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Diboron glycol ester as well as preparation method, intermediate and application thereof

A biboronic acid glycol ester and halogen technology, applied in the field of biboronic acid glycol ester, can solve the problems of single structure of biboronic acid glycol ester and the like

Active Publication Date: 2020-07-24
宁波赜军医药科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] The technical problem to be solved by the present invention is that the existing diol diborate has a single structure, so the present invention provides a diol diborate, its preparation method, its intermediate and its application

Method used

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  • Diboron glycol ester as well as preparation method, intermediate and application thereof
  • Diboron glycol ester as well as preparation method, intermediate and application thereof
  • Diboron glycol ester as well as preparation method, intermediate and application thereof

Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

[0092] Preparation Example 1 Preparation of Chiral Diol

[0093]

[0094] Select a suitable three-necked bottle, weigh the magnesium scraps (19.5g, 0.81mol, 1.5eq) with a smooth and dry surface and replace the nitrogen three times, add re-distilled THF (200ml) and two iodine under nitrogen protection, and then add an appropriate amount of aryl Bromine reagent (total 0.54mol, 1.0eq), then heated with a hair dryer to initiate the Grignard reagent, the solution yellow faded and turned colorless, continue to add aryl bromide, keep the reaction system slightly boiling, indicating that the Grignard reaction has been initiated, and the addition of aromatic After the base bromide, the unsubstituted or substituted methyl R-mandelate (0.11mol, 0.2eq) was dissolved in re-distilled THF (50mL) solution, added dropwise to the Grignard reagent, and the reaction was heated to reflux for about 4 hours. After completion, the reaction was cooled to room temperature, quenched by pouring into s...

preparation example 2

[0113] Preparation Example 2 Preparation of Chiral Diboron DB4~DB7

[0114]

[0115] Select a suitable Schlenk tube, add diol 5 (30g, 86mmol, 2.0eq), tetrahydroxydiboron (3.9g, 43mmol, 1.0eq) and an appropriate amount of 4A molecular sieves, pump nitrogen three times, add redistilled THF under nitrogen protection (150ml), the system was placed in a 70°C oil bath to reflux, and the reaction was completed in about 4 hours. The reaction system was cooled to room temperature, filtered through diatomaceous earth, washed with dichloromethane, the filtrate was spin-dried, washed with petroleum ether, and filtered again. The white solid powder of the filter cake was 28.7 g of the double boron product, and the yield was 94%. (DB4).

[0116]

[0117] White solid; 94% yield; Optical rotation: [α] D 29 =275.2°[c=1.10, CHCl 3 ]. 1 H NMR (400MHz, CDCl 3 ): δ7.70(s, 2H), 7.26(s, 2H), 7.07-6.99(m, 14H), 6.73(m, 2H), 6.59(m, 4H), 2.45(s, 6H), 2.14( s,6H),1.92(s,6H),1.53(s,6H). 13...

Embodiment 1

[0130] Example 1 Asymmetric reduction of aromatic imines to conjugate substrates

[0131]

[0132] In a clean and dry shlenk tube, aryl aldehyde (0.2 mmol, 1.0 eq) was added, the system was purged with nitrogen three times, and under nitrogen protection, ammonia methanol solution (7.0 M, 3.0 mmol, 15.0 eq) was added, and The solvent was evaporated to tetrahydrofuran (2 mL), the system was sealed, the reaction was stirred at room temperature for 1 h, under nitrogen protection, DB4 (0.11 mmol, 0.55 eq) was added, and the mixture was stirred at room temperature (20-30 °C) for 12-24 h. The system was rotary evaporated to remove excess ammonia, 1 mL of methanol was added, hydrochloric acid (3.0 M, 1 mL) was added to adjust the pH to about 3, washed with dichloromethane, the organic phase was concentrated, and the chiral diol diol5 (95% recovery) was recovered by beating with n-hexane. Rate). The aqueous phase was added with sodium hydroxide solution to adjust the pH to about 12...

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Abstract

The invention discloses diboron glycol ester as well as a preparation method, an intermediate and application thereof. The diboron glycol ester can be used for inducing reductive coupling reaction with imine as a substrate, and the substrate can be obtained by reaction of aldehyde and ammonia and is very easy to obtain and quite low in cost. The product can be separated from a reaction system onlyby acid-base operation without column chromatography purification, and the post-treatment mode is convenient and easy to operate. The yield of the obtained product is high, and protective group operation is not needed. The diboron glycol ester has chirality, the stereoselectivity of the reductive coupling reaction is generally excellent, and 99% ee chiral diamine can be obtained only through simple recrystallization. The diboron glycol ester can be obtained by reacting diol with diboron glycol ester, the diol is convenient to prepare and easy to amplify, the diol can be recycled from a reaction solution through simple acid-base operation, the recovery rate reaches 95%, and the preparation cost is further saved.

Description

technical field [0001] The present invention relates to a diboronic acid glycol ester, its preparation method, its intermediate and its application. Background technique [0002] Biboronic acid glycol ester has the advantages of non-toxicity, stability, easy operation, etc., and has a wide range of uses in organic synthesis. According to different sources of diols, it can be divided into achiral diboronic acid diol ester and chiral diboronic acid diol ester. Among them, achiral diboronic acid glycol ester was widely used in Miyaura coupling reaction to prepare organoboronate compounds (Org. Synth. 2000, 77, 176-185). With the development of organic chemistry in recent years, it has also been gradually applied to the addition of alkenes, alkynes, aldehydes (ketones), imines and other compounds and the C-H boron substitution of aromatic compounds (Chem.Rev.2016, 116,9091). Compared with achiral diboronic acid diol esters, due to the limited sources of chiral diols and the g...

Claims

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Application Information

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IPC IPC(8): C07F5/02C07C33/26C07C43/23C07C209/00C07C211/29C07C211/30C07C213/02C07C217/58C07C227/10C07C229/38C07C251/24C07D307/52C07D333/20C07B43/04
CPCC07F5/022C07C33/26C07C43/23C07C209/00C07C211/29C07C213/02C07C217/58C07C227/10C07C229/38C07C211/30C07D307/52C07D333/20C07C251/24C07B43/04Y02P20/55
Inventor 汤文军徐广庆周明康
Owner 宁波赜军医药科技有限公司
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