Synthesis and structure of potential Lewis acid–Lewis base bifunctional catalysts: 2- N, N-Diisopropylaminophenylboronate derivatives

• Published in: Journal of organometallic chemistry Vol. 690; no. 21; pp. 4784 - 4793
• Main Authors: Coghlan, Samuel W., Giles, Richard L., Howard, Judith A.K., Patrick, Leonard G.F., Probert, Michael R., Smith, Gillian E., Whiting, Andrew
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.11.2005; Elsevier
• Subjects: Arylamine; Arylboronate; Aryldifluoroborane; Boronic acid; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Metallation; NMR; Physical Sciences; Science & Technology; X-ray; Metallation; Aryldifluoroborane; NMR; Arylboronate; Boronic acid; X-ray; Arylamine; ORGANOBORON COMPOUNDS; DESIGN; BORON; boronic acid; arylboronate; CONVENIENT; ALDEHYDES; arylamine; aryldifluoroborane; ENANTIOSELECTIVE CYANOSILYLATION; ARYLBORONIC ACIDS; KETONES; metallation
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2005.07.108

Directed ortho-metallation is used to introduce a boron function into N, N-diisopropylbenzamide, resulting in the formation of both borinate and boronate derivatives. N, N-Diisopropylbenzamide ortho-boronate pinacol ester can be reduced with sodium borohydride–TMSCl resulting in N, N-diisopropylbenzylamino ortho-boronic acid; X-ray crystallography and 11B NMR shows that the hindered isopropylamino groups are sufficient to prevent B–N intramolecular coordination, which contrasts with N, N-dimethylbenzylamino ortho-boronic acid. Directed ortho-metallation is used to introduce a boron function into N, N-diisopropylbenzamide, resulting in the formation of both borinate and boronate derivatives. N, N-Diisopropylbenzamide ortho-boronate pinacol ester can be reduced with sodium borohydride–TMSCl resulting in N, N-diisopropylbenzylamino ortho-boronic acid. X-ray crystallography and 11B NMR of this compound clearly shows that the hindered isopropylamino groups are sufficient to prevent B–N intramolecular coordination, which contrasts with N, N-dimethylbenzylamino ortho-boronic acid.