Borylative Difunctionalization of Unsaturated Hydrocarbons Using Borylcopper Species

Abstract This account summarizes the Cu-catalyzed borylative functionalizations of unsaturated hydrocarbons that we have developed over the past decade. First, we focus on the regioselective hydroboration of unsymmetrical internal alkynes and 1,2-dienes. Secondly, a borylative allyl–allyl coupling using 1,2-dienes, B2pin2, and an allyl phosphate is presented. Thirdly, we introduce the boroacylation and boroformylation of 1,2-dienes by using an acid anhydride or formate, respectively, as the electrophile. Lastly, we describe the synthesis of 2-boryl-1,3-butadienes and cyclic allylborates. These reactions offer a versatile method for synthesizing a broad range of useful compounds and also provide a detailed understanding of the reaction mechanism, which could lead to the development of catalysts that are both more efficient and more selective. 1 Introduction 2 Hydroboration of Alkynes 3 Hydroboration of 1,2-Dienes and 1,3-Dienes 4 Synthesis of 2-Boryl-1,3-butadienes 5 Boroallylation of 1,2-Dienes 6 Boroacylation of 1,2-Dienes 7 Boroformylation of 1,2-Dienes and 1,3-Dienes 8 Synthesis of Cyclic Allylborates 9 Conclusion and Outlook