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Central chirality induced axial chirality diphosphine ligand and method for synthesizing same

A technology of chiral induction and bisphosphine ligands, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve problems such as unsatisfactory resolution results, and achieve easy raw materials, The synthesis process is simple, the effect of simplifying the synthesis process

Inactive Publication Date: 2008-07-30
WUHAN UNIV
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

The staff will spend a lot of time and money on the splitting process, and even the splitting effect is not ideal

Method used

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  • Central chirality induced axial chirality diphosphine ligand and method for synthesizing same
  • Central chirality induced axial chirality diphosphine ligand and method for synthesizing same
  • Central chirality induced axial chirality diphosphine ligand and method for synthesizing same

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Synthesis of 3-tert-butyl-5-bromophenol (3a)

[0033] Under nitrogen protection, 25.017 g (about 85.7 mmoL) (1-tert-butyl-3,5-dibromobenzene 2a) and 200 mL of THF were added to the Schlenk bottle. At -80°C, add 42.8mL (2.00M, about 85.7mmoL) of n-BuLi, and lithiate for 3h. Add B(OC 2 h 5 ) 3 14.5mL (about 85.7mmoL), after stirring for 4h, add H 2 o 2 9mL and 1mL of NaOH solution (10moL / L). After stirring for 1h, add NaOH 2 SO 3 6.5g stirred. with saturated NH 4 Cl neutralizes, CH 2 Cl 2 Extract and spin dry to obtain crude product. Distillation under reduced pressure gave 16.662 g of compound (3a), with a yield of 84.9%.

[0034] 1 H NMR (CDCl 3 , TMS, 300MHz) δ1.27(s, 9H), 6.80(d, J=11.4Hz, 2H), 7.08(s, 1H)\; 13 C NMR (CDCl 3 , TMS, 75MHz) δ31.07, 34.87, 111.71, 115.79, 121.26, 122.45, 154.99, 156.12; HRMS Calcd.for C 10 h 13 BrO: 229.1136, found: 230.1436;

Embodiment 2

[0036] Synthesis of 1-tert-butyl-3-bromo-5methoxybenzene (4a)

[0037] Dissolve 21.106g (0.09moL) of (3a) and 3.603g of NaOH (0.09moL) in 80mL of water, in an ice-water bath, stirring constantly, add 8.6mL (90mmoL) of (CH 3 ) 2 SO 4 , rise to room temperature after 1h. use CH 2 Cl 2 Extract and spin dry. Distillation under reduced pressure yielded 19.813 g of compound (4a), with a yield of 88.4%.

[0038] 1 H NMR (CDCl 3 , TMS, 300MHz) δ1.28(s, 9H), 3.78(s, 3H), 6.85(s, 2H), 7.10(s, 1H); 13 C NMR (CDCl 3 , TMS, 75MHz) δ31.11, 34.93, 55.40, 111.26, 113.40, 121.28, 122.53, 154.58, 160.08; HRMS Calcd.for C 11 h 15 BrO: 243.1402, found: 266.1047;

Embodiment 3

[0040] (5a) Synthesis of (3-diphenylphosphineoxy-5-tert-butylanisole)

[0041] In the there-necked flask equipped with dropping funnel and reflux condenser, magnetic stirring, add 1.656g (57.5mmoL) Mg, a little I 2 and 70 mL of THF. Under slightly boiling conditions, the mixed liquid of 50mL of THF and 13.984g (57.5mmoL) of (4a) was added dropwise, and it took 1h to complete the dropwise. Keep boiling for 3h, the solution is yellow or earthy gray. In an ice-water bath, add 10.4 mL (57.5 mmoL) of PPh 2 Cl, after 3h, ice-water bath, add 13mL (125mmoL) of H 2 o 2 . After 4h, add Na 2 SO 3 19g stirred. use CH 2 Cl 2 Extract and spin dry to obtain crude product. with Et 2 Washed with O to obtain a white powder and 15.326 g of compound (5a). Yield 73.2%.

[0042] 1 H NMR (CDCl 3 , TMS, 300MHz) δ1.24(s, 9H), 3.77(s, 1H), 6.99(d, J=13.8Hz, 10H), 7.10(s, 1H), 7.26(d, J=13.2Hz, 1H ); 13 C NMR (CDCl 3 , TMS, 75MHz) δ31.35, 35.17, 55.56, 113.41----159.67; HRMS Calcd.for...

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Abstract

The invention relates to central chiral induced axial chiral diphosphine ligand, which adopts the structural formula that in the formula, R1 is benzyl or substituted benzyl; R is tertiary butyl or trifluoromethyl. The invention adopts the preparation method that 1-R-3, 5-dibromo benzene is used as the raw material, to produce 3-R-5- bromophenol; and then methylation is performed to obtain 1-R-3- bromine -5- anisole; after lithium realization of 3-dihydro pjosphinyl-5-R methyl phenoxide which reacts with dihydro phosphonic chloride and is obtained through oxidation, the product of the reaction with iodine reacts with boron tribromide, 2-iodine-3-dihydro pjosphinyl-5-R phenol obtained through demethylation and then reacts with central chiral 2, 4- pentanediol derivative, to obtain 2, 4-di (2-iodine-3- dihydro pjosphinyl-5- substituent phenoxy oxygen) pentane; <6, 61 -(2, 4- pentanediol oxygen)>-(4, 41)- disubstituent -(2, 21)-di (dialkyl pjosphinyl)-(1, 11)- biphenyl is produced through coupling, and finally reaction is performed with tri-butylamine and trichlorosilane, to obtain the diphosphine ligand.

Description

technical field [0001] The invention relates to an axial chiral bisphosphine ligand based on central chirality induction and a synthesis method thereof. Background technique [0002] Since Knowles and Homer first applied the complexes of chiral trigonium ligands and ruthenium as catalysts for homogeneous asymmetric hydrogenation in the 1960s, the synthesis of chiral trigonium ligands has been continuously innovated, and the representative ones are DIOP and BINAP series, with C 2 Bidentate chiral ligands with symmetry axes play an important role. [0003] Homogeneous asymmetric catalytic hydrogenation is currently the most widely used method for chiral synthesis in industrial production, such as the industrial synthesis of L-dopa and naproxen. [0004] In the synthesis of chiral ligands, some guiding theories gradually formed. Such as stereoselectivity, electrical properties, steric hindrance, etc. For chiral bisphosphine ligands with biphenyl and binaphthyl as the backbo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/655
Inventor 王春江王储备陈栋陶海燕
Owner WUHAN UNIV
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