AU - Iwanaga, T. JF - J. Fluorine Chem. PY - 2009/// VL - 130 SP - 684 EP - 688 DO - 10.1016/j.jfluchem.2009.05.004 ER - TY - JOUR AU - Fonseca, T. A. O. AU - Freitas, M. P. AU - Cormanich, R. A. AU - Ramalho, T. C. AU - Tormena, C. F. AU - Rittner, R. JF - Beilstein J. Org. Chem. PY - 2012/// VL - 8 SP - 112 EP - 117 DO - 10.3762/bjoc.8.12 ER - TY - JOUR AU - de Rezende, F. M. P. AU - Moreira, M. A. AU - Cormanich, R. A. AU - Freitas, M. P. JF - Beilstein J. Org. Chem. PY - 2012/// VL - 8 SP - 1227 EP - 1232 DO - 10.3762/bjoc.8.137 ER - TY - JOUR AU - Silla, J. M. AU - Cormanich, R. A. AU - Rittner, R. AU - Freitas, M. P. JF - J. Phys. Chem. A PY - 2013/// VL - 117 SP - 1659 EP - 1664 DO - 10.1021/jp311791g ER - TY - JOUR AU - Cormanich, R. A. AU - Freitas, M. P. AU - Tormena, C. F. AU - Rittner, R. JF - RSC Adv. PY - 2012/// VL - 2 SP - 4169 EP - 4174 DO - 10.1039/c2ra00039c ER - TY - BOOK AU - Weinhold, F. AU - Landis, C. R. T1 - Discovering Chemistry with Natural Bond Orbitals PY - 2012/// PB - Wiley CY - Hoboken, New Jersey, USA ER - TY - BOOK AU - Bader, R. F. W. T1 - Atoms in Molecules: A Quantum Theory PY - 1990/// PB - Oxford CY - Clarendon ER - TY - JOUR AU - Bader, R. F. W. JF - Chem. Rev. PY - 1991/// VL - 91 SP - 893 EP - 928 DO - 10.1021/cr00005a013 ER - TY - JOUR AU - Bader, R. F. W. JF - J. Phys. Chem. A PY - 1998/// VL - 102 SP - 7314 EP - 7323 DO - 10.1021/jp981794v ER - TY - JOUR AU - Koch, U. AU - Popelier, P. L. A. JF - J. Phys. Chem. PY - 1995/// VL - 99 SP - 9747 EP - 9754 DO - 10.1021/j100024a016 ER - TY - JOUR AU - Erdogdu, Y. AU - Güllüoğlu, M. T. AU - Kurt, M. JF - J. Raman Spectrosc. PY - 2009/// VL - 40 SP - 1615 EP - 1623 DO - 10.1002/jrs.2309 ER - TY - COMP T1 - Spartan Pro, 1.0.5 PY - 2000/// PB - Wavefunction, Inc. CY - Irvine ER - TY - COMP T1 - Gaussian, 09, Revision A.02 PY - 2009/// PB - Gaussian, Inc. CY - Wallingford, CT, USA ER - TY - JOUR AU - Cancès, E. AU - Mennucci, B. JF - J. Math. Chem. PY - 1998/// VL - 23 SP - 309 EP - 326 DO - 10.1023/A:1019133611148 ER - TY - COMP T1 - NBO, 5.0 PY - 2001/// PB - Theoretical Chemistry Institute, University of Wisconsin CY - Madison ER - TY - COMP T1 - AIMAll, 13.02.26 PY - 2013/// UR - http://aim.tkgristmill.com PB - TK Gristmill Software CY - Overland Park KS, USA ER -