Department of Applied Chemistry, Faculty of Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan.
Org Biomol Chem. 2011 Feb 21;9(4):1244-54. doi: 10.1039/c0ob00671h. Epub 2011 Jan 4.
We have newly synthesized the non-symmetrical "phthalimidoyl active ester" bi-dentate cross-linking reagents having an acid chloride, 2-benzothiazole, or 1-benzotriazole group (i.e., 9, 15, and 16) on the basis of the reactivity study of the "active ester" model compounds, 11-14, toward the various nucleophiles and examined their reaction selectivity towards the same nucleophiles. Then, we applied for the modification of cholesterol at the more reactive site of the bi-dentate linkers to give 3β-cholesteryl 4-(phthalimidoyloxycarbonyl)butyrate (39), and the subsequent reaction of 39 with several amines, such as benzylamine, 4-chlorobenzylamine, 2-phenylethylamine, L-phenylalanine methyl ester, or diphenylalanine benzyl ester as a protein model of the cholesterol antigen.
我们根据“活性酯”模型化合物 11-14 对各种亲核试剂的反应性研究，新合成了具有酰氯、2-苯并噻唑或 1-苯并三唑基团（即 9、15 和 16）的非对称“邻苯二甲酰亚胺活性酯”双齿交联试剂，并考察了它们对相同亲核试剂的反应选择性。然后，我们申请了在双齿接头的更活泼部位对胆固醇进行修饰，得到 3β-胆甾醇 4-（邻苯二甲酰亚氨基甲酰基）丁酸酯（39），随后 39 与几种胺，如苄胺、4-氯苄胺、2-苯乙胺、L-苯丙氨酸甲酯或二苯丙氨酸苄酯反应，作为胆固醇抗原的蛋白质模型。
