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Type: Artigo de periódico
Title: Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids
Author: Silla, JM
Cormanich, RA
Rittner, R
Freitas, MP
Abstract: A (1TS)J(F), 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 center dot center dot center dot F hydrogen bond in comparison to an n(F)-> p(B) interaction, which mimics the quantum n(F)->sigma* (OH) hydrogen bond that would be expected in 2-fluorophenol. 2-Fluorophenylborane (3), which does not experience hydrogen bonding, was used to verify whether n(F)-> p(B) interaction governs the conformational equilibrium in 1 due to a predominant OH center dot center dot center dot 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 center dot center dot center dot F hydrogen bond in 1 is quite stabilizing and dictates the (1h)J(F),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 pi(CC)-> p(B) resonance. Thus, the results found earlier for 2-fluorophenol about the lack of intramolecular hydrogen bonding are now corroborated.
Subject: conformational analysis
hydrogen bond
interactions with boron
monosubstituted phenylboranes
phenylboronic acids
Country: Alemanha
Editor: Beilstein-institut
Citation: Beilstein Journal Of Organic Chemistry. Beilstein-institut, v. 9, n. 1127, n. 1134, 2013.
Rights: aberto
Identifier DOI: 10.3762/bjoc.9.125
Date Issue: 2013
Appears in Collections:Unicamp - Artigos e Outros Documentos

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