Chiral spiro phosphine-nitrogen-sulfur tridentate ligand and preparation method and application thereof
一种螺环、手性的技术，应用在羧酸酰胺旋光异构体制备、羧酸酯制备、羧酸酰胺制备等方向，达到活性高、反应条件温和、效率高的效果
- Summary
- Abstract
- Description
- Claims
- Application Information
AI Technical Summary
Problems solved by technology
Method used
Image
Examples
Embodiment 1
[0032] (R)-N-(2-(phenylthio)ethyl)-7-bis-(3,5-di-tert-butylphenyl)phosphino-7'-amino-1,1'-spirodihydro Synthesis of Indene(Ia)
[0033]
[0034] In a nitrogen atmosphere, weigh (R)-7'-bis-(3,5-di-tert-butylphenyl)phosphino-7'-amino-1,1'-spirodihydroindene (193mg, 0.3mmol ), pyridine (119 mg, 1.5 mmol) and 2 mL of dichloromethane in a 15 mL dry Schlenk tube. After stirring at room temperature to dissolve the solid, a dichloromethane solution (2 mL) of thiophenylacetyl chloride (84 mg, 0.45 mmol) was added dropwise to the system under cooling in an ice-water bath. After the drop was completed, after stirring at room temperature for 2 hours, TLC detected that the reaction was complete (petroleum ether: ethyl acetate = 10:1). The organic phase was washed with saturated brine, dried over anhydrous magnesium sulfate, and allowed to stand. The desiccant was removed by suction filtration, and the filtrate was desolvated by a rotary evaporator, and the crude product obtained was ...
Embodiment 2
[0039] (R)-N-(2-(phenylthio)ethyl)-7'-bis-(3,5-dimethylphenyl)phosphino-7'-amino-1,1'-spirodihydro Synthesis of Indene(Ib)
[0040]
[0041] Refer to Example 1 for specific operation, white solid, yield: 65%.
[0042] Mp 58-60°C, 277.0 (c 0.5, CHCl 3 ). 1 H NMR (400MHz, CDCl 3 )δ7.28-7.08(m, 8H), 7.03(t, J=7.6Hz, 1H), 6.84(s, 1H), 6.81(s, 1H), 6.72-6.63(m, 3H), 6.58(d , J=7.1Hz, 2H), 5.92(d, J=7.9Hz, 1H), 3.17-3.11(m, 1H), 3.08-2.96(m, 4H), 2.78(td, J=12.9, 6.5Hz, 1H), 2.68-2.53(m, 2H), 2.53-2.43(m, 1H), 2.43-2.33(m, 2H), 2.33-2.23(m, 1H), 2.17(s, 6H), 2.16(s, 6H); 31 P NMR (162MHz, CDCl 3 )δ-22.6(s); 13 C NMR (101MHz, CDCl 3)δ153.1 (d, J=25.3Hz), 144.6 (d, J=2.8Hz), 144.1 (d, J=7.7Hz), 143.5 (d, J=1.8Hz), 139.5 (d, J=13.0 Hz), 137.3(d, J=6.0Hz), 137.1(d, J=8.1Hz), 136.2(d, J=13.3Hz), 135.8, 135.0, 134.8, 134.4(d, J=2.9Hz), 133.4 (d, J=3.4Hz), 132.5, 132.2, 130.9, 130.7, 130.4, 130.1, 129.5, 129.0, 128.1, 127.5, 126.4, 126.0, 113.7, 107.9, 61.7 (d, J=3.2Hz), 41...
Embodiment 3
[0044] Synthesis of (R)-N-(2-(phenylthio)ethyl)-7'-diphenylphosphino-7'-amino-1,1'-spiroindene (Ic)
[0045]
[0046] See Example 1 for specific operation, white solid, yield: 51%.
[0047] Mp 55-58°C, 245.5 (c 0.5, CHCl 3 ). 1 H NMR (400MHz, CDCl 3 )δ7.31-6.91(m, 19H), 6.65(d, J=7.3Hz, 1H), 5.93(d, J=7.9Hz, 1H), 3.27-3.18(m, 1H), 3.11-2.93(m , 4H), 2.93-2.81(m, 1H), 2.68(t, J=6.5Hz, 2H), 2.53-2.33(m, 3H), 2.32-2.23(m, 1H), 2.18-2.08(m, 1H ); 31 P NMR (162MHz, CDCl 3 )δ-22.3(s); 13 C NMR (101MHz, CDCl 3 )δ153.3 (d, J=25.3Hz), 144.6 (d, J=3.1Hz), 144.3 (d, J=7.8Hz), 143.4, 139.7 (d, J=13.9Hz), 136.8 (d, J =14.0Hz), 135.6, 134.5(d, J=2.5Hz), 134.34, 134.25, 134.1, 134.0, 133.3, 133.2(d, J=3.5Hz), 133.1, 130.0, 129.0, 128.4(d, J=3.6 Hz), 128.1(d, J=5.5Hz), 128.0(d, J=7.3Hz), 127.7(d, J=9.9Hz), 126.4, 126.3, 113.8, 108.0, 61.7(d, J=3.2Hz) , 41.3, 40.0 (d, J=5.3Hz), 36.2, 33.9, 31.5, 31.1. HRMS (MALDI) Calcd for C 37 h 35 NPS[M+H] + : 556.2222; Found: 556.2216.
PUM
Login to View More Abstract
Description
Claims
Application Information
Login to View More 
PatSnap Eureka turns technology decisions into work you can execute. Powered by our Innovation Knowledge Graph, it runs expert workflows across engineering, life sciences, materials and intellectual property. Get your review-ready output in minutes.
