138076-08-1Relevant academic research and scientific papers
Nitrogen-phosphorus ligand, and preparation method and application thereof
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Paragraph 0079; 0081; 0083, (2020/01/03)
The invention belongs to the field of organic chemical ligands, and discloses a nitrogen-phosphorus ligand which has a structure shown in a general formula I, wherein R is hydrogen or alkoxy, R iscyclohexyl, naphthyl and optionally substituted phenyl, and R is hydrogen, phenyl or alkyl. The invention also discloses four synthesis methods of the nitrogen-phosphorus ligand and an applicationof the nitrogen-phosphorus ligand in a Sonogashira asymmetric cross-coupling reaction. According to the invention, the nitrogen-phosphorus compound with a novel structure is synthesized through derivatization by taking quinine and cinchonine as core frameworks, and the nitrogen-phosphorus compound can be used as a ligand for the asymmetric reaction. Particularly, the electronic effect and steric hindrance effect of phosphorus on the ligand can be regulated and controlled, so that the nitrogen-phosphorus compound has the following unique advantages in the free radical asymmetric reaction: catalytic efficiency is high, the application range of substrates is wide, the yield is high, and enantioselectivity is good.
Method for synthesizing alkyne through catalytic asymmetric cross coupling (by machine translation)
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Paragraph 1137; 1142; 1144, (2020/01/12)
The invention belongs to the field of, asymmetric synthesis, and discloses a method for catalyzing asymmetric cross- coupling to synthesize: an alkyne, and the L method comprises, the following steps, of A: preparing B a cuprous, salt and C a: ligand; preparing a catalyst; adding a base; reacting the compound with the compound with the compound; and reacting the compound with the compound. Of these, one of them, X is selected from the group consisting of, R halogens. 1 Optionally substituted heteroarylsulfonylcyanamide groups selected from the, group consisting, of optionally substituted, phenyl groups In-flight vehicle, R6 Trialkyl silyl groups or alkyl radicals, R2 Cycloalkyl radicals optionally substituted with an, optionally substituted alkyl, (CH radical2 )n R4 Multi,layer chain, n=0-10,R saw blade4 A group selected, from, the group consisting of phenyl, alkenyl, aralkynyls, noonyloxy,and, noonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylphenyl disiloxy-radicals. R3 A ligand, selected from hydrogen or any of the functional groups, is selected from the group consisting of, hydrogen and any L other functional group. The method, R disclosed by the, A invention has the, advantages of good catalytic, R ’ effect, wide application range. and high catalytic efficiency, and the, method disclosed by the, invention has the. advantages of good catalytic effect, wide application range and high catalytic efficiency. (by machine translation)
Method for synthesizing AMG837
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Paragraph 0096; 0098, (2020/01/03)
The invention relates to a method for synthesizing a compound, in particular to a method for synthesizing AMG837. The method comprises the following steps: a step of preparing an intermediate D by a reaction of an intermediate E with propyne; a step of de
Assembly of a coordination cage with four aromatic channel receptors on the outside
Miller, Philip W.,Nieuwenhuyzen, Mark,Xu, Xingling,James, Stuart L.
, p. 2008 - 2009 (2007/10/03)
Silver salts and triphosphine ligands with biphenyl substituents assemble to give coordination cages with four external aromatic channel receptors in a pseudo-tetrahedral arrangement.
Reductive cleavage of the carbon-phosphorus bond with alkali metals. I. Cleavage of functionalised triphenylphosphines; formation of secondary and primary phosphines
Budzelaar, Peter H. M.,Doorn, Johannes A. van,Meijboom, Nico
, p. 420 - 432 (2007/10/02)
The reductive cleavage reaction of functionalised triphenylphosphines 1-34 with Na/NH3 and Li/THF depends strongly on the nature of the functionality and on the reducing agent. No reduction occurs with 11, 24, 30, 31 and 32 in Na/NH3.Compounds 3, 4, 5, 10, 12, 13, 15, 19, 23, 25, 26 and 27 cleave to give the secondary phosphide in high yield with Na/NH3, whereas 2, 7 and 9 give a high yield with Li/THF.Reduction occurs but cleavage is poor with 6, 7, 14, 29 and 34 and Na/NH3, or with 11 and Li/THF.Primary ortho-functionalised phenyl phosphines are obtained by a double cleavage reduction from 2, 5, 12, 25, 26 and 27 with Na/NH3.This unprecedented reaction proceeds via the secondary phosphine, which is formed by protonation of the corresponding phosphide with NH3.It occurs when the aryl group contains a strongly electron-donating substituent.Multiple cleavage of aryl groups with extended ? systems occurs with 7 and 34 when they are made to react with Li/THF.Halogens are cleaved from the phenyl group (16, 17, 18, 28 and 33, with Na/NH3), whereas SCH3 groups are converted to the corresponding mercapto group (20, 21 and 22).Birch reduction (2 and 10) can take place in NH3 but not in the aprotic solvent THF; it occurs only when other reactions are slow.Sodium amide is obtained via reaction of 8 in Na/NH3.Restricted Hartree-Fock calculations were carried out for a number of substituted phenylphosphines.From the correlation between the energies and coefficients of the LUMO (always an aryl ?* orbital) and the experimental cleavage data, it was concluded that there are three requirements for successful cleavage.The LUMO energy should be neither too high (no reduction) nor too low (radical anion too stable) and, further, the coefficient of the LUMO on the carbon attached to phosphorus must be large.
