1,1′-Bi-2-naphthol (BINOL) has been extensively used as the chirality source in the fields of molecular recognition, asymmetric synthesis, and materials science. The direct electrophilic substitution at the aromatic rings of the optically active BINOL has been developed as one of the most convenient strategies to structurally modify BINOL for diverse applications. High regioselectivity has been achieved for the reaction of BINOL with electrophiles. Depending upon the reaction conditions and substitution patterns, various functional groups can be introduced to the specific positions, such as the 6-, 5-, 4-, and 3-positions, of BINOL. Ortho-lithiation at the 3-position directed by the functional groups at the 2-position of BINOL have been extensively used to prepare the 3- and 3,3′-substituted BINOLs. The use of transition metal-catalyzed C–H activation has also been explored to functionalize BINOL at the 3-, 4-, 5-, 6-, and 7-positions. These regioselective substitutions of BINOL have allowed the construction of tremendous amount of BINOL derivatives with fascinating structures and properties as reviewed in this article. Examples for the applications of the optically active BINOLs with varying substitutions in asymmetric catalysis, molecular recognition, chiral sensing and materials are also provided.

中文翻译：

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联苯酚的区域选择性取代


1,1'-Bi-2-萘酚（BINOL）已广泛用作分子识别、不对称合成和材料科学领域的手性源。光学活性 BINOL 芳环上的直接亲电取代已被开发为针对多种应用进行结构修饰的最便捷策略之一。 BINOL 与亲电子试剂的反应已实现高区域选择性。根据反应条件和取代模式，可以将各种官能团引入BINOL的特定位置，例如6-、5-、4-和3-位。由BINOL 2-位官能团引导的3-位邻位锂化已被广泛用于制备3-和3,3'-取代BINOL。还探索了使用过渡金属催化的 C-H 活化来在 3-、4-、5-、6-和 7-位上官能化 BINOL。 BINOL 的这些区域选择性取代使得能够构建大量具有令人着迷的结构和性质的 BINOL 衍生物，如本文所述。还提供了具有不同取代基的光学活性联醇在不对称催化、分子识别、手性传感和材料中的应用示例。