Modification and Unexpected Reactivity of 2-Borylbenzaldimines: Acylated and Silylated Derivatives as Well as Dimeric Compounds

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• 作者：Benedikt Neue ; Atsushi Wakamiya ; Roland Fr枚hlich ; Birgit Wibbeling ; Shigehiro Yamaguchi ; Ernst-Ulrich W眉rthwein
• 刊名：Journal of Organic Chemistry
• 出版年：2013
• 出版时间：December 6, 2013
• 年：2013
• 卷：78
• 期：23
• 页码：11747-11755
• 全文大小：462K
• 年卷期：v.78,no.23(December 6, 2013)
• ISSN：1520-6904

文摘

Various novel N-alkyl and N-benzyl 2-borylbenzaldimines 3 were prepared by condensation of 2-(dimesitylboryl)benzaldehyde (1) with amines. Further functionalization of compound 3e was possible by deprotonation and subsequent regioselective reaction with electrophiles to give compounds 4. Applying similar conditions to 3a led to the unexpected formation of hitherto unknown dimeric compounds (5 and 6). All structural types were fully characterized, including by X-ray diffraction (XRD). Furthermore, quantum chemical calculations on the SCS-MP2 and DFT levels gave insights into the reaction mechanisms and the stereoselectivity. The B/N bonding situation in these molecules was analyzed using Wiberg bond indices. Preliminary UV鈥搗is and fluorescence measurements indicate that the substitution reaction leading to compounds 4 can be utilized to tune the photophysical properties of these compounds.