TITLE

Fixed stereochemical control in the synthesis of new mono- and disubstituted 2-phenyl-6-aza-1,3-dioxa-2-borabenzocyclononenes

AUTHOR(S)
Beltrán, Hiram I; Alas, S Jesús; Santillan, Rosa; Farfán, Norberto
PUB. DATE
July 2002
SOURCE
Canadian Journal of Chemistry;Jul2002, Vol. 80 Issue 7, p801
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Five new boronates of the type 2-phenyl-6-aza-1,3-dioxa-2-borabenzocyclononenes (6a–e) were prepared from substituted 2-[(2-hydroxyethylamino)methyl]phenols (4a–e) and phenylboronic acid (5) in benzene-EtOH (4:1) mixtures. Tridentate ligands 4a–e and boronates 6a–e were characterized by [sup 1] H, [sup 13] C, [sup 15] N, and 2D-NMR (HETCOR, NOESY, and COLOC) experiments, FT-IR, mass spectra, and elemental analysis, as well as [sup 11] B NMR for the boron derivatives. Suitable monocrystals of 2-[(2-hydroxyethylamino)methyl]phenol hydrochloride (4a), cis-2-phenyl-6-aza-1,3-dioxa-2-borabenzocyclononene (6a), (2S,5R,6S)-2,5-diphenyl-6-aza-1,3-dioxa-2-borabenzocyclononene (6b), and (2S,4R,5R,6S)-2,4-diphenyl-5-methyl-6-aza-1,3-dioxa-2-borabenzocyclononene (6e) were obtained and their structures are discussed. The X-ray structures of 6a, 6b, and 6e, as well as the NMR data established that the configurations at the nitrogen and boron atoms are both "S" and the transannular fusion is cis. A semi-empirical (SAM1) study was used to calculate the energy for all possible stereoisomers, showing that the stabilization increases as the THC (tetrahedral character of the boron atom) increases and also as the NB bond distance decreases, in agreement with the experimental results and previous work related to amino acid boronates.Key words: boron compounds, X-ray structures, NMR, boronates, synthesis.On a préparé cinq nouveaux boronates du type 2-phényl-6-aza-1,3-dioxa-2-borabenzocyclononènes (6a–e) en faisant réagit des 2-[(2-hydroxyéthylamino)méthyl]phénols substitués (4a–e) avec de l'acide phénylboronique (5) dans des mélanges 4:1 de benzène-éthanol. Les ligands tridentates (4a–e) et les boronates (6a–e) ont été caractérisés par les analyses élémentaires, par infrarouge à transformée de Fourier, par des expériences de RMN du [sup 1] H, du [sup 13] C, du [sup 15] N et par RMN-2D (HETCOR, NOESY et COLOC) ainsi que par RMN du [sup 11] B pour les dérivés du bore. On a obtenu des monocristaux appropriés du chlorhydrate du 2-[(2-hydroxyéthylamino)méthyl]phénol (4a), du cis-2-phényl-6-aza-1,3-dioxa-2-borabenzocyclononène (6a), du (2S,5R,6S)-2,5-diphényl-6-aza-1,3-dioxa-2-borabenzocyclononène (6b) et du (2S,4R,5R,6S)-2,4-diphényl-5-méthyl-6-aza-1,3-dioxo-2-borabenzo-cyclononène (6e) et on discute de leurs structures. Les structures des composés 6a, 6b et6e déterminées par diffraction des rayons-X ainsi que les données de la RMN ont permis d'établir que les configurations au niveau des atomes d'azote et du bore sont toutes les deux S et que la fusion transannulaire est cis. On a fait appel à des calculs semi-empiriques (SAM1) pour calculer l'énergie des tous les stéréoisomères possibles; ils montrent que la stabilisation augmente avec une augmentation du caractère tétraédrique de l'atome de bore ainsi qu'avec une diminution de la longueur de la distance NB, en accord avec les données expérimentales obtenues ici et avec celles obtenues dans un travail antérieur sur des boronates apparentés d'acides aminés.Mots clés : composés du bore, structures par diffraction des rayons X, RMN, boronates, synthèse.[Traduit par la Rédaction]
ACCESSION #
10577121

 

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