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Preparation method of axially chiral biaryl compound and chiral fluorenol compound

A compound and biaryl technology, which is applied in the field of preparation of axial chiral biaryl compounds and chiral fluorenol compounds, can solve problems such as complex catalysts and limited application range, and achieve good tolerance, universality and low price Inexpensive, the effect of reducing the amount of use

Active Publication Date: 2020-09-15
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, most of these methods need pre-synthesized substrates with special functional groups, or require more complex catalysts, which greatly limits the scope of use of these methods

Method used

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  • Preparation method of axially chiral biaryl compound and chiral fluorenol compound
  • Preparation method of axially chiral biaryl compound and chiral fluorenol compound
  • Preparation method of axially chiral biaryl compound and chiral fluorenol compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Preparation of Compound I-1

[0050]

[0051] Under argon protection, palladium acetate (2.3 mg, 0.01 mmol), potassium carbonate (34.6 mg, 0.25 mmol) and dry acetonitrile (1.0 mL) were added to a dry reaction tube equipped with a magnetic stirrer, and then ( 1S,4R)-2-norbornene-2-carboxylic acid ethyl ester (8.3mg, 0.05mmol), 1-iodonaphthalene (38.1mg, 0.15mmol), 2-bromo-3-methylbenzoate (22.9 mg, 0.1 mmol) and tert-butyl acrylate (19.2 mg, 0.15 mmol). The resulting mixture was reacted at 105° C. for 24 hours under an argon atmosphere. After the reaction was completed, it was cooled to room temperature, the mixture was filtered with diatomaceous earth, washed with ethyl acetate, the solvent was distilled off under reduced pressure, and purified by column chromatography to obtain compound I-1 (colorless oily liquid, 78% yield, 96% ee) . 1 H NMR (400MHz, CDCl 3 ):δ8.23–8.20(m,1H),7.89–7.82(m,3H),7.71(d,J=16.3Hz,1H),7.57–7.50(m,2H), 7.45–7.43(m,1H ),7.38–7.34(m,1H)...

Embodiment 2～19

[0053] Preparation of Compounds I-2~I-19

[0054] The operation steps are the same as in Example 1, except that the olefins used are: ethyl acrylate, benzyl acrylate, N,N-dimethylacrylamide, N,-methyl-N-methoxyacrylamide, acrolein , vinyl sulfone, vinyl phosphate, vinyl trimethylsilane, vinyl ethyl ether, 2-methyl-3-buten-2-ol, allyl alcohol, homoallyl alcohol, 5-hexyl- 1-alcohol, styrene, 4-fluorostyrene, 4-methoxystyrene, 4-nitrostyrene, 3-vinylbenzothiophene. Axial chiral biaryl products with different substituent terminations were obtained, and the results are shown in Table 1.

[0055] Table 1 Example 2~19 obtained axial chiral biaryl compound result

[0056]

Embodiment 20

[0058] Preparation of Compound I-20

[0059]

[0060] The operation steps were the same as in Example 1, except that the structure of the alkene (52.9 mg) used was as follows to obtain compound I-20 (yellow oily liquid, 96% yield, 97% ee). 1 H NMR (400MHz, CDCl 3 ):δ8.31–8.27(m,1H),7.93–7.89(m,1H),7.84(d,J=8.4Hz,1H),7.80(dd,J=8.1,1.2Hz,1H),7.76– 7.72(m,2H),7.69–7.67(m,2H),7.56–7.50(m,2H),7.41(d,J=7.2Hz,1H),7.36–7.32(m,3H),7.30–7.24( m,2H), 6.88–6.84(m,2H),6.67(d,J=16.5Hz,1H),5.14–5.05(m,1H),3.53(s,3H),2.00(s,3H),1.66 (s,6H),1.21(s,3H),1.20(s,3H); 13 C NMR (100MHz, CDCl 3 ):δ195.01,173.31,168.25,159.55, 141.86,141.27,137.35,137.07,136.95,134.30,133.75,133.25,132.45,132.06,131.73,131.11, 130.80,130.41,128.69,127.67,127.62,127.42,127.37,126.42, 126.11, 125.80, 125.61, 117.23, 79.45, 69.45, 52.02, 25.49, 21.66, 20.67; HRMS (ESI-TOF): calc'd for C 41 h 38 NaO 6 [M+Na] + 649.2561, found 649.2559; HPLC: Daicel chiralpak AD-H column, 15% i PrOH in n Hexane, 1 mL / min, λ=...

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Abstract

The invention discloses a preparation method of an axially chiral biaryl compound and a chiral fluorenol compound. The preparation method comprises the following steps: stirring and reacting aryl iodide, aryl bromide and olefin which are taken as starting raw materials in an organic solvent at 50-150 DEG C under the action of a palladium catalyst, a phosphine ligand, a chiral norbornene derivativeand an alkali to obtain the biaryl axial chiral compound and the chiral fluorenol compound. The method has the advantages of cheap and easily available raw materials, mild reaction conditions, good substrate universality, high yield and simple preparation process. The prepared biaryl axial chiral compound can be applied to synthesis of novel chiral ligands and chiral catalysts.

Description

technical field [0001] The invention relates to a preparation method of an axial chiral biaryl compound and a chiral fluorenol compound, belonging to the field of organic synthesis. Background technique [0002] The axial chiral biaryl skeleton is a very important structural unit, which widely exists in biologically active natural products, drug molecules and chiral materials ([1] Q.Li, L.Green, N.Venkataraman, I .Shiyanovskaya, A.Khan, A. Urbas, J.W.Doane, J.Am.Chem.Soc.2007, 129, 12908; [2] J.E.Smyth, N.M.Butler, P.A.Keller, Nat.Prod.Rep.2015, 32, 1562; [3] J. Clayden, W.J. Moran, P.J. Edwards, S.R. LaPlante, Angew. Chem. Int. Ed. 2009, 48, 6398). In addition, chiral ligands and catalysts based on axial chiral biaryl groups play an important role in asymmetric catalytic reactions ([1] R. Noyori, H. Takaya, Acc. Chem. Res. 1990, 23, 345; [ 2] Y.Chen, S. Yekta, A.K.Yudin, Chem.Rev.2003, 103, 3155; [3] D.Parmar, E.Sugiono, S.Raja, M.Rueping, Chem.Rev.2014, 114, 9047). In ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/38C07C41/30C07C67/343C07C201/12C07C231/12C07C253/30C07C259/06C07C315/04C07D213/64C07D221/16C07D295/192C07D333/60C07F7/08C07F7/18C07F9/40C07F9/53C07J1/00C07C69/76C07C233/11C07C205/57C07C69/92C07C317/44C07C255/57C07C233/65C07C205/06C07C35/44C07C35/52C07C43/23C07C235/66C07C205/13C07B37/04C07B37/10
CPCC07B37/04C07B37/10C07C29/38C07C41/30C07C67/343C07C201/12C07C231/12C07C253/30C07C259/06C07C315/04C07D213/64C07D221/16C07D295/192C07D333/60C07F7/081C07F7/083C07F7/1892C07F9/4003C07F9/4075C07F9/5325C07J1/0059C07C2601/02C07C2601/14C07C2602/28C07C2603/40C07C2603/54C07C69/76C07C233/11C07C205/57C07C69/92C07C317/44C07C255/57C07C233/65C07C205/06C07C35/44C07C35/52C07C43/23C07C235/66C07C205/13
Inventor 周强辉刘泽水
Owner WUHAN UNIV
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