Chirality phosphine nitrogen compound containing N-aryl as well as synthetic method and application thereof

Abstract

The invention provides a chirality phosphine nitrogen compound containing N-aryl as well as a synthetic method and application thereof. The phosphine nitrogen compound is based on axial chirality or comprises a helical chirality skeleton, and is synthetized by taking optically pure axial chirality or helical chirality glycols compound, phosphorus trichloride and aromatic secondary amine as raw material for reaction. The raw material used in the method is easy to obtain, the reaction condition is mild, and the products are easy to separate and purify. The N-aryl phosphine nitrogen compound base on the axial chirality or the helical chirality skeleton synthetized by the method can be effectively applied in substitution reaction of allyl catalyzed by metal iridium, so that the product can be obtained with high enantioselectivity and regioselectivity, and the substrate scope of the product is greatly widened.

Description

technical field [0001] The present invention relates to N-aryl phosphine nitrogen compounds based on axial chiral or helical chiral skeleton, a synthesis method and application thereof. The method can synthesize the ligand with a high yield and successfully apply the ligand to a In a series of metal iridium-catalyzed asymmetric allyl substitution reactions. Background technique [0002] Metal iridium-catalyzed asymmetric allyl substitution reactions can construct carbon-carbon bonds and carbon-heterobonds with high enantioselectivity and regioselectivity, and have been widely used in synthesis. At present, the ligands for such reactions are mainly Ferringa ligands and their derivatives [(a) Feringa, B.L.Acc.Chem.Res. 2000, 33, 346. (b) Alexakis, A.; Rosset, S.; Allamand, J. ; March, S.; Guillen, F.; Benhaim, C. Synlett 2001, 1375-1378. (c) Naasz, R.; Arnold, L.A.; Minnaard, A.J.; Feringa, B.L. Angew. Chem. 40, 927-930. (d) Polet, D.; Alexakis, A. Synthesis 2004, 2586-2590....

AI Technical Summary

Problems solved by technology

The synthesis of this kind of ligand is relatively complicated. Although it has been commercialized, the price is very expensive. More importantly, it has great limitations and the universality of the substrate is not very good.

Such as poor enantioselectivity control for ortho-substituted cinnamon carbonate substrates [(a) López, F.; Ohmura, T.; Hartwig, J.F.J. Am. Chem. Soc. 2003, 125, 3426. (b ) Polet, D.; Alexakis, A.; Tissot-Croset, K.; Corminboeuf, C.; .;Hartwig, J.F.J.Am.Chem.Soc.2007,129,7508.(d)Pouy,M.J.;Leitner,A.;Weix,D.J.;Ueno,S.;Hartwig,J.F.Org.Lett.2007,9,3949 .(e) Liu, W.-B.; He, H.; Dai, L.-X.; You, S.-L. Org. Lett. 2008, 10, 1815. (f) Liu, W.- B.;Zheng,C.;Zhuo,C.-X.;Dai,L.-X.;You,S.-L.J.Am.Chem.Soc.2012,134,4812.]; The control of diastereoselectivity in substituent reactions is also relatively poor [(a) Wu, Q.-F.; He, H.; Liu, W.-B.; You, S.-L.J.Am.Chem.Soc. 2010,132,11418.(b)Zhuo,C.-X.;Liu,W.-B.;Wu,Q.-F.;You,S.-L.Chem.Sci.2012,3,205.]

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