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Bis-chiral sulfoxide-alkene ligand compound, and preparation method and application thereof

A compound and bichiral technology, applied in the field of bichiral sulfoxide-ene ligand compounds and their preparation, can solve the problems of few literature reports, lack of independent originality, application limitations, etc., and achieve simple steps and excellent region selection The effect of sex, good enantioselectivity

Inactive Publication Date: 2015-09-09
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the ligands reported in the literature are basically synthesized from known chiral sources, lacking independent originality
At the same time, this type of ligand is basically used in asymmetric addition reactions, and its application is limited.
Although asymmetric allylation catalyzed by metal rhodium has been studied, there are few reports in the literature, the mechanism is not perfect, and there are few reports of new ligands catalyzing this type of reaction.

Method used

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  • Bis-chiral sulfoxide-alkene ligand compound, and preparation method and application thereof
  • Bis-chiral sulfoxide-alkene ligand compound, and preparation method and application thereof
  • Bis-chiral sulfoxide-alkene ligand compound, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1～8

[0037] Synthesis of 3-Substituted Propyl o-Aminophenyl Sulfides

[0038] The reaction equation is

[0039]

[0040]In a dry argon-protected reaction tube, sequentially add compound 2 (1.0 mmol), o-nitrobenzenesulfonyl hydrazide (NBSH) (2.0 mmol) and triethylamine (4.0 mmol), add THF (5.0 mL) and iPrOH (5.0 mL). Reaction at 30°C for 12h. After the reaction was completed, the residue was subjected to column chromatography after removing the solvent under reduced pressure to obtain the target product 3 (petroleum ether / ethyl acetate=10:1, v / v)

[0041] When R 1 At the same time, the structure and properties of the target product 3 are as follows:

Embodiment 1

[0043] Target product 3: (R)-2-(1-phenylpropylthio)aniline

[0044]

[0045] White solid, melting point 89.5-90.4°C, 85% yield, 97% ee[chiral column OD-H (0.46cm x25cm); n-hexane / isopropanol=90 / 10; flow rate=1.0mL / min; detection wavelength = 214nm; t R =6.378(minor),7.212(major)min].

[0046] [α] D 20 =+120.3°(c 1.0, CHCl 3 ).

[0047] 1 H NMR (400MHz, CDCl 3 )δ=7.26-7.19(m,3H),7.31-7.13(m,3H),7.10-7.06(m,1H),6.66(d,J=8.0Hz,1H),6.58(t,J=7.2Hz ,1H),4.20(br,2H),3.86(dd,J=6.4,6.8Hz,1H),2.05-1.92(m,2H),0.89(t,J=7.2Hz,3H)ppm.

[0048] 13 C NMR (100MHz, CDCl 3 )δ=149.0, 141.9, 137.4, 130.0, 128.2, 127.6, 126.9, 118.1, 116.9, 114.7, 54.8, 28.7, 12.3ppm.

[0049] IR(KBr):ν max (cm -1 )=3458,3354,3067,3024,2963,2925,2869,1596,1474,1304,734,701.

[0050] HRMS(ESI+)calcd for C 15 h 17 NNaOS[M+Na] + :282.0923,Found:282.0925.

Embodiment 2

[0052] Target product 3: (S)-2-(1-(3-methoxyphenyl)propylthio)aniline

[0053]

[0054] White solid, melting point 72.8-73.8°C, 88% yield, 94% ee[chiral column AD-H (0.46cm x25cm); n-hexane / isopropanol=90 / 10; flow rate=1.0mL / min; detection wavelength = 214nm; t R =7.836(minor),9.287(major)min].

[0055] [α] D 20 =-150.2°(c 1.0, CHCl 3 ).

[0056] 1 H NMR (400MHz, CDCl 3 )δ=7.18-7.14(m,2H),7.10-7.06(m,1H),6.78-6.73(m,2H),6.65(d,J=7.6Hz,1H),6.58(dt,J=1.2, 7.6Hz, 1H), 4.20(br, 2H), 3.82(dd, J=6.4, 6.4Hz, 1H), 3.72(s, 3H), 2.01-1.92(m, 2H), 0.90(t, J=7.2 Hz,3H)ppm.

[0057] 13 C NMR (100MHz, CDCl 3 )δ=159.4, 149.1, 143.6, 137.4, 130.1, 129.2, 119.9, 118.2, 117.0, 114.7, 113.8, 112.6, 55.1, 54.8, 28.6, 12.3ppm.

[0058] IR(KBr):ν max (cm -1 )=3462,3048,2963,2925,2873,2826,1257,743,700.

[0059] HRMS(ESI+)calcd for C 16 h 19 NNaO 2 S[M+Na] + :298.1080,Found:282.1082.

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Abstract

The invention relates to a bis-chiral sulfoxide-alkene ligand compound, and a preparation method and application thereof. The preparation method comprises the following steps: preparing a 3-substituted allyl o-aminothiophenol ether compound by subjecting raw materials--sodium o-aminothiophenol and an allyl methyl carbonate compound to a reaction for 12 to 24 h in an organic solvent under the action of an additive, with reaction temperature controlled to be 15 and 40 DEG C and an iridium complex produced by reaction of [Ir(COD)Cl]2 with ligand as a catalyst; subjecting the 3-substituted allyl o-aminothiophenol ether compound to reduction so as to obtain a 3-substituted propyl o-aminothiophenol ether compound; then oxidizing the 3-substituted propyl o-aminothiophenol ether compound with m-chloroperoxybenzoic acid so as to obtain an o-aminosulfoxide compound; and finally, subjecting the o-aminosulfoxide compound and 3-substituted alpha,beta-unsaturated aldehyde to condensation and carrying out reduction with sodium borohydride so as to obtain the bis-chiral sulfoxide-alkene ligand. The method has simple and concise steps; and a chiral source and the structural framework of the ligand are original. Meanwhile, the bis-chiral sulfoxide-alkene ligand compound can be used in the metallic rhodium-catalyzed asymmetric allylation and produces good results.

Description

technical field [0001] The invention belongs to the field of metal catalysis, and in particular relates to bichiral sulfoxide-ene ligand compounds and their preparation methods and applications. Background technique [0002] In the field of metal-catalyzed asymmetric reactions, the synthesis of chiral ligands has always been the most important hotspot and difficulty. The currently well-known ligands mainly focus on chiral phosphorus-containing ligands, chiral nitrogen-containing ligands, chiral sulfur-containing ligands and chiral oxygen-containing ligands. Chiral sulfur ligands are concentrated in chiral sulfoxide ligands. The chiral sulfoxide ligands reported in the literature have excellent catalytic effects. (a) Masdeu-Bultü, A.M.; Déguez, M.; Maryin, E.; Gümez, M. Coord. Chem. Rev. 2003, 242, 159. (b) Fernández, I. Khiar, N. 103, 3651. (c) Mellah, M.; Voituriez, A.; Schulz, E. Chem. Rev. 2007, 107, 5133. (d) Khiar, N.; Fernandez, I.; Alcudia, F. Tetrahedron Lett .19...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C317/36C07C315/04C07D333/20B01J31/22C07C69/618C07C69/65C07C69/734C07C69/738C07C67/343C07C67/32
Inventor 赵晓明张敏张红波
Owner TONGJI UNIV