575-41-7Relevant articles and documents
Type 1 ring-opening reactions of cyclopropanated 7-oxabenzonorbornadienes with organocuprates
Carlson, Emily,Haner, Jamie,McKee, Mary,Tam, William
, p. 1776 - 1779 (2014)
For the first time, nucleophilic ring-openings of cyclopropanated 7-oxabenzonorbornadiene were investigated, providing a novel approach to the preparation of 2-methyl-1,2-dihydronaphthalen-1-ols. Satisfactory yields (up to 95%) were achieved using n-Bu2CuCNLi2 as the nucleophile and Et2O as the solvent. The reaction demonstrated successful incorporation of primary, secondary, tertiary and aromatic nucleophiles, as well as ring-openings of substrates bearing arene substituents and C1-bridgehead substituents. A generalized mechanism for these transformations is also proposed.
Experiment and Theory of Bimetallic Pd-Catalyzed α-Arylation and Annulation for Naphthalene Synthesis
Ence, Chloe C.,Ess, Daniel H.,Gassaway, Kyle J.,Himes, Samuel R.,Larsen, Samantha G.,Martinez, Erin E.,Matu, Manase F.,Michaelis, David J.,Moreno, Mariur Rodriguez,Nazari, S. Hadi,Smith, Stacey J.,Valdivia-Berroeta, Gabriel A.
, p. 10394 - 10404 (2021/08/31)
We report the synthesis of bimetallic Pd(I) and Pd(II) complexes with bidentate 2-phosphinoimidazole ligands and their catalytic activity to generate substituted naphthalenes. This process involves the coupling of an aryl iodide and 2 equiv of a ketone via sequential ketone α-arylation and then annulation to generate disubstituted and tetrasubstituted naphthalenes in a regioselective manner. Excellent substrate scope for both aryl iodide and ketone partners is demonstrated, including that for heteroaryl iodides. Bimetallic Pd complexes are much more reactive than monometallic Pd catalysts in this transformation. Density functional theory calculations, isotope effect experiments, and substrate competition experiments were used to examine bimetallic mechanisms, reactivity, and selectivity.
Intermediacy of Ni-Ni Species in sp2 C-O Bond Cleavage of Aryl Esters: Relevance in Catalytic C-Si Bond Formation
Somerville, Rosie J.,Hale, Lillian V. A.,Gómez-Bengoa, Enrique,Burés, Jordi,Martin, Ruben
, p. 8771 - 8780 (2018/06/25)
Monodentate phosphine ligands are frequently employed in the Ni-catalyzed C-O functionalization of aryl esters. However, the extensive body of preparative work on such reactions contrasts with the lack of information concerning the structure and reactivity of the relevant nickel intermediates. In fact, experimental evidence for a seemingly trivial oxidative addition into the C-O bond of aryl esters with monodentate phosphines and low-valent nickel complexes still remains elusive. Herein, we report a combined experimental and theoretical study on the Ni(0)/PCy3-catalyzed silylation of aryl pivalates with CuF2/CsF additives that reveals the involvement of unorthodox dinickel oxidative addition complexes in C-O bond cleavage and their relevance in C-Si bond formation. We have obtained a mechanistic picture that clarifies the role of the additives and demonstrates that dinickel complexes act as reservoirs of the propagating monomeric nickel complexes by disproportionation. We believe this study will serve as a useful entry point to unravelling the mechanistic underpinnings of other related Ni-catalyzed C-O functionalization reactions employing monodentate phosphines.
