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O-aminophenyl chiral diallyl sulfide compound and its preparation method

A technology of allyl sulfide and aminophenyl, which is applied in the field of o-aminothiophenol chiral allyl sulfide compounds, can solve the problems of great difficulty in synthesis and difficult reaction, and achieve good yield , easy operation and high regional selectivity

Inactive Publication Date: 2013-05-15
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, chiral sulfur compounds are formed by metal-catalyzed allylation reactions, due to the poisoning effect of sulfur nucleophiles on metal catalysts (precipitating metals from solution or forming some non-catalytically active forms that make the reaction difficult to proceed), It is very difficult to synthesize in traditional metal-catalyzed reactions

Method used

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  • O-aminophenyl chiral diallyl sulfide compound and its preparation method
  • O-aminophenyl chiral diallyl sulfide compound and its preparation method
  • O-aminophenyl chiral diallyl sulfide compound and its preparation method

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Experimental program
Comparison scheme
Effect test

Embodiment 1-16

[0026] In an organic solvent, at -20°C-30°C, using allyl carbonate compounds and o-aminothiophenol sodium salts as raw materials, [Ir(COD)Cl] 2 The iridium complex generated by the interaction with the ligand is used as a catalyst, and reacted for 2-48 hours under the action of the additive to obtain an o-aminothiophenol allyl sulfide compound, which can be represented by the following formula

[0027]

[0028] Among them, mol refers to mole, Additive refers to additive, Solvent refers to solvent, T refers to temperature, and L refers to ligand.

[0029] Table 1 is the reaction structure table of the nucleophilic allyl thioetherification reaction of sodium o-aminothiophenate catalyzed by iridium complexes under different additives, temperatures, solvents and ligands:

[0030] Table 1

[0031]

[0032]

[0033] Among them: the solvent DCM is dichloromethane, Toluene is toluene, THF is tetrahydrofuran; NR means no reaction, trace means a small amount of product, DBACO ...

Embodiment 17-26

[0037] Iridium complex-catalyzed nucleophilic allyl thioetherification of o-aminothiophenol sodium salt Applicability:

[0038]

[0039]

[0040] In a dry argon-protected reaction tube, sequentially add [Ir(COD)Cl] 2 (0.002mmol), chiral ligand (0.004mmol), n-propylamine (0.3mL) and THF (0.5mL), react at 50°C for 30 minutes, cool to room temperature naturally, and pump dry. Add sodium o-aminothiophenate (0.2 mmol), potassium acetate (1.0 mmol), allyl carbonate (0.5 mmol), and DCM (2 mL) to the reaction tube in turn, and stir at room temperature for reaction. After the reaction, the solvent was removed under reduced pressure and the residue was subjected to thin-layer chromatography to obtain the target product (petroleum ether / dichloromethane=20 / 1, or petroleum ether / ethyl acetate=20:1, v / v).

Embodiment 27

[0042] Synthesis of chiral nitrogen-sulfur heterocycles

[0043]

[0044] This structure has potential pharmaceutical activity or can be used as a synthetic backbone of natural products.

[0045] P1: (R)-2-(1-allylphenylthio)aniline

[0046]

[0047] White solid, 83% yield, 96%ee[Diacel CHIRALPAKAD-H (0.46cmx25cm); n-hexane / isopropanol=90 / 10, flow rate=1.0mL / min, detection wavelength=214nm; tR=7.16min(minor ), 7.82min (major)].

[0048] [α] D 20 =-24.8° (c 1.0, CHCl 3 );

[0049] 1 H NMR (400MHz, CDCl 3 )δ=7.35-7.26(m, 4H), 7.24-7.21(m, 2H), 7.10(dd, J=8.0, 7.2Hz, 1H), 6.70(d, J=8.0Hz, 1H), 6.61(dd , J=7.6, 7.2Hz, 1H), 6.13(ddd, J=16.8, 9.6, 8.8Hz, 1H), 5.00(d, J=10.0Hz, 1H), 4.90(d, J=16.8Hz, 1H) , 4.62 (d, J=8.4Hz, 1H), 4.55-4.16 (m, 2H).

[0050] 13 C NMR (100MHz, CDCl 3 )δ=149.0, 140.4, 137.6, 137.3, 130.4, 128.5, 127.7, 127.3, 118.2, 116.9, 116.2, 114.8, 55.9;

[0051] IR(KBr)ν 3461, 3359, 3061, 3018, 1747, 1604, 1479, 1449, 1412, 1311, 1265, 1159, 981,...

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Abstract

The invention relates to an o-aminophenyl chiral diallyl sulfide compound and its preparation method. The compound is an optically pure compound with a structural formula as the following, wherein R1 is arbitrarily selected from an alkyl group of C1-C16, an N, O or S-containing heterocyclic group of C4-C10 or an N, O or S-containing heteroaryl group and aryl group of C4-C10, and R2 is arbitrarily selected from an alkyl group of C1-C16, an N, O or S-containing heterocyclic group of C4-C10 or an N, O or S-containing heteroaryl group and aryl group of C4-C10. Compared with the prior art, the method provided in the invention has the advantages of easily available and high catalytic activity catalyst, mild conditions, and wide application range of substrate.

Description

technical field [0001] The present invention relates to a kind of sulfur-containing compound, especially relate to a kind of allyl thioetherification reaction of allyl carbonate and o-aminothiophenate sodium catalyzed by metal iridium complex, the reaction can be high-response and high-efficiency Enantioselective synthesis of optically active o-aminothiophenol chiral allyl sulfide compounds. Background technique [0002] Sulfur-containing compounds can be found in most living tissues, which play an important role in life chemistry, for example, vitamin H, flavoring agents, protein cross-linking reagents, and ligands in bio-inorganic complexes, all contain S atoms . Optically active chiral sulfur-containing compounds are of great significance in organic synthesis and drug synthesis [a) Fraústo da Silva, J.R.; Williams, R.J.P.The Biological Chemistry of the Elements; Oxford University Press: New York, 2001.b)P .Metzner, A.Thuillier, Sulfur Reagents in Organic Synthesis, Acad...

Claims

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Application Information

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IPC IPC(8): C07B53/00C07C319/14C07C323/36C07C323/49C07D333/18C07D281/18B01J31/24
Inventor 赵晓明高宁郑生财杨为康
Owner TONGJI UNIV
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