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A kind of preparation method of substituted 2,3-dihydrobenzo[d][1,3]oxaphosphorine ligand

A ligand and unsubstituted technology, applied in the field of organic catalysis, can solve the problems of low efficiency, high production cost, and low flexibility

Active Publication Date: 2017-03-22
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In addition, although the existing methods for synthesizing such ligands can be scaled up (Org. Lett. 2010, 12, 176-179), they have many steps, low efficiency, high production costs, and low flexibility

Method used

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  • A kind of preparation method of substituted 2,3-dihydrobenzo[d][1,3]oxaphosphorine ligand
  • A kind of preparation method of substituted 2,3-dihydrobenzo[d][1,3]oxaphosphorine ligand
  • A kind of preparation method of substituted 2,3-dihydrobenzo[d][1,3]oxaphosphorine ligand

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preparation example Construction

[0104] Ligand preparation method

[0105] The invention also discloses a new method for preparing the compound of the formula I of the invention. The method has mild reaction conditions and few reaction steps, and is suitable for industrial production.

[0106] The preparation method of the ligand of formula I of the present invention is specifically described below, but these specific methods do not constitute any limitation to the present invention.

[0107]The ligand of formula I of the present invention can be prepared by the following method, but the specific conditions of the method, such as reactants, solvents, the amount of the compound used, reaction temperature, time required for the reaction, etc. are not limited to the following explanations. The compound of the present invention can also be conveniently prepared by optionally combining various synthetic methods described in the specification or known in the art. Such a combination can be easily performed by those ...

Embodiment 13

[0145] Preparation of Example 13-tert-butyl-4-hydroxyl-2,3-dihydrobenzo[d][1,3]oxaphosphorine

[0146]

[0147] step 1)

[0148] Compound 1 (9.06mL, 69.2mmol, 1.10equiv) was dissolved in THF (50mL), cooled to 0°C, N 2 Slowly add n-BuLi n-hexane solution (30.0mL, 69.2mmol, 1.10equiv, 2.5M) dropwise to the solution under protection, keep the internal temperature below 0°C, and continue stirring at 0°C for 2h to obtain the lithium salt Solution 2 and save for future use.

[0149] step (2)

[0150] Compound t-BuPCl 2 (10.00g, 62.9mmol, 1.00equiv) was dissolved in 50mLTHF, the temperature was lowered to 0°C, and the lithium salt solution 2 obtained above was slowly added dropwise to the solution, keeping the internal temperature below 0°C, and continued stirring at 0°C for 1h, Then warm to room temperature and stir for 2h. Add 10mL H to the system 2 O, continue to stir at room temperature for 3h to obtain compound 3.

[0151] step (3)

[0152] N 2Add NaOH (5.10 g, 2.00 ...

Embodiment 23

[0169] Preparation of Example 23-phenyl-4-hydroxyl-2,3-dihydrobenzo[d][1,3]oxaphosphorine

[0170]

[0171] step 1)

[0172] Compound 1 (6.28mL, 48.65mmol, 1.1equiv) was dissolved in THF (40mL), cooled to -78°C, N 2 Slowly add n-BuLi n-hexane solution (19.48mL, 48.65mmol, 1.1equiv, 2.5M) dropwise to the solution under protection, keep the internal temperature below 0°C, and continue stirring at 0°C for 2h to obtain the lithium salt Solution 2 and save for future use.

[0173] step (2)

[0174] Compound PhPCl 2 (6mL, 44.25mmol, 1.0equiv) was dissolved in 40mLTHF, cooled to -78°C, and the lithium salt solution 2 obtained above was slowly added dropwise to the solution, keeping the internal temperature at -78°C, and continued to stir at -78°C for 1h. Add 10mL H to the system 2 O, continue stirring at room temperature for 1 h to obtain compound 3.

[0175] step (3)

[0176] N 2 Add NaOH (3.53 g, 2 equiv) and HCHO (5 mL mL, 1.50 equiv, concentration 40%) to the above mix...

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Abstract

The invention relates to a preparation method of a substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand. The preparation method of the substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand comprises the following concrete steps: (b) in presence of alkali and a hydroxymethylation reagent, carrying out hydroxymethylation on a compound show in a formula II to obtain a compound shown in a formula C; (c) in presence of a halogenating reagent, carrying out halogenating reaction on the compound shown in the formula C to obtain a compound shown in a formula D; (d) in presence of Lewis acid or Bronsted acid and alkali, carrying out demethylation cyclization reaction on a compound shown in the formula D to obtain a compound shown in a formula E; and (e) in presence of a reducing agent, carrying out reduction reaction on the compound shown in the formula E to obtain the ligand shown in a formula I, wherein groups in each formula are defined in the specification. The invention also discloses a compound shown in the formula II and a preparation method thereof. The preparation method of the substituted 2,3-dihydrobenzo[d][1,3] oxa-phosphole ligand is simple in steps, mild in reaction conditions and applicable to industrial production.

Description

technical field [0001] The invention relates to the technical field of organic catalysis, in particular to a preparation method of a substituted 2,3-dihydrobenzo[d][1,3]oxaphosphorine ligand. Background technique [0002] Substituted 2,3-dihydrobenzo[d][1,3]oxaphosphorine ligand compounds have been widely used in the field of organic chemistry. At present, a variety of excellent chiral or achiral ligands have been developed and have been used for asymmetric hydrogenation (Angew.Chem., Int.Ed.2013, 52, 4235-4238; Org.Lett.2010, 12, 176-179; Org. Lett. 2010, 12, 1104-1107), cross-coupling (Chem. Eur. J., 2013, 19, 2261; Org. Lett. 2012, 14, 2258–2261; Adv. Syn.Cat.2011, 353, 1671-1675; Org.Lett.2011, 13, 1366-1369; Adv.Asy.Cat.2011, 353, 533-537; Angew.Chem., Int.Ed.2010, 49 , 5879-5883), and catalytic nucleophilic substitution reactions (J.Org.Chem.2013, 78, 6350-6355; Adv.Syn.Cat.2013, 355, 1297-1302; J.Am.Chem.Soc.2010 , 132, 7600-7601) and other important organic reacti...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/6571C07F9/46
Inventor 汤文军付文振
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI