Method for preparing chiral dihydrobenzofuran compounds and catalyst used thereby

A technology of chroman and compounds, applied in the field of a method and the catalyst used, can solve the problems of difficulty in obtaining optically pure axial chiral ligands, poor substrate applicability, complex separation methods, etc., and achieve a simple synthesis method , avoid waste of resources, high reactivity effect

Inactive Publication Date: 2009-04-22
SHANGHAI JIAO TONG UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Through these literatures, it can be found that the defects and deficiencies in the design and development of axial chiral metal complexes are: Looking at the development of axial chiral metal catalysts in recent decades, people first obtain axial chiral ligands, and then coordinate with the metal axial chiral metal catalyst
From the point of view of atom economy, the ligands designed in this way have obvious limitations: it is difficult to obtain optically pur

Method used

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  • Method for preparing chiral dihydrobenzofuran compounds and catalyst used thereby
  • Method for preparing chiral dihydrobenzofuran compounds and catalyst used thereby
  • Method for preparing chiral dihydrobenzofuran compounds and catalyst used thereby

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Embodiment 1

[0041] Embodiment 1: Compound (S, aS)-II(R 1 = Ph, R 2 = R 3 = R 4 =H, M=Pd) synthesis

[0042] Under nitrogen, V (7.4mg, 10.08□mol) was mixed with Pd(OCOCF 3 ) 2 (6.7 mg, 20.15 mol) was dissolved in tetrahydrofuran and stirred for 10 minutes to obtain a bimetallic axial chiral catalyst (S, aS)-II with a yield of 95%.

[0043] Its characteristic parameters are: 1 H NMR (400MHz, acetone-d 6 )δ7.90-8.00 (m, 6H, ArH), 7.35-7.39 (m, 12H, ArH), 7.01-7.04 (m, 8H, ArH), 5.11 (dd, J=7.2, 10.8Hz, 4H, OCH ), 4.88 (dd, J=9.2, 10.4Hz, 4H, NCH), 4.49 (dd, J=6.4, 9.6Hz, 4H, OCH).

Embodiment 2

[0044] Embodiment 2: Compound (S, aS)-II(R 1 =t-Bu,R 2 =R 3 =R 4 =H, M=Pd) synthesis

[0045] The preparation method of this embodiment is the same as that of Example 1.

[0046] The characterization parameters are: 1 H NMR (400MHz, acetone-d 6 ): δ8.32(d, J=3.6Hz, 4H, ArH), 8.18(dd, J=7.2, 8.4Hz, 2H, ArH), 4.53(t, J=9.2, 4H, NCH), 4.45(dd , J=5.2, 9.2Hz, 4H, OCH), 3.95(dd, J=5.6, 10.0Hz, 4H, OCH), 0.83(s, 36H, CH 3 ).

Embodiment 3

[0047] Embodiment 3: Compound (S, aS)-II(R 1 =i-Pr,R 2 =R 3 =R 4 =H, M=Pd) synthesis

[0048] The preparation method of this embodiment is the same as that of Example 1.

[0049] The characterization parameters are: 1 H NMR (400MHz, acetone-d 6 ): δ8.33(d, J=8.0Hz, 4H, ArH), 8.21(dd, J=7.2, 8.8Hz, 2H, ArH), 4.57(t, J=9.2, 4H, NCH), 4.26(dd , J=6.0, 8.8Hz, 4H, OCH), 3.65-3.71(m, 4H, OCH), 1.32(d, J=6.4Hz, 12H, CH 3 ), 1.03-1.12 (m, 4H, CH), 0.49 (d, J=6.8Hz, 12H, CH 3 ).

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Abstract

The invention relates to a method for preparing a chiral dihydrobenzofuran compound and a catalyst used by the same, which belongs to the technical field of chemical industry. The method prepares a chiral dihydrobenzofuran derivative IV by using a 2-allyl phenols compound III as a raw material and using an axial chiral metal complex as a catalyst in a reaction solvent in the presence of an oxidant, wherein the structural formula of the compounds III and IV are as above. The method uses the metal complex as the catalyst which has higher reactivity and enantioselectivity up to 99 percent and can be applied to various asymmetric catalytic reactions, wherein R5 is hydrogen, phenyl, naphthyl, halogen, benzyl, or alkyl with carbons of between 1 and 8; and R6 is hydrogen, phenyl, naphthyl, benzyl, or alkyl with carbons of between 1 and 8.

Description

technical field [0001] The invention relates to a method for preparing compounds in the technical field of chemical industry and a catalyst used therefor, in particular to a method for preparing chiral chroman compounds and the catalyst used therefor. Background technique [0002] Since the metal ruthenium complex of the axial chiral ligand BINAP has been successfully applied to the preparation of spices, medicines and their intermediates such as (-)-menthol, naproxen, vitamin E, morphine and carbapenicillin, the new axial chiral As a main research field of asymmetric catalysis, the synthesis and application of metal complexes have attracted more and more attention. To this end, a large number of axial chiral metal complexes have been developed and successfully applied to various reactions. [0003] After searching the prior art documents, it was found that "New Chiral Phosphorus Ligands for Enantioselective Hydrogenation" published by Professor Zhang Xumu et al. in "Chem.R...

Claims

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Application Information

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IPC IPC(8): C07D307/79C07B53/00B01J31/22B01J31/26
Inventor 张万斌张勇健王飞军
Owner SHANGHAI JIAO TONG UNIV
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