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Preparation method of (2R,3R)-or (2S,3S)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol

A technology of bismethoxybenzyl cyclosulfite and dimethoxy is applied in the field of preparation of C2 symmetrical chiral diols and achieves the effects of short synthetic route, easy operation and low cost

Inactive Publication Date: 2014-05-21
SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2008, Pietruszk, J. et al [Bischop, M.; Cmrecki, V.; Ophoven, V.; Pietruszk, J.Synthesis2008, 2488.] improved the preparation method: replaced expensive and toxic DDQ for oxidation, but still use LiAlH 4
Although the boron chemical method we researched and developed avoids oxidation and reduction procedures, it does not use expensive and toxic DDQ, LiAlH 4 and other reagents, but the NaH / MeI system is still used for methylation, and HF is used for hydrolysis, and there are still many problems in terms of cost and environment
[0004] Based on the above situation, the present invention provides a kind of optically pure tartrate as a chiral source, and the 2,3-position secondary hydroxyl group of chiral 1,1,4,4-tetraphenylbutanetetraol is protected and Deprotection, introducing a methoxy group through a substitution reaction between (4R,5R)- or (4S,5S)-4,5-diphenylchloromethyl cyclosulfite and methanol, avoiding the traditional NaH / MeI methyl group The prepared (4R,5R)- or (4S,5S)-4,5-bismethoxybenzhydryl cyclosulfite removes the sulfinyl protecting group under the catalysis of a certain concentration of base to prepare (2R,3R)- or (2S,3S)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol, the synthesis method has not been reported yet

Method used

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

Examples

Experimental program
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Embodiment 1

[0015] Example 1: The preparation method of (2R,3R)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol, the steps are as follows:

[0016] Step 1: Preparation of (2R,3R)-1,1,4,4-tetraphenylbutanetetraol

[0017] The THF solution of (2R,3R)-diethyl tartrate was added dropwise in 6 equivalents of THF solution of phenylmagnesium bromide which was stirring, after the reaction was completed, it was quenched with saturated aqueous ammonium chloride solution, extracted with ether, concentrated, (2R,3R)-1,1,4,4-Tetraphenylbutadiol was obtained by silica gel column chromatography, yield: 50%, m.p.:149-150℃; [α] D 25 =+154.0(c1.2,CHCl 3 );IR(KBr):3436,3058,2916,1598,1492,1447,1063,698; 1 H-NMR (CDCl 3 ,300MHz):δ7.37–7.13(m,20H,Ar-H);4.65(d,J=7.2Hz,2H,OH)4.41(d,J=4.7Hz,2H,CH);3.77(d, J=5.3Hz,2H,OH). 13C-NMR(CDCl3,75MHz)δ143.8;142.7;134.6;131.5;129.3;128.3;128.2;127.9;127.5;126.7;125.5;81.3,69.7.

[0018] Step 2: Preparation of (4R,5R)-4,5-diphenylchloromethyl cyclosulfite

[0019] ...

Embodiment 2

[0025] Example 2: The preparation of (2S,3S)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol, the steps are as follows:

[0026] Step 1 and Step 2: Only the raw material (2R,3R)-diethyl tartrate is replaced with (2S,3S)-diethyl tartrate, and the rest of the operations are the same as in Example 1 to obtain (4S,5S)-4, 5-Diphenylchloromethylcyclosulfite.

[0027] Step 3: Preparation of (4S,5S)-4,5-bismethoxybenzhydryl cyclic sulfite

[0028] (4S,5S)-4,5-bisdiphenylchloromethyl cyclosulfite and triethylamine (1:4 molar ratio) were dissolved in anhydrous methanol, heated at 70°C for 3 hours, concentrated, and cooled to Precipitation of (4S,5S)-4,5-bismethoxybenzhydryl cyclosulfite at room temperature, yield: 95%, m.p.: 125-128℃, [α] D 20 =+209(c1,CH 2 Cl 2 ). 1 H-NMR (300MHz, CDCl 3 ):δ7.46-7.25(m,20H),5.87(d,J=1.8Hz,1H),5.55(d,J=1.5Hz,1H),3.00(s,3H),2.64(s,3H) . 13 C-NMR (75MHz, CDCl 3 ): δ134.9, 134.1, 133.9, 133.6, 132.5, 132.3, 132.2, 131.9, 90.8, 88.9, 57.9, 56.5. ...

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Abstract

The invention discloses a preparation method of (2R,3R)-or (2S,3S)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol. The preparation method comprises the steps of phenylating optically pure diethyl tartrate to obtain (2R,3R)-or (2S,3S)-1,1,4,4-tetraphenyl butantetraol; reacting with sulfoxide chloride to generate (4R,5R)-or (4S,5S)-4,5-bis diphenyl chloromethyl cyclic sulfite; with presence of alkali, implementing substitution reaction with methanol in a suitable medium to introduce a methoxy group, thus preparing (4R,5R)-or (4S,5S)-4,5-bismethoxy diphenylmethyl cyclic sulfite; and with presence of alkali, removing a sulfinyl protecting group in a suitable medium to obtain (2R,3R)-or (2S,3S)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol. The method disclosed by the invention is easily available in raw material, simple and convenient to operate, and low in cost.

Description

technical field [0001] The present invention relates to C 2 The preparation method of symmetrical chiral diols belongs to the technical field of preparation methods of chiral compounds, and specifically discloses a (2R,3R)- or (2S,3S)-1,4-dimethoxy-1,1, The preparation method of 4,4-tetraphenyl-2,3-butanediol. Background technique [0002] C 2 Chiral diols such as enantiopure binaphthols [(a) Whitesell, J.K.Chem.Rev.1989, 89, 1581; (b) Brunel, J.M.Chem.Rev.2005, 105, 857-897; (c) Chen, Y .;Yekta,S.;Yudin,A.K.Chem.Rev.2003,103,3155–3212;(d)Periasamy,M.Aldrichim.Acta.2002,35,89.] and TADDOLs[(a)Pellissier,H. Tetrahedron2008,64,10279;(b)Seebach,D.;Beck,A.K.;Heckel A.Angew.Chem.Int.Ed.2001,40,92.] have been widely used in asymmetric synthesis reactions and supramolecular chemistry . tartaric acid derived C 2 Chiral diol (2R,3R)-1,4-dimethoxy-1,1,4,4-tetraphenyl-2,3-butanediol as chiral auxiliary, especially chiral boronic acid The protecting group of ester is widely used ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C43/178C07C41/26
CPCY02P20/55C07C41/26C07D327/10C07C43/1785
Inventor 胡晓允单自兴陈东志
Owner SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES
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