Jakubowski Rafał, Pietrzak Anna, Friedli Andrienne C, Kaszyński Piotr
Centre of Molecular and Macromolecular Studies, Polish Academy of, Sciences, Sienkiewicza 112, 90-363, Łódź, Poland.
Department of Chemistry, Middle Tennessee State University, Murfreesboro, TN, 37132, USA.
Chemistry. 2020 Dec 23;26(72):17481-17494. doi: 10.1002/chem.202002997. Epub 2020 Nov 19.
C(1)-vinylation of [closo-1-CB H ] (A) and [closo-1-CB H ] (B) with 4-benzyloxystyryl iodide followed by hydrogenation of the double bond and reductive deprotection of the phenol functionality led to C(1)-(4-hydroxyphenethyl) derivatives. The phenol functionality was protected as the acetate. The esters were then treated with PhI(OAc) and the resulting isomers were separated kinetically (for derivatives of anion A) or by chromatography (for derivatives of anion B) giving the difunctionalized building blocks in overall yields of 9 % and 50 %, respectively. A similar series of reactions was performed starting with anions A and B and 4-methoxystyryl bromide and iodide. Significant differences in the reactivity of derivatives of the two carborane anions were rationalized with DFT computational results. Application of the difunctionalized carboranes as building blocks was demonstrated through preparation of two ionic liquid crystals. The extensive synthetic work is accompanied by single crystal XRD analysis of six derivatives.
用4-苄氧基苯乙烯基碘对[闭式-1-CB₉H₁₀]（A）和[闭式-1-CB₁₁H₁₂]（B）进行C(1)-乙烯基化，随后对双键进行氢化以及对酚官能团进行还原脱保护，得到C(1)-(4-羟基苯乙基)衍生物。酚官能团被保护为乙酸酯。然后将酯用PhI(OAc)₂处理，所得异构体通过动力学方法（对于阴离子A的衍生物）或通过色谱法（对于阴离子B的衍生物）进行分离，分别以9%和50%的总收率得到双官能化的结构单元。从阴离子A和B以及4-甲氧基苯乙烯基溴和碘开始进行了一系列类似的反应。通过密度泛函理论（DFT）计算结果解释了两种碳硼烷阴离子衍生物反应性的显著差异。通过制备两种离子液晶证明了双官能化碳硼烷作为结构单元的应用。大量的合成工作伴随着六种衍生物的单晶X射线衍射（XRD）分析。
