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Chiral sulfinamide monophosphine ligand based on ferrocene skeleton and preparation method for full configurations of chiral sulfinamide monophosphine ligand

A technology of sulfenamide mono- and phosphine ligands, applied in chemical instruments and methods, metallocene, organic chemistry, etc., can solve the problems of difficult transformation, low yield, and expensive raw materials

Pending Publication Date: 2020-04-17
FUDAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, problems such as expensive raw materials, long synthetic routes, low yields, and difficult transformation largely restrict the development of chiral phosphine ligands.

Method used

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  • Chiral sulfinamide monophosphine ligand based on ferrocene skeleton and preparation method for full configurations of chiral sulfinamide monophosphine ligand
  • Chiral sulfinamide monophosphine ligand based on ferrocene skeleton and preparation method for full configurations of chiral sulfinamide monophosphine ligand
  • Chiral sulfinamide monophosphine ligand based on ferrocene skeleton and preparation method for full configurations of chiral sulfinamide monophosphine ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1，9

[0090] Example 1, 9a(S,R s )Synthesis

[0091] Step 1: In a 250mL dry single-necked bottle, add under nitrogen atmosphere (20mmol, 6.88g) and 30mL THF, stirred at -25°C for 10 minutes, added dropwise n-BuLi (1.0eq., 12.5mL, 1.6M n-hexane solution), continued to stir for 1.5 hours, added dropwise ClPPh 2 (1.0eq., 3.57mL), slowly rose to room temperature and continued to stir for 12 hours, separated the layers, extracted the aqueous layer three times with ethyl acetate, combined the organic phases, washed with water and saturated sodium chloride, and dried over anhydrous sodium sulfate. filtered, spin-dried, and purified by column chromatography to obtain The yield was 71%. 1 H NMR (400MHz, CDCl 3 ):δ7.40-7.30(m,10H),4.42(t,J=2.4Hz,2H),4.32(t,J=2.5Hz,2H),4.15(q,J=2.5Hz,2H),3.99 (t,J=2.5Hz,2H); 31 P NMR (160MHz, CDCl 3 ): δ-15.94; HRMS (ESI) calculated for [C 28 h 24 o 2 P][M+H] + :448.9752; found: 448.9742..

[0092] Among them, n-BuLi is n-butyllithium; ClPPh 2...

Embodiment 2

[0098] Example 2, 9b(R,R s ) synthesis (reference scheme 1)

[0099] The specific operation refers to Example 1, the metal reagent used is phenyllithium, and the yield is 40%. 1 H NMR (400MHz, CDCl 3 )δ7.38-7.27(m,15H),5.10(d,J=5.6Hz,1H),4.30-4.26(m,3H),4.09-4.01(m,3H),4.10-4.05(m,1H) ,3.95-3.91(m,1H),3.71(d,J=5.6Hz,1H),1.19(s,9H); 13 C NMR (100MHz, CDCl 3 )δ142.3, 138.5(d, J=9.8Hz), 133.6(d, J=20.0Hz), 129.6, 129.5, 128.8, 127.3(d, J=6.8Hz), 127.3, 79.0, 75.9, 74.8(d, J =14.0Hz), 73.0(d, J=3.0Hz), 71.6, 69.2, 58.0, 23.8; 31 P NMR (202MHz, CDCl 3 )δ-17.40; HRMS (ESI) calculated for [C 33 h 34 FeNOPS][M+H] + :580.1521; found: 580.1513..

Embodiment 3

[0100] Example 3, 9c(R,R s ) synthesis (reference scheme 1)

[0101] Concrete operation with reference to embodiment 1, metal reagent used is t BuLi, 81% yield. 1 H NMR (400MHz, CDCl 3 )δ7.40-7.28(m,10H),4.65(s,1H),4.60(s,1H),4.32(s,1H),4.21(s,1H),4.08(s,2H),4.02(s ,1H),3.89(s,1H),3.83(s,1H),3.63(s,1H),1.28(s,9H),0.75(s,9H); 13 C NMR (100MHz, CDCl 3 )δ138.5(d, J=10.0Hz), 133.6(d, J=20.0Hz), 129.5, 128.8(d, J=7.2Hz), 79.5, 74.0, 74.6(d, J=13.8Hz), 73.0 (d, J=3Hz), 70.6, 69.6, 57.5, 36.1, 23.9, 22.1; 31 PNMR (202MHz, CDCl 3 )δ-17.33; HRMS (ESI) calculated for [C 31 h 38 FeNOPS][M+H] + :560.1834; found: 560.1829..

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Abstract

The invention belongs to the technical field of organic chemistry, and particularly relates to a chiral sulfinamide monophosphine ligand based on a ferrocene skeleton and a preparation method for fullconfigurations of the chiral sulfinamide monophosphine ligand. Four optically pure chiral monophosphine ligands 1(S, R<s>), 1 (R, R<s>), 1 (S, S<s>) and 1 (R, S<s>) are obtained by using chiral sulfinyl imide with two configurations including R<S> and S<S> through two ways including a step-by-step method and a one-pot method. The synthesized sulfonamide chiral monophosphine ligand (denoted as HK-Phos) based on the ferrocene skeleton shows certain reaction activity and stereoselectivity as a chiral ligand in the research of asymmetric synthesis catalyzed by transition metal, and has potentialand wide application value.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a class of chiral sulfinamide monophosphine ligands based on a ferrocene skeleton and a preparation method for the full configuration thereof. Background technique [0002] Chirality exists widely in nature and is one of the basic properties of substances in nature. In organisms, the vast majority of biomolecules such as proteins, nucleotides, and sugars are chiral molecules. Chiral substances are like the left and right hands of a human being. The two enantiomers are mirror images of each other but cannot be completely superimposed. Seemingly similar two enantiomers often have different optical properties, physicochemical properties and different or even opposite biological activities. Such as chiral ethambutol, its (S,S) configuration isomer can treat tuberculosis, but (R,R) configuration isomer can cause blindness. In addition, (R)-thalidomide can be u...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02C07F19/00
CPCC07F17/02C07F19/00
Inventor 张俊良储豪科
Owner FUDAN UNIV
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