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Preparation method of (2R,3R)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol and (2S,3S)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol

A dimethoxy, tetraphenyl technology, applied in the field of chiral compound preparation chemistry, to achieve the effects of high product yield, easy operation, easy protection and deprotection

Inactive Publication Date: 2010-12-22
WUHAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although Pietruszka improved the yield after optimizing the reaction [Luithle, J.E.A.; Pietruszka, J.J.Org.Chem.1999, 64, 8287-8297.], in recent years some people have also achieved a certain degree of success in deprotection with new systems [(a) Srimurugan, S.; Suresh, P.; Viswanathan, B.; Varadarajan, T.K. Syn. Commu. 2007, 37, 2483-2490. (b) Bischop, (M.; V.; Pietruszka, J.Synthesis 2008, 2488-2490], but there are still many problems in terms of cost and environment

Method used

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  • Preparation method of (2R,3R)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol and (2S,3S)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Example 1: Preparation of enantiopure 1,1,4,4-tetraphenyl substituted butanetetraol

[0029] According to the conventional reaction method, the enantiomerically pure (2R, 3R)- or (2S, 3S)-diethyl tartrate solution in tetrahydrofuran was added dropwise to four to ten equivalents of phenyl magnesium bromide in tetrahydrofuran solution. . After the reaction is completed, it is quenched with saturated aqueous ammonium chloride solution, extracted with ether, and (2R, 3R)- or (2S, 3S)-1,1,4,4-tetraphenylbutanetetraol is separated from the organic phase . After silica gel column chromatography, the yield of (2R, 3R)- or (2S, 3S)-1,1,4,4-tetraphenyltetramole is about 50%.

[0030] (2S,3S)-1,1,4,4-tetraphenyltetramethylenetetraol: m.p.: 149-150°C; [α] D 25 =-156.6(c=1.1, in CHCl 3 ).IR: 3437, 3058, 2916, 1598, 1492, 1447, 1062, 698. 1 H-NMR: 7.37-7.13 (m, 20H, Ar-H), 4.63 (d, 2H, J=4.8 Hz, OH, add D 2 Disappear after O), 4.42 (d, 2H, J = 4.5 Hz, CH); 3.69 (d, 2H, J = 4.8, OH, add ...

Embodiment 2

[0032] Example 2: Preparation of Chiral Spiroborate Sodium Salt

[0033] Add 1,1,4,4-tetraphenyltetramethylenetetraol and THF into a two-neck round bottom flask, stir to dissolve, and then add H 3 BO 3 , NaOH and water, stir to dissolve, heat to reflux until all the raw material 1,1,4,4-tetraphenylbutanetetraol disappears, remove the solvent THF by rotary evaporation, treat with water, filter with suction, and crystallize the solid with ethanol to obtain chiral spiroboronic acid Sodium, the yield is 96%, mp>300℃, [α] D 25 = +10.79 (c 1.0, THF). 1 H NMR(300MHz, DMSO-d 6 ): δ7.15-6.85(m, 32H, 32Ph-H), 6.76(s, 8H), 4.46(s, 4H, 4OC-H), 4.18(s, 4H, 4O-H, add D 2 Disappear after O). 13 C NMR(75MHz, DMSO-d 6 ): δ153.2, 148.9, 133.2, 132.7, 131.8, 131.0, 85.6, 83.0. Ms: 883(M+1) + .

Embodiment 3

[0034] Example 3: Preparation of Chiral Spiroborate Sodium Salt

[0035] 1,1,4,4-Tetraphenylbutanetetraol and sodium borohydride were refluxed in THF until all the tetraols of the raw materials disappeared, and then spin-dried to obtain a white solid, which was stirred with water and filtered. The solid was crystallized with ethanol. The yield was 95%.

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Abstract

The invention relates to a preparation method of (2R,3R)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol and (2S,3S)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol, which comprises the steps of preparing chiral 1,1,4,4-tetraphenyl butantetraol by carrying out hydrocarbylation on antipode purity (2R,3R)-tartaric ester and (2S,3S)-tartaric ester with a phenyl Grignard reagent; and then reacting with a boron compound in the presence of a metal compound or an amino compound to generate chiral spiral borate to obtain the (2R,3R)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol and (2S,3S)-1,4-dimethoxyl-1,1,4,4-tetraphenyl-2,3-butanediol with high yield. The method has the remarkable characteristics of easy obtaining of raw materials (no need of special reagents or expensive reagents), simple process, convenient and simple operation, good reaction selectivity, high yield of products, and the like.

Description

Technical field [0001] The present invention relates to a new method for preparing (2R, 3R)- and (2S, 3S)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol, belonging to Chiral compound preparation chemistry field. Background technique [0002] Has C 2 -Chiral diols with symmetry axis have been widely used in asymmetric synthesis reactions and supramolecular chemistry. Such as the chiral 1,1,4,4-tetrasubstituted 1,4-butanediol compound TADDOL derived from tartaric acid [Seebach, D.; Beck, AK; Imwinkelried, R.; Roggo, S.; Wonnacott, A. Helv Chim. Acta 1987, 70, 954-74.] There have been a lot of studies [important comments in recent years: Pellissier, H. Tetrahedron 2008 64(45) 10279-10317; Seebach, D.; Beck, AK and Heckel, A. Angew. Chem. Int. Ed. 2001, 40, 92-138]. Among them, chiral (2R, 3R)- and (2S, 3S)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol derived from tartrate In the asymmetric cyclopropanation reaction [(a) Luithle, JEA; Pietruszka, J. Liebigs Ann. Chem. / Rec. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C43/178C07C41/18
Inventor 单自兴宋少军
Owner WUHAN UNIV
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