Employing a single catalyst and substrate, the selective synthesis of all probable products upon varying the reaction conditions is uniquely challenging and exciting to explore. Utilizing methanol, cyclometalated (NNC)Ru(II) complex catalyzed selective transformation of a wide variety of ketones to the corresponding alcohols, β-methylated alcohols, and α-methylated ketones is disclosed. Notably, by changing the reaction parameters, the selective synthesis of all the probable products for the reactions of ketones with methanol was achieved. For these transformations, the role of different ancillary ligands (DMSO, CH₃CN and PPh₃) coordinated to the Ru(II) center was investigated. This protocol was successfully applied for the functionalization of a few pharmaceutically important molecules and to sterically hindered α, α′-disubstituted and α, α′, α′′-trisubstituted ketones. Several control experiments, kinetic studies, Hammett studies, and DFT calculations were carried out to understand this catalytic process.

中文翻译：

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(NNC)Ru(II) 配合物催化酮与甲醇的选择性功能化：了解辅助配体的作用

使用单一催化剂和底物，在改变反应条件下选择性合成所有可能的产物是独特的挑战和令人兴奋的探索。公开了利用甲醇、环金属化 (NNC) Ru(II) 配合物催化多种酮选择性转化为相应的醇、β-甲基化醇和 α-甲基化酮。值得注意的是，通过改变反应参数，实现了酮与甲醇反应的所有可能产物的选择性合成。对于这些转化，不同辅助配体（DMSO、CH ₃ CN 和 PPh ₃) 协调到 Ru(II) 中心进行了调查。该协议已成功应用于一些药学上重要分子的功能化和空间受阻的 α、α'-二取代和 α、α'、α''-三取代酮。进行了几个控制实验、动力学研究、Hammett 研究和 DFT 计算以了解该催化过程。