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Chiral carboxylic acid compound as well as synthesis method and application thereof

A chiral carboxylic acid and compound technology, applied in the field of organic synthesis, can solve the problem of less chiral carboxylic acid and achieve high yield and enantioselectivity

Active Publication Date: 2021-08-03
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The development of chiral ligands plays a vital role in asymmetric reactions, but currently there are too few types of chiral carboxylic acids in the field of asymmetric carbon-hydrogen bond activation, and many asymmetric carbon-hydrogen bond activation reactions No chiral carboxylic acid matches for chiral control

Method used

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  • Chiral carboxylic acid compound as well as synthesis method and application thereof
  • Chiral carboxylic acid compound as well as synthesis method and application thereof
  • Chiral carboxylic acid compound as well as synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] The preparation of embodiment 1 (S)-2'-(diisopropylcarbamoyl)-[1,1'-binaphthyl]-2-carboxylic acid:

[0030]

[0031] In the first step, 2.5 mmol of (S)-[1,1'-binaphthalene]-2,2'-dicarboxylic acid and 1.25 mmol of silver carbonate were mixed in 20 mL of organic solvent acetone, and 7.5 mmol of methyl iodide Add dropwise to the above reaction solution, the dropping temperature is 40°C, react at 40°C for 6 hours after dropping, after the reaction is complete, add ethyl acetate, filter, the filtrate is concentrated to dryness under reduced pressure, and the monoester compound B is obtained by column chromatography .

[0032] In the second step, the product obtained in the first step (2.2 mmoles of product B) was added to 20 mL of organic solvent dichloromethane, 5 drops of N,N'-dimethylformamide was added dropwise, and 3.3 mmoles of oxalyl chloride was added dropwise to To the above reaction solution, the dropwise addition temperature was 0°C, and after the dropwise rea...

Embodiment 2

[0035] Embodiment 2 Preparation of other various chiral carboxylic acids

[0036] The preparation process is the same as in Example 1, but the amine added in the third step is replaced by other correspondingly substituted amines to obtain the corresponding chiral carboxylic acid data as follows:

[0037] (S)-2'-(pyrrolidine-1-carbonyl)-[1,1'-binaphthyl]-2-carboxylic acid

[0038]

[0039] 1 H NMR (400MHz, CDCl 3 )δ14.61(s,1H),8.04(dd,J=8.5,2.8Hz,2H),7.94(t,J=9.0Hz,2H),7.83(d,J=8.5Hz,1H),7.56– 7.44(m,3H),7.31(dd,J=8.4,7.0Hz,1H),7.28(s,1H),7.12(d,J=8.5Hz,1H),7.01(d,J=8.6Hz,1H ),3.61–3.55(m,1H),3.43–3.30(m,2H),3.10–3.03(m,1H),1.92–1.74(m,2H),1.69–1.63(m,1H),1.47–1.35 (m,1H). 13 C NMR (100MHz, CDCl 3 ) Δ171.2,170.9,135.0,134.1,134.0,133.9,132.5,132.0, 139.5, 129.3,128.2,127.9,126.8,125.7,25.7,25.7,25.7,25.7,25.7,25.3,3.3,3.3,3.3,3.3,3.3,3.3,3.3,3.3,3.3. , 24.1. HRMS (ESI) calcd for C 26 h 20 NO 3 - (M-H) - :394.1449,found:394.1446.

[0040] (S)-2'-(Diethylcarbamoyl...

Embodiment 3

[0064] Example 3 Chiral carboxylic acid was used as a ligand for ruthenium-catalyzed cyclization reaction of sulfoximine derivative 1a with α-carbonylsulfide ylide derivative 2a to prepare chiral sulfoximine derivative 3aa.

[0065] 0.1 mmol of sulfoximine derivative 1a, 0.1 mmol of α-carbonylsulfide ylide derivative 2a, 0.0025 mmol of p-cymene ruthenium(II) dichloride dimer, 0.02 mmol of hexa Silver fluoroantimonate, 0.01 mmol of (S)-2'-(diisopropylcarbamoyl)-[1,1'-binaphthyl]-2-carboxylic acid mixed in 2 ml of 1,2-dichloroethane In alkanes, the reaction was carried out at 35° C. for 12 hours under the protection of nitrogen. After the reaction, the product chiral sulfoximine derivative 3aa was obtained by thin-layer silica gel plate chromatography.

[0066]

[0067] Characterization of typical product 3aa:

[0068] (S)-1,3-Diphenylbenzo[e][1,2]thiazine 1-oxide

[0069]

[0070] Yield 96%, ee 98%. HPLC [AD-H] (n-hexane / isopropanol=80 / 20, 1.2 ml / min) λ=254nm, tr=13.9m...

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Abstract

The invention relates to a preparation method and application of chiral carboxylic acid. The chiral carboxylic acid compound has a structure shown in a formula (1), the chiral carboxylic acid compound has a chiral binaphthalene skeleton and a chiral spirobiindane skeleton, and carboxylic acid and amide substituent groups are respectively arranged on 2 and 2' sites of the binaphthalene skeleton and 7 and 7' sites of the spirobiindane skeleton. The chiral carboxylic acid compound can be synthesized by taking [1,1'-binaphthalene]-2,2'-dicarboxylic acid and 1,1'-spirobiindane-7,7'-dicarboxylic acid with optical activity as starting raw materials, the reaction condition is mild, and the operation is simple and convenient. The chiral carboxylic acid is a novel protonic acid chiral catalyst. The chiral carboxylic acid compound is especially suitable for asymmetric reaction catalyzed by transition metal, and the product has high yield and enantioselectivity.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a novel synthesis method of chiral carboxylic acid and its application in ruthenium-catalyzed asymmetric synthesis of chiral sulfoximine derivatives. Background technique [0002] Transition metal-catalyzed asymmetric carbon-hydrogen bond activation can construct a variety of chiral frameworks through one-step tube energization reactions of carbon-hydrogen bonds that are widely present in organic matter. Compared with the traditional asymmetric synthesis, it is simpler and more efficient and has great potential application value. It has developed into a frontier and hot field of asymmetric catalysis research. In the activation of carbon-hydrogen bonds catalyzed by high-valent metals such as palladium, rhodium, iridium, cobalt, and ruthenium, carboxylate groups are often added to assist in the completion of the alkali-assisted metallation process, so it is generally be...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C233/65C07D295/192C07C231/02C07C231/12C07C67/10C07C69/76B01J31/22C07D279/02C07D417/04
CPCC07C233/65C07D295/192C07C231/02C07C231/12C07C67/10B01J31/2295B01J31/2213C07D279/02C07D417/04C07B2200/07C07C2601/14C07C2603/94B01J2531/821B01J2531/0225C07C69/76
Inventor 史炳锋周涛
Owner ZHEJIANG UNIV
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