Liu, XiaocuiMing, WenboLuo, XiaolingFriedrich, AlexandraMaier, JanRadius, UdoSantos, Webster L.Marder, Todd B.2021-01-052021-01-052020-041434-193Xhttp://hdl.handle.net/10919/101740The NaOtBu-catalyzed mixed 1,1-diboration of terminal alkynes using the unsymmetrical diboron reagent BpinBdan (pin = pinacolato; dan = 1,8-diaminonaphthalene) proceeds in a regio- and stereoselective fashion affording moderate to high yields of 1,1-diborylalkenes bearing orthogonal boron protecting groups. It is applicable to gram-scale synthesis without loss of yield or selectivity. The mixed 1,1-diborylalkene products can be utilized in Suzuki-Miyaura cross-coupling reactions which take place selectivly at the C-B site. DFT calculations suggest the NaOtBu-catalyzed mixed 1,1-diboration of alkynes occurs through deprotonation of the terminal alkyne, stepwise addition of BpinBdan to the terminal carbon followed by protonation with tBuOH. Experimentally observed selective formation of (Z)-diborylalkenes is supported by our theoretical studies.application/pdfenCreative Commons Attribution 4.0 InternationalBoronate estersBorylationCross-couplingSynthesis designStructure elucidationArticle - Refereedhttps://doi.org/10.1002/ejoc.202000128202013323627801099-0690