Dalian Institute of Chemical Physics, Chinese Academy of Sciences (CAS), 457 Zhongshan Road, Dalian, Liaoning, 116023, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2016 Jan 18;55(3):862-75. doi: 10.1002/anie.201507521. Epub 2015 Dec 7.
Transition-metal-catalyzed C-alkylation of ketones and secondary alcohols, with alcohols, avoids use of organometallic or environmentally unfriendly alkylating agents by means of borrowing hydrogen (BH) or hydrogen autotransfer (HA) activation of the alcohol substrates. Water is formed as the only by-product, thus making the BH process atom-economical and environmentally benign. Diverse homogeneous and heterogeneous transition-metal catalysts, ketones, and alcohols can be used for this transformation, thus rendering the BH process promising for replacing those procedures that use traditional alkylating agents. This Minireview summarizes the advances during the last five years in transition-metal-catalyzed BH α-alkylation of ketones, and β-alkylation of secondary alcohols with alcohols. A discussion on the application of the BH strategy for C-C bond formation is included.
过渡金属催化的酮和仲醇的 C-烷基化反应，使用醇作为烷基供体，通过醇底物的 borrowing hydrogen (BH) 或 hydrogen autotransfer (HA) 活化，避免了使用有机金属试剂或对环境不友好的烷基化试剂。反应的唯一副产物是水，因此 BH 过程具有原子经济性和环境友好性。多种均相和多相过渡金属催化剂、酮和醇都可用于这种转化，因此 BH 过程有望替代使用传统烷基化试剂的那些方法。本文综述了过去五年中过渡金属催化的酮的 BH α-烷基化和仲醇的 BH β-烷基化反应的最新进展。还讨论了 BH 策略在 C-C 键形成中的应用。
