1437307-89-5Relevant academic research and scientific papers
Access to 2′-substituted binaphthyl monoalcohols via complementary nickel-catalyzed kumada coupling reactions under mild conditions: Key role of a P,O ligand
Handa, Sachin,Mathota Arachchige, Yohan L. N.,Slaughter, Legrande M.
, p. 5694 - 5699 (2013)
Two complementary Kumada coupling methods for the conversion of monotriflated 1,1′-binaphthalene-2,2′-diol (BINOL) into 2′-substituted binaphthyl monoalcohols under mild conditions are reported. A protocol using NiCl2(dppe), in combination with
Competing amination and C-H arylation pathways in Pd/xantphos-catalyzed transformations of binaphthyl triflates: Switchable routes to chiral amines and helicene derivatives
Ruch, Aaron A.,Handa, Sachin,Kong, Fanji,Nesterov, Vladimir N.,Pahls, Dale R.,Cundari, Thomas R.,Slaughter, Legrande M.
supporting information, p. 8123 - 8140 (2016/09/09)
A Pd(OAc)2/xantphos catalyst system was found effective for benzylaminations of binaphthyl 2-triflates bearing a variety of alkyl, benzyl, and substituted phenyl substituents at the 2′-position. With 2′-aryl substituents, an intramolecular Pd-catalyzed C-H arylation was observed as a competing side reaction under some conditions. By adjusting the solvent and quantity of the amine, the reaction was optimized to favor either the amination or the C-H arylation pathway, affording two distinct and potentially useful sets of products. The amines represent tunable chiral ligand precursors, while the C-H arylation pathway affords a series of benzofused [5]helicene derivatives. Kinetic studies and activation parameters for the C-H arylation pathway, supported by DFT calculations, are consistent with a concerted metalation-deprotonation (CMD) mechanism involving a Pd-bound carbonate as the base. Xantphos is proposed to facilitate the turnover-limiting inner-sphere CMD step by acting as a hemilabile ligand, while its wide bite angle engenders a low reductive elimination barrier.
