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Preparation method of axially chiral biaryl phosphine oxide and axially chiral biaryl phosphine

A biaryl and axial chirality technology, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve the problems of many synthesis steps, large dosage and high cost, and avoid The effect of many steps, simple operation and high synthesis efficiency

Active Publication Date: 2014-07-09
SUN YAT SEN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the required chiral inducing reagent is expensive, the amount used is large, and the synthesis steps are many, resulting in high cost of preparation

Method used

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  • Preparation method of axially chiral biaryl phosphine oxide and axially chiral biaryl phosphine
  • Preparation method of axially chiral biaryl phosphine oxide and axially chiral biaryl phosphine
  • Preparation method of axially chiral biaryl phosphine oxide and axially chiral biaryl phosphine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Example 1: Compound preparation of

[0021]

[0022] Under nitrogen protection, 103mg (0.25mmol) (1-bromo-2-naphthyl)-diphenylphosphine oxide, 68mg (0.5mmol) 2-methylphenylboronic acid, 159mg (0.75mmol) K 3 PO 4 , 5.77mg (0.012mmol) Ligand L1, 4.58mg (0.005mmol) Pd 2 (dab) 3 Add to reaction tube. 3mL of anhydrous and oxygen-free toluene was used as solvent, and reacted at 100°C for 72 hours. The reaction system was filtered to remove insoluble matter, concentrated, and the crude product was separated and purified by a silica gel column to obtain a light yellow solid (racemate). Yield: 80%. Enantioselectivity 67%ee (HPLC, Chiralcel OD-H column, 25°C, n-hexane:isopropanol=90:10, 0.5mL / min, 230nm, t R =13.71min, 15.62min). [α] 25 D -0.8 (c=5.0, CHCl 3 ), ESI-MS: 419.3[M+H] + .

[0023] 1 H NMR (300MHz, CDCl 3 )δ7.88(dd, J=8.6,2.9Hz,2H),7.72(dd,J=11.5,8.5Hz,1H),7.58-7.20(m,13H),7.14-7.09(m,1H),6.92 (d,J=7.4Hz,1H),6.89(d,J=7.1Hz,1H),6.83(d,J=7.7Hz,1H),1.6...

Embodiment 5

[0041] Example 5: Compounds preparation of

[0042]

[0043] Under nitrogen protection, 47.6mg (0.1mmol) (1-trifluoromethylsulfonate-2-naphthyl)-diphenylphosphine oxide, 40.0mg (0.2mmol) 2-biphenylboronic acid, 64mg ( 0.3mmol) K 3 PO 4 , 3.6mg (0.0048mmol) Ligand L2, 1.8mg (0.002mmol) Pd(OAc) 2 Add to reaction tube. 2mL of anhydrous and oxygen-free tetrahydrofuran was used as solvent, and reacted at 70°C for 24-120 hours. The reaction system was filtered to remove insoluble matter, concentrated, and the crude product was separated and purified by a silica gel column to obtain a light yellow solid. Yield: 46%. Enantioselectivity 65%ee (HPLC, Chiralcel OD-H column, 25°C, n-hexane:isopropanol=75:25, 1.0mL / min, 230nm, t R =7.35min, 10.42min). [α] 25 D -14.8 (c=1.0, CHCl 3 ), ESI-MS: 503.3[M+Na] + .

[0044] 1 H NMR (300MHz, CDCl 3 )δ7.76(d,J=8.4Hz,1H),7.71(d,J=8.17Hz,1H),7.32-7.50(m,15H),7.12-7.19(m,4H),686-6.97(m ,4H)ppm;

[0045] 13 C NMR (75MHz, CDCl 3 )δ...

Embodiment 6

[0047] Example 6: Compounds preparation of

[0048] Method steps are the same as in Example 5, yield: 50%, enantioselectivity 25%ee (high performance liquid chromatography, Chiralcel OD-H column, 25°C, n-hexane:isopropanol=75:25, 1.0mL / min , 230nm, t R =17.35min, 20.46min). [α] 25 D -8.8 (c=1.0, CHCl 3 ), ESI-MS: 503.3[M+Na] + .

[0049] 1 H NMR (300MHz, CDCl 3 )δ6.73-6.80(m,2H),6.84-6.87(m,4H),6.95-6.99(m,4H),7.04-7.10(m,1H),7.18-7.39(m,8H),7.49- 7.55(m,1H),7.60-7.69(m,5H)ppm;

[0050] 31 P NMR (121MHz, CDCl 3 )δ28.83ppm.

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Abstract

The invention discloses a preparation method of axially chiral biaryl phosphine oxide and axially chiral biaryl phosphine and particularly relates to a preparation method of axially chiral biaryl phosphine oxide with the structure shown as formula (I). The preparation method comprises the following steps: in an environment of an alkali and a solvent, directly preparing axially chiral biaryl phosphine oxide in one step through a catalytic asymmetric Suzuki reaction by taking 2-bi(aryl) phosphine oxide-1-aryl halide or sulphonate thereof and 2-substituted arylboronic acid or corresponding borate or borate as a reaction primer and metal palladium as a catalyst; then, recrystallizing the solvent to obtain the optically pure axially chiral biaryl phosphine oxide; and further obtaining corresponding axially chiral biaryl phosphine by adopting a silane reduction method or other common methods. The preparation method is simple to operate, economic and high in synthetic efficiency without common splitting process, so that the defect of existing preparation method which is more in step and raw material-wasting can be avoided. The preparation method provides a more convenient path for synthesizing axially chiral biaryl phosphine oxide and corresponding axially chiral biaryl phosphine.

Description

technical field [0001] The invention relates to an axial chiral biaryl phosphine oxide and a preparation method of the axial chiral biaryl phosphine. Background technique [0002] Monophosphine ligands with biaryl structure have important application value in organic synthesis [(a) Wolfe, J.P.; ;(b)Wolfe,J.P.;Buchwald,S.L.Angew.Chem.,Int.Ed.Engl.1999,38,2413-2416;(c)Martin,R.;Buchwald,S.L.Acc.Chem.Res.,2008, 41,1461–1473;(d)Yang,Y.;Buchwald,S.L.J.Am.Chem.Soc.2013,135,10642-10645.], which can participate in numerous carbon-carbon bond formation reactions and construct complex organic molecules. In metal-catalyzed asymmetric reactions, the importance of monophosphine ligands with chiral biaryl structures is becoming more and more significant, and their applications are becoming more and more extensive (Hayashi, T.Acc.Chem.Res.2000, 33, 354-362.) . In 1991, Hayashi's research group prepared (S)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthalene (MOP) through a multi-step reac...

Claims

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Application Information

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IPC IPC(8): C07F9/53
Inventor 邱立勤周有桂
Owner SUN YAT SEN UNIV
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