Phosphamide-(di) secondary amine dual-functional catalyst and synthesis method thereof

Abstract

The invention discloses a phosphamide-(di) secondary amine dual-functional catalyst and a synthesis method thereof. The structure of the catalyst is represented as follows, and the synthesis method comprises the steps of performing reaction on simple and readily available chiral 1,2-diamine and various phosphoryl chloride, and performing reaction with an aldehyde compound to prepare the phosphamide-(di) secondary amine dual-functional catalyst with chirality and efficient catalysis activity. The prepared catalyst is novel in structure and stable in property; the synthesis method is simple, and the catalysis activity is high; the synthesis method is simple and has the outstanding characteristics of wide application range, mild reaction condition, simplicity and convenience in operation and the like. The structural formula of the catalyst is shown in the description.

Description

technical field [0001] The invention belongs to the technical field of organic compounds, and relates to a novel phosphoramide-(primary) secondary amine bifunctional catalyst and a synthesis method thereof. Background technique [0002] Bifunctional catalysts refer to compounds containing two functional groups in the same catalyst molecule. Since there are two functional groups in the molecule at the same time, it is possible for one functional group to deactivate the electrophile and the other to deactivate the nucleophile in the reaction, which not only shortens the spatial distance between the two reaction substrates, making the reaction similar to Occurs within the molecule, and at the same time due to the dual activation, the reaction substrate is better activated, thereby improving the activity and selectivity of the reaction. [0003] Hydrogen bond donor bifunctional catalyst means that one functional group in the catalyst molecule is a hydrogen bond donor functional...

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Problems solved by technology

[0004] Although phosphoramide catalysts have the advantages described above, in the literature survey, it was found that phosphoramide chiral catalysts are rarely used in asymmetric catalytic reactions

In particular, there are fewer reports on the application of combined phosphoramides as chiral bifunctional catalysts in the catalysis of small organic molecules.

In 2011, a class of cinchona base-derived tertiary amine-phosphoramide bifunctional catalysts (M.Ding, F.Zhou, Y.-L.Liu, C.-H.Wang, X.-L.Zhao, J.Zhou , Chem.Sci.2011,2,2035.), and applied it to the research on the asymmetric Michael addition reaction of 3-substituted oxindole and nitroalkene; although the tertiary amine-phosphoramide derived from cinchona base It has been reported, but there is almost no report on the bifunctional catalyst of phosphoramide-(primary) secondary amine. Only Shi Min's group and Song group reported that hypophosphoramide-secondary amine was used as a metal ligand for diethylzinc reagent pair. Addition reaction of imines and aldehydes[a)M.Shi,W.Zhang,Tetrahedron Asymmetric 2003,14,3407.b)H.Huang,H.Zong,G.Bian,L.Song,J.Org. Chem.2012,77,10427-10434.]; In addition, Zhou Zhenghong and Wang Youming's group developed a thiophosphoramide-secondary amine salt catalyst for the asymmetric Michael addition of ketones to aryl nitroalkenes Synthesis reaction research (A.Lu, R.Wu, Y.Wang, Z.-H.Zhou, G.Wu, J.Fang, C.Tang, Eur.J.Org.Chem.2010,2057.)

However, phosphoramidite-(primary) secondary amine bifunctional catalysts based on chiral 1,2-diamine derivatives have not been reported yet.

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