Abbey Eric R, Lamm Ashley N, Baggett Andrew W, Zakharov Lev N, Liu Shih-Yuan
Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, USA.
J Am Chem Soc. 2013 Aug 28;135(34):12908-13. doi: 10.1021/ja4073436. Epub 2013 Aug 19.
The protecting group-free synthesis of a versatile 1,2-azaborine synthon 5 is described. Previously inaccessible 1,2-azaborine derivatives, including the BN isostere of phenyl phenylacetate and BN1 triphenylmethane were prepared from 5 and characterized. The structural investigation of BN phenyl phenylacetate revealed the presence of a unique NH-carbonyl hydrogen bond that is not present in the corresponding carbonaceous analogue. The methyne CH in BN triphenylmethane was found to be less acidic than the corresponding proton in triphenylmethane. The gram-quantity synthesis of the parent 1,2-azaborine 4 was demonstrated, which enabled the characterization of its boiling point, density, refractive index, and its polarity on the ET(30) scale.
本文描述了一种通用的1,2-氮杂硼环合成子5的无保护基合成方法。从5制备了以前难以获得的1,2-氮杂硼环衍生物，包括苯乙酸苯酯的BN等电子体和BN1三苯甲烷，并对其进行了表征。对BN苯乙酸苯酯的结构研究表明，存在一种独特的NH-羰基氢键，而相应的碳类似物中不存在这种氢键。发现BN三苯甲烷中的次甲基CH的酸性低于三苯甲烷中相应的质子。实现了母体1,2-氮杂硼环4的克级合成，从而能够表征其沸点、密度、折射率及其在ET(30)标度上的极性。
