%0 Generic %A Medina, Jose M. %A Kang, Taeho %A Erbay, Tuğçe G. %A Shao, Huiling %A Gallego, Gary M. %A Yang, Shouliang %A Tran-Dubé, Michelle %A Richardson, Paul F. %A Derosa, Joseph %A Helsel, Ryan T. %A Patman, Ryan L. %A Wang, Fen %A Ashcroft, Christopher P. %A Braganza, John F. %A McAlpine, Indrawan %A Liu, Peng %A Engle, Keary M. %D 2019 %T Cu-Catalyzed Hydroboration of Benzylidenecyclopropanes: Reaction Optimization, (Hetero)Aryl Scope, and Origins of Pathway Selectivity %U https://acs.figshare.com/articles/dataset/Cu-Catalyzed_Hydroboration_of_Benzylidenecyclopropanes_Reaction_Optimization_Hetero_Aryl_Scope_and_Origins_of_Pathway_Selectivity/10274804 %R 10.1021/acscatal.9b03557.s003 %2 https://acs.figshare.com/ndownloader/files/18601607 %K phosphine ligands grant access %K reaction conditions %K copper-catalyzed hydroboration %K Hetero %K activation energies %K Scope %K benzylidenecyclopropane %K rigidity %K cyclopropane opening %K Pathway Selectivity %K cyclopropylboronic ester products %K steric environment %K versatility %K intermediate %K benzylcopper %K β- carbon elimination %K benzaldehyde %K Cu-Catalyzed Hydroboration %K insight %K Origins %K protodecupration %K derivatization reactions %K bis-phosphine ligands influence %K heterocycle %K Computational studies %K variety %K method %K Reaction Optimization %K drug development %K Benzylidenecyclopropane %X The copper-catalyzed hydroboration of benzylidenecyclopropanes, conveniently accessed in one step from readily available benzaldehydes, is reported. Under otherwise identical reaction conditions, two distinct phosphine ligands grant access to different products by either suppressing or promoting the cyclopropane opening via β-carbon elimination. Computational studies provide insight into how the rigidity and steric environment of these different bis-phosphine ligands influence the relative activation energies of β-carbon elimination versus protodecupration from the key benzylcopper intermediate. The method tolerates a wide variety of heterocycles prevalent in clinical and preclinical drug development, giving access to valuable synthetic intermediates. The versatility of the tertiary cyclopropylboronic ester products is demonstrated through several derivatization reactions. %I ACS Publications