Advances in Synthetic Methods of (R)-α-Lipoic Acid

doi:10.11944/j.issn.1000-0518.2020.11.200151

Chinese Journal of Applied Chemistry ›› 2020, Vol. 37 ›› Issue (11): 1236-1248.DOI: 10.11944/j.issn.1000-0518.2020.11.200151

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Advances in Synthetic Methods of (R)-α-Lipoic Acid

HAN Xiu^a, KANG Chuanqing^b*

^aCollege of Chemistry,Sichuan University,Chengdu 610000,China;
^bChangchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China

Received:2020-05-19 Revised:2020-06-28 Accepted:2020-07-23 Published:2020-11-01 Online:2020-11-04
Contact: KANG Chuanqing, professor; Tel:0431-85262291; E-mail:kangcq@ciac.ac.cn; Research interests:asymmetric synthesis, synthesis, self-assembly, and bioactivity of functional organic molecules

Abstract

Abstract: The methods for the effective synthesis of (R)-α-lipoic acid have been widely investigated since (R)-α-lipoic acid can be widely used for the treatment of diabetes and diabetic complications. It is also extensively used in health care products. Therefore, asymmetric synthesis of (R)-α-lipoic acid has attracted broad interests from the community of both academia and industry. To date, the reported routes for the synthesis of (R)-α-lipoic acid include asymmetric synthesis catalyzed by the enzymatic and chemical catalysts, chiral resolution, and chiral substrate-controlled synthesis. Based on this classification, this paper summarizes the advances of the methods for asymmetric synthesis of (R)-α-lipoic acid and predicts future prospects.

Key words: lipoic acids, chiral resolution, asymmetric synthesis

CLC Number:

O629.9

HAN Xiu, KANG Chuanqing. Advances in Synthetic Methods of (R)-α-Lipoic Acid[J]. Chinese Journal of Applied Chemistry, 2020, 37(11): 1236-1248.

References

[1] Reed L J,Debusk B G,Gunsalus I C,et al. Crystalline α-Lipoic Acid:A Catalytic Agent Associated with Pyruvate Dehydrogenase[J]. Science,1951,11(2952):93-94.
[2] Reed L J,Koike M,Levitch M E,et al. Studies on the Nature and Reactions of Protein-Bound Lipoic Acid[J]. Biol Chem,1958,232(1):143-158.
[3] Bast A,Hanen G. Interplay Between Lipoic Acid and Glutathione in the Protection Against Microsomal Lipid-Peroxidation[J]. Biochem Biophys Acta,1988,963(3):558-561.
[4] Kagen V E,Serbinova E A,Forte T,et al. Recycling of Vitamin E in Human Low Density Lipoproteins[J]. Lipid Res,1992,33:385-397.
[5] Bingham P M,Zarchar Z. Lipoic Acid Derivatives and Their Treatment of Disease:Int Appl,WO 0024,734[P],2000.
[6] Zhang S,Chen X,Zhang J,et al. An Enantioselective Formal Synthesis of (+)-(R)-Alpha-Lipoic Acid by an L-Proline-Catalyzed Aldol Reaction[J]. Synthesis,2008,3:383-386.
[7] Biewenga G P,Haenen G R M M,Bast A. The Role of Lipoic Acid in the Treatment of Diabetic Polyneuropathy[J]. Gen Pharmacol,1997,29(4):315-531.
[8] Gunasalus I C,Barton L S,Gruber W. Biosynthesis and Structure of Lipoic Acid Derivatives[J]. J Am Chem Soc,1956,78(8):1763-1766.
[9] Gopalan A S,Jacobs H K. Stereochemical Control of Yeast Reductions:Synthesis of R-(+)-α-Lipoic Acid[J]. Tetrahedron Lett,1989,30(42):5705-5708.
[10] Hirama M,Shimizu M,Iwashita M. Enantiospecific Synthesis of Trifunctional (R)-3-Hydroxy Esters by Bakers-Yeast Reduction[J]. J Chem Soc Chem Commun,1983,10:599-600.
[11] Zhou B,Gopalan A S,Vanmiddlesworth F,et al. Stereochemical Control of Yeast Reductions.1.Asymmetric-Synthesis of L-Catnitine[J]. J Am Chem Soc,1983,105(18):5925-5926.
[12] Gopolan A S,Jacobs H K. Baker's Yeast Reduction of Alkyl 6-Chloro-3-Oxohexanoates: Synthesis of (R)-(+)-α-Lipoic Acid[J]. J Chem Soc Perkin Trans,1990:1897-1900.
[13] Zhang Y,Zhang W,Zheng G,et al. Identification of an ε-Keto Ester Reductase for the Efficient Synthesis of an (R)-α-Lipoic Acid Precursor[J]. Adv Synth Catal,2015,357:1697-1702.
[14] Xu Y,Chen Q,Zhang Y,et al. Coevolution of the Activity and Thermostability of an ε-Keto Ester Reductase for Better Synthesis of an (R)-α-Lipoic Acid[J]. Chembiochem,2020,21:1341-1346.
[15] Fadnavis N,Koteshwar K. Remote Control of Stereoselectivity:Lipase Catalyzed Enantioselective Esterification of Racemic α-Lipoic Acid[J]. Tetrahedron:Asymm,1997,8(2):337-339.
[16] Yan H,Wang Z,Chen L. Kinetic Resolution of α-Lipoic Acid via Enzymatic Differentiation of a Remote Stereocenter[J]. J Ind Microbiol Biotechnol,2009,36:643-648.
[17] Martinez-Palou R. Ionic Liquid and Microwave-Assisted Organic Synthesis:A “Green” and Synergic Couple[J]. J Mex Chem Soc,2007,51:252-264.
[18] Yu D,Wang Y,Wang C,et al. Microwave-Assisted Enzymatic Resolution of (R,S)-2-Octanol in Ionic Liquid[J]. Process Biochem,2012,47:479-484.
[19] Liu N,Wang L,Wang Z,et al. Microwave-Assisted Resolution of α-Lipoic Acid Catalyzed by an Ionic Liquid Co-lyophilized Lipase[J]. Molecules,2015,20:9949-9960.
[20] Adger B,Bes M T,Grogan G,et al. Application of Enzymic Baeyer-Villiger Oxidations of 2-Substituted Cycloalkanones to the Total Synthesis of (R)-(+)-Lipoic Acid[J]. J Chem Soc Chem Commun,1995:253-261.
[21] Adger B,Bes M T,Grogan G,et al. The Syntesis of (R)-(+)-Lipoic Acid Using a Monooxygenase-Catalyzed Biotransformation as the Key Step[J]. Bioorg Organ Chem,1997,5(2):253-261.
[22] Zhou W,Ni Y,Zheng G,et al. Enzymatic Resolution of a Chiral Chlorohydrin Precursor for (R)-α-Lipoic Acid Synthesis via Lipase Catalyzed Enantioselective Transacylation with Vinyl Acetate[J]. J Mol Catal B-Enzym,2014,99:102-107.
[23] Elliott J D,Steele J,Jhonson W S. Asymmetric Synthesis via Acetal Templates.12.Highly Diastereoselective Coupling Reactions with a Ketene Acetal-An Efficient, Asymmetric Synthesis of R-(+)-Alpha-Lipoic Acid[J]. Tetrahedron Lett,1985,26(21):2535-2538.
[24] Page P C B,Rayner C M,Sutherland L O. An Enantioselective Synthesis of R-(+)-α-Lipoic Acid[J]. J Chem Soc Perkin Trans,1990:1615-1618.
[25] Zimmer R,Hain U,Berndt M,et al. Enantioselective Synthesis of (S)- and (R)-6-Hydroxy-Nonene-Carboxylates by Asymmetric Catalysis:A Formal Synthesis of (R)-α-Lipoic Acid and Its (S)-Antipode[J]. Tetrahedron:Asymm,2000,11:879-887.
[26] Tolstikov A G,Khakhalina N V,Savateeva E E,et al. Enantiospecific Synthesis of Methyl-Esters of R-(+)-alpha-Lipoic Acid and Its Optical Antipode[J]. Bioorg Khim,1990,16(12):1670-1674.
[27] Upadhya T T,Nikalje M D,Sudalai A. Asymmetric Dihydroxylation and Hydrogenation Approached to the Enantioselective Synthesis of R-(+)-α-Lipoic Acid[J]. Tetrahedron Lett,2001,42:4891-4893.
[28] Kaku H,Okamoto N,Nishii T,et al. Enantioselectve Total Synthesis of (R)-α-Lipoic Acid:An Application of Thermodynamically Controlled Deracemiztion of (±)-2-(2-Methoxyethyl)Cyclohexanone[J]. Synhesis,2010,17:2931-2934.
[29] Chavan S P,Pawar K P. Chirality Induction and Chiron Approaches to Enantioselective Total Synthesis of α-Lipoic Acid[J]. Tetrahedron,2015,71:4213-4218.
[30] Chavan S P,Praveen C. Enantioselective Synthesis of R-(+)-Alpha and S-(-)-Alpha-Lipoic Acid[J]. Tetrahedron Lett,2004,5(31):421-423.
[31] Villani F,Nardi A,Salvi A,et al. Process for the Production of R-(+)-α-Lipoic Acid. U.S.Patent 6670484 B2[P],2003.
[32] Bose D S,Fatima L,Rajender S. An Efficient, Highly Enantioenriched Route to L-Carnitine and α-Lipoic Acid via Hydrolytic Resolution[J]. Synthesis,2006,11:1863-1867.
[33] Purude A N,Pawar K P,Patil N B,et al. Total Synthesis of (R)-Llipoic Acid and (S)-Lipoic Acid via an Mn(III)-Salen-Catalyzed Oxidative Kinetic Resolution[J]. Tetrahedron:Asymm,2015,26:281-187
[34] ZHOU Peng,XU Zujian,XU Zhaohui. Effecient Synthesis of 4-Formylphenyl(2,3,4,6-O-tetraacetyl)-β-D-Glucose Derivatives[J]. Chinese J Appl Chem,2019,36(5):509-514(in Chinese).
周鹏,许祖俭,许招会. 4-甲酰基苯基(2,3,4,6-O-四乙酰基)-β-D-葡萄糖苷衍生物的有效合成[J]. 应用化学,2019,36(5):509-514.
[35] Fengler-Veith M,Schwardt O,Kautz U,et al. (1'R)-(-)-2,4-O-Ethylidene-D-Erythrose and Ethyl (E)-(α)-46-O-Ethylidene-(4S,5R,1'R)-4, 5, 6-Trihydroxy 2-Hexenoate[J]. Org Synth,2002,78:123-128.
[36] Dener J M,Rice K D,Newcomb W S,et al. Dibasic Inhibitors of Human Mast Cell Tryptase.Part 3:Identification of a Series of Potent and Selective Inhibitors Containing the Benzamidine Functionality[J]. Bioorg Med Chem Lett,2001,11(13):1629-1633.
[37] Shu Z,Zhu J,Liao S,et al. Facile and Controllable Synthesis of Multiply Substituted Benzenes via a Formal [3+3] Cycloaddition Approach[J]. Tetrahedron,2013, 69(1): 284-292.
[38] Mathieson J E, Crawford J J, Schmidtmann M,et al. Fast and Efficient One Step Synthesis of Dienamides[J]. Org Biomol Chem,2009,7(10):2170-2175.
[39] Chaven S P,Harale K R,Pawar K P. A Short Synthesis of (2S,3S)-3-Hydroxypipecolic Acid[J]. Tetrahedron Lett,2013,54(36):4851-4853.
[40] HU Aixi,YUAN Shuai,WU Xiaoyun,et al. Pd-Catalyzed Hydrodebromination of 5-Bromo-6-Methoxy-2-Propionylnaphthalene[J]. Chinese J Appl Chem,2002,19(6):582-584(in Chinese)

Advances in Synthetic Methods of (R)-α-Lipoic Acid

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