Mechanism of Absolute Asymmetric Synthesis and Solid-State CD Spectroscopy of BPOB

Abstract

以苯乙酮与间苯二甲酸甲酯为原料经由Claisen缩合制备了1,3-二(3-苯基-3-氧代丙烯醇)苯(BPOB).用元素分析、MS、1H NMR、UV吸收光谱、X射线单晶衍射和固体CD光谱等对其进行了表征.晶体结构数据显示,BPOB属于Sohncke空间群P212121,UV和1H NMR谱表明,BPOB在溶液中主要以烯醇式存在,固体CD光谱和重结晶实验证明,BPOB手性晶体的形成是结晶诱导的绝对不对称合成.1,3-bis(3-phenyl-3-oxopropanoyl)benzene (BPOB) was prepared by Claisen condensation of aceto-phenone and dimethyl isophthalate and characterized by elemental analysis, MS, 1H NMR, UV absorption spectrum, solid-state circular dichroism (CD) spectra, and X-ray single-crystal diffraction. The X-ray crystallographic data indicated that BPOB crystallized in a Sohncke group P212121, UV and 1H NMR showed that the enol tautomer was the most dominant form in solution, and the solid-state CD spectra and repeated recrytallization revealed that the formation of chiral BPOB crystals could be regarded as crystallization-induced asymmetric synthesis.国家自然科学基金(20773098);; 福建省自然科学基金(2005YZ1020);; 厦门大学科技创新工程基金(系列2,XDKJCX20061027)资

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