2785-97-9Relevant articles and documents
A substituted 2, 3 - dihydrobenzo [d] [1, 3] oxa phosphorus mixed cyclopentadiene ligand preparation method
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Paragraph 0146; 0147; 0148, (2017/08/25)
The invention relates to a preparation method of a substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand. The preparation method of the substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand comprises the following concrete steps: (b) in presence of alkali and a hydroxymethylation reagent, carrying out hydroxymethylation on a compound show in a formula II to obtain a compound shown in a formula C; (c) in presence of a halogenating reagent, carrying out halogenating reaction on the compound shown in the formula C to obtain a compound shown in a formula D; (d) in presence of Lewis acid or Bronsted acid and alkali, carrying out demethylation cyclization reaction on a compound shown in the formula D to obtain a compound shown in a formula E; and (e) in presence of a reducing agent, carrying out reduction reaction on the compound shown in the formula E to obtain the ligand shown in a formula I, wherein groups in each formula are defined in the specification. The invention also discloses a compound shown in the formula II and a preparation method thereof. The preparation method of the substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand is simple in steps, mild in reaction conditions and applicable to industrial production.
PHOSPHORUS LIGANDS AND METHODS OF USE
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Paragraph 0124, (2016/11/07)
In one embodiment, the application discloses ligands, such as a ligand from a dihydrobenzo [1,3] oxaphosphole scaffold, and palladium or other transition metal complexes comprising the ligands and methods for performing cross coupling reactions and asymmetric cross coupling reactions with high selectivity and efficiency, under aqueous micellar catalysis conditions.
Concepts for stereoselective acrylate insertion
Neuwald, Boris,Caporaso, Lucia,Cavallo, Luigi,Mecking, Stefan
supporting information, p. 1026 - 1036 (2013/05/08)
Various phosphinesulfonato ligands and the corresponding palladium complexes [{((PaO)PdMeCl)-μ-M}n] ([{( X1-Cl)-μ-M}n], (PaO) = κ2- P,O-Ar2PC6H4SO2O) with symmetric (Ar = 2-MeOC6H4, 2-CF3C6H4, 2,6-(MeO)2C6H3, 2,6-(iPrO)2C 6H3, 2-(2′,6′-(MeO)2C 6H3)C6H4) and asymmetric substituted phosphorus atoms (Ar1 = 2,6-(MeO)2C6H 3, Ar2 = 2′-(2,6-(MeO)2C 6H3)C6H4; Ar1 = 2,6-(MeO)2C6H3, Ar2 = 2-cHexOC 6H4) were synthesized. Analyses of molecular motions and dynamics by variable temperature NMR studies and line shape analysis were performed for the free ligands and the complexes. The highest barriers of ΔGa = 44-64 kJ/mol were assigned to an aryl rotation process, and the flexibility of the ligand framework was found to be a key obstacle to a more effective stereocontrol. An increase of steric bulk at the aryl substituents raises the motional barriers but diminishes insertion rates and regioselectivity. The stereoselectivity of the first and the second methyl acrylate (MA) insertion into the Pd-Me bond of in situ generated complexes X1 was investigated by NMR and DFT methods. The substitution pattern of the ligand clearly affects the first MA insertion, resulting in a stereoselectivity of up to 6:1 for complexes with an asymmetric substituted phosphorus. In the consecutive insertion, the stereoselectivity is diminished in all cases. DFT analysis of the corresponding insertion transition states revealed that a selectivity for the first insertion with asymmetric (P aO) complexes is diminished in the consecutive insertions due to uncooperatively working enantiomorphic and chain end stereocontrol. From these observations, further concepts are developed.