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

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 ...

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

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