NNN ligand, metal complexes thereof, preparation methods and application

Abstract

The invention discloses an NNN ligand, metal complexes thereof, preparation methods and application, and particularly provides an NNN ligand 1, a metal complex 2 of the NNN ligand, a metal complex 3 of the NNN ligand and preparation methods of the NNN ligand 1 and the metal complexes, as well as application of the metal complex 3 of the NNN ligand to catalysis on hydroboration reaction of bis-substituted olefin, especially application of the metal complex 3 to catalysis on asymmetric hydroboration reaction of 1, 1-bis-substituted olefin. The metal complex 3 of the NNN ligand has good catalytic activity in the hydroboration reaction of the bis-substituted olefin, especially asymmetric hydroboration reaction of the 1, 1-bis-substituted olefin, has excellent regioselectivity and enantioselectivity, and is high in yield and mild in reaction conditions; besides, the preparation methods of the NNN ligand and the metal complexes thereof are simple, environment-friendly, mild in reaction conditions, relatively high in yield, and simple in post-processing, and the raw materials are low in cost and easy to obtain, so that the preparation methods are suitable for industrial production. (The formulas of the NNN ligand 1, metal complex 2 and metal complex 3 are shown in the description).

Description

technical field [0001] The invention relates to NNN ligand, its metal complex, preparation method and application. Background technique [0002] Enantioselective transformation of 1,1-disubstituted alkenes, considered the most challenging work in asymmetric synthesis (Thomas, S.P.; Aggarwal, V.K. Angew. Chem. Int. Ed. 2009, 48, 1896.) . As far as we know, for the enantioselective transformation of 1,1-disubstituted alkenes, only hydrogenation (Cui, X.; Burgess, K. Chem. Rev. 2005, 105, 3272); (Diéguez, M.; Mazuela , J.; Pàmies, O.; Verendel, J.J.; Andersson, P.G.J.Am.Chem.Soc.2008, 130, 7208); (Roseblade, S.J.; Pfaltz, A.Acc.Chem.Res. 2007, 40, 1402. ) and dihydroxylation (Wang, X.; Zak, M.; Maddess, M.; O'Shea, P.; Tillyer, R.; Grabowski, E.J.J.; Reider, P.J. Tetrahedron Lett.2000, 41, 4865); ( Becker, H.; King, S.B.; Taniguchi, M.; Vanhessche, K.P.M.; Sharpless, K.B.J.Org.Chem. 1995, 60, 3940) can obtain an ee value of 90% or more. The asymmetric hydroboration of alken...

AI Technical Summary

Problems solved by technology

Traditional pyridine bisoxazoline ligands (NNN ligands) have been widely used in asymmetric catalysis, but the reports on complexes formed by coordination of such ligands with cheap metals such as iron and cobalt are very limited. The enantioselectivity is also poor in the examples of (Tondreau, A.M.; Darmon, J.M.; Wile, B.M.; Floyd, S.K.; Lobkovsky, E.; Chirik, P.J., Organometallics 2009, 28, 3928.)

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