Spiro-diphosphine ligand

A technology of bisphosphine ligand and spiro ring, which is applied in the field of synthesis of chiral compounds, can solve the problems of inconvenient operation and poor stability, and achieve the effects of high stereoselectivity, high conversion number and high reactivity

Inactive Publication Date: 2003-09-03
NANKAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these ligands have high enantioselectivity, they all have certain disadvantages, that is, poor stability. In most cases, they must be used in degassed solvents and inert gas atmospheres, and the operation is extremely inconvenient.

Method used

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  • Spiro-diphosphine ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Example 1 Preparation of (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'spirodihydroindene

[0014] Add (S)-spirobiphenol (5.0g, 19.8mmol), pyridine (7.0mL, 86.7mmol) and 100mL CH in a 250mL reaction flask 2 Cl 2 , Trifluoromethanesulfonic anhydride (8.2 mL, 43.7 mmol) was added dropwise at 0° C., and the mixture was stirred overnight at room temperature. The reaction solution was concentrated and filtered with a silica gel column to obtain (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spiroindene 9.9 g, yield: 97%; white solid, Melting point: 62-64℃; [α] D -64(c0.5CH 2 Cl 2 ).

[0015] 1 H NMR(300MHz, CDCl 3 )δ 2.35(m, 4H, CH 2 ), 3.10(m, 4H, CH 2 ), 7.15 (dd, 2H, J=1.8 and 6.6 Hz, Ar-H), 7.26-7.30 (m, 4H, Ar-H); 13 C NMR(75MHz, CDCl 3 )δ31.1, 38.6, 59.4, 115.9, 118.5, 120.1, 124.4, 129.4, 138.2, 145.8, 147.7; IR (KBr) 2958, 1622, 1579, 1466, 1405, 1214, 1144, 994, 934, 860, 830cm -1 ; MS(EI)m / z516(M + ); elemental analysis (theoretical value) C 19 H 14 F 6 O 6 S 2 : C43....

Embodiment 2

[0016] Example 2 Preparation of (S)-7-diphenylphosphono-7'-trifluoromethanesulfonyloxy-1,1'-spiroindene

[0017]Add (S)-7,7'-bis(trifluoromethanesulfonyloxy)-1,1'-spiroindene (4.0g, 7.75mmol), diphenylphosphine oxide (3.13 g, 15.5 mmol), palladium acetate (87 mg, 0.39 mmol), 1,4-diphenylphosphinobutane (dppb, 166 mg, 0.39 mmol), and 25 mL of DMSO. Diisopropylethylamine (4.1 g, 32 mmol) was added with stirring, and the mixture was heated to 100° C. to react for 6 hours. Cooled to room temperature, diluted with EtOAc, filtered, the filtrate was subjected to silica gel column chromatography after removing the solvent (eluent: petroleum ether / EtOAc=3 / 1) to obtain (S)-7-diphenylphosphono-7'- Trifluoromethanesulfonyloxy-1,1'-spiroindene 4.0 g, yield 90%; white solid, melting point: 173-175°C; [α] D -74(c0.5 CH 2 Cl 2 ).

[0018] 1 H NMR(300MHz, CDCl 3 )δ2.20-2.39(m, 4H CH 2 ), 3.08(m, 2H, CH 2 ), 3.23-3.41(m, 2H, CH 2 ), 6.21 (d, 2H, J=8.1 Hz, Ar-H), 7.14-7.20 (m, 11H, Ar-H); 31 PNMR(1...

Embodiment 3

[0019] Example 3 Preparation of (R)-7-dimethylphenylphosphono-7'-trifluoromethanesulfonyloxy-1,1'-spiroindene

[0020] The preparation method is the same as in Example 2. Yield: 81%; white solid, melting point: 222-224°C; [α] D +116(c 0.5 CH 2 Cl 2 ).

[0021] 1 H NMR(300MHz, CDCl 3 )δ2.18-2.42(s, 3H, CH 3 ), 2.32(s, 3H, CH 3 ), 2.39(s, 3H, CH 3 ), 3.05(m, 3H, CH 2 ), 3.21-3.19(m, 2H, CH 2 ), 6.24 (d, 2H, J = 8.1 Hz, Ar-H), 7.00-7.10 (m, 2H, Ar-H), 7.10-7.23 (m, 10H, Ar-H), 7.20-7.23 (m, 2H, Ar-H), 7.29(d, 2H, Ar-H); 31 P NMR(121 MHz, CDCl 3 )δ31.73(s); 13 C NMR(121 MHz, CDCl 3 ): δ21.5, 30.7, 31.8, 39.8, 40.0, 61.9, 115.6, 117.5, 123.7, 125.9, 126.2, 127.5, 127.6, 127.9, 128.2, 128.6, 128.8, 128.9, 131.3, 131.5, 131.7, 131.8, 132.2, 133.2, 133.4, 133.6, 140.9, 141.3, 144.9, 145.9, 146.1, 149.7, 152.9, 152.9; IR (KBr) 3061, 2943, 1462, 1439, 1415, 1398, 1209, 1142, 853cm -1 ; MS(EI)m / z 596(M + ); elemental analysis (theoretical value) C 32 H 28 F 3 O 4 PS: 64.16 (64.42); H4.92 (4....

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Abstract

A spirocyclo-biphosphine ligand is prepared from spirocyclo-biphenol through esterifying by trifluoro methylsulfonic acid anhydride, coupling with diaryloxyphosphine under catalysis of Pd, and reduction reacting on trichlorosilane. It includes d-and levo-spricyclo-biphosphine ligands, whose mixture is dl-spirocyclo-biphosphine ligand. It can be used for asymmetrical catalytic hydrogenation reaction of latent chiral ketone with high stereo selectivity and e.e. value up to 99.5%.

Description

Technical field [0001] The invention belongs to the synthesis of chiral compounds, in particular to the synthesis of a spirocyclic bisphosphine ligand with a C2 axis of symmetry, and the application of its ruthenium complex in the asymmetric catalytic hydrogenation of latent chiral ketones. Background technique [0002] Asymmetric hydrogenation of latently unsaturated substrates (alkenes, ketones, imines, etc.) is an important way to synthesize various chiral substances. In asymmetric hydrogenation reactions catalyzed by transition metals, chiral ligands play a key role in the optical purity of the product. In the past 30 years, people have made great achievements in the research of asymmetric catalytic reactions (such as: the enantiomeric excess of the product can reach 100% ee), and it has been applied to many important drugs (such as: Industrial synthesis of barium, naproxen, ibuprofen) and natural products (such as nerol, etc.). However, there are still many reactions whose a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/28C07F9/50C07F15/00
Inventor 周其林谢建华程旭付煜王立新
Owner NANKAI UNIV
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