Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
          
          https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
        Synthesis  2008(3): 383-386  
DOI: 10.1055/s-2008-1032022
   DOI: 10.1055/s-2008-1032022
PAPER
© Georg Thieme Verlag Stuttgart · New YorkAn Enantioselective Formal Synthesis of (+)-(R)-α-Lipoic Acid by an l-Proline-Catalyzed Aldol Reaction
Further Information
            
               
                  
                        
                              Received
                              12 September 2007 
                      
Publication Date:
10 January 2008 (online)
            
         
      
   Publication History
Publication Date:
10 January 2008 (online)

Abstract
An efficient, highly stereocontrolled formal synthesis of (+)-(R)-α-lipoic acid was achieved, which utilizes an l-proline-catalyzed highly enantio- and diastereoselective cross-aldol reaction as the key step.
Key words
aldehyde - aldol reaction - ketone - lipoic acid - proline
- 1a 
             
            Sigel H. Angew. Chem., Int. Ed. Engl. 1982, 21: 389
- 1b 
             
            Yadav JS.Mysorekar SV.Garyali K. J. Sci. Ind. Res. 1990, 49: 400 ; and references cited therein
- 2 
             
            Packer L.Tritschler HJ.Wessel K. Free Rad. Biol. Med. 1997, 22: 359
- 3 
             
            Baur A.Harrer T.Peukert M.Jahn G.Kalden JR.Fleckenstein B. Klin. Wochenschr. 1991, 69: 722 ; Chem. Abstr. 1992, 116, 207360
- 4  
            Bingham PM, andZachar Z. inventors; WO 0024734. ; Chem. Abstr. 2000, 132, 3081921Reference Ris Wihthout Link
- For examples of racemic syntheses of lipoic acid, see:
- 5a 
             
            Segre A.Viterbo R.Parisi G. J. Am. Chem. Soc. 1957, 79: 3503
- 5b 
             
            Tsuji J.Yasuda H.Mandai T. J. Org. Chem. 1978, 43: 3606
- 5c 
             
            Menon RB.Kumar MA.Ravindranathan T. Tetrahedron Lett. 1987, 28: 5313
- 5d 
             
            Crevisy C.Herbage B.Marrel M.-L.Toupet L.Gree R. Eur. J. Org. Chem. 1998, 1949
- 5e 
             
            Chavan SP.Shivsankar K.Pasupathy K. Synthesis 2005, 1297
- For examples of using chiral auxiliaries or precursors for asymmetric syntheses of lipoic acid, see:
- 6a 
             
            Brookes MH.Golding BT.Howes DA.Hudson AT. J. Chem. Soc., Chem. Commun. 1983, 1051
- 6b 
             
            Elliott JD.Steele J.Johnson WS. Tetrahedron Lett. 1985, 26: 2535
- 6c 
             
            Rama Rao AV.Mysorekar SV.Gurjar MK.Yadav JS. Tetrahedron Lett. 1987, 28: 2183
- 6d 
             
            Brookes MH.Golding BT.Hudson AT. J. Chem. Soc., Perkin Trans. 1 1988, 9
- 6e 
             
            Silks LA.Peng J.Odom JD.Dunlap RB. J. Chem. Soc., Perkin Trans. 1 1991, 2495
- For examples of enzymatic reactions for asymmetric syntheses of lipoic acid, see:
- 7a 
             
            Brooks DW.Kellogg RP.Cooper CS. J. Org. Chem. 1987, 52: 192
- 7b 
             
            Gopalan AS.Jacobs HK. Tetrahedron Lett. 1989, 30: 5705
- 7c 
             
            Dasaradhi L.Fadnavis NW.Bhalerao UT. J. Chem. Soc., Chem. Commun. 1990, 729
- 7d 
             
            Gopalan AS.Jacobs HK. J. Chem. Soc., Perkin Trans. 1 1990, 1897
- 7e 
             
            Adger B.Bes MT.Grogan G.McCague R.Pedragosa-Moreau S.Roberts SM.Villa R.Wan PWH.Willetts AJ. J. Chem. Soc., Chem. Commun. 1995, 1563
- 7f 
             
            Laxmi YRS.Lyengar DS. Synthesis 1996, 594
- 7g 
             
            Bezbarua MS.Saikia AK.Barua NC.Kalita D.Ghosh AC. Synthesis 1996, 1289
- 7h 
             
            Adger B.Bes MT.Grogan G.McCague R.Pedragosa-Moreau S.Roberts SM.Villa R.Wan PWH.Willetts AJ. Bioorg. Med. Chem. 1997, 5: 253
- 7i 
             
            Fadnavis NW.Babu RL.Vadivel SK.Deshpande AA.Bhalerao UT. Tetrahedron: Asymmetry 1998, 9: 4109
- For examples of asymmetric syntheses of lipoic acid catalyzed by organometallic reagents, see:
- 8a 
             
            Page PCB.Rayner CM.Sutherland IO. J. Chem. Soc., Chem. Commun. 1986, 1408
- 8b 
             
            Page PCB.Rayner CM.Sutherland IO. J. Chem. Soc., Perkin Trans. 1 1990, 1615
- 8c 
             
            Zimmer R.Hain U.Berndt M.Gewald R.Reissig H.-U. Tetrahedron: Asymmetry 2000, 11: 879
- 8d 
             
            Upadhya TT.Nikalje MD.Sudalai A. Tetrahedron Lett. 2001, 42: 4891
- 8e 
             
            Zimmer R.Peritz A.Czerwonka R.Schefzig L.Reissig H.-U. Eur. J. Org. Chem. 2002, 3419
- 8f 
             
            Chavan SP.Praveen C.Ramakrishna G.Kalkote UR. Tetrahedron Lett. 2004, 45: 6027
- 8g 
             
            Bose DS.Fatima L.Rajender S. Synthesis 2006, 1863
- For selected recent reviews of organocatalysis, see:
- 9a 
             
            Dalko PI.Moisan L. Angew. Chem. Int. Ed. 2001, 40: 3726
- 9b 
             
            Dalko PI.Moisan L. Angew. Chem. Int. Ed. 2004, 43: 5138
- 9c 
             
            List B. Tetrahedron 2002, 58: 5573
- 9d 
             
            Notz W.Tanaka F.Barbas CF. Acc. Chem. Res. 2004, 37: 580
- 9e 
             
            Jarvo ER.Miller SJ. Tetrahedron 2002, 58: 2481
- 9f Special issue on Asymmetric Organocatalysis: Acc. Chem. Res. 2004, 37: 487
- For l-proline-promoted aldol reactions, see:
- 10a 
             
            List B.Lerner RA.Barbas CF. J. Am. Chem. Soc. 2000, 122: 2395
- 10b 
             
            Northrup AB.MacMillan DWC. J. Am. Chem. Soc. 2002, 124: 6798
- 10c 
             
            Enders D.Grondal C. Angew. Chem. Int. Ed. 2005, 44: 1210
- 10d 
             
            Casas J.Engqvist M.Ibrahem I.Kaynak B.Córdova A. Angew. Chem. Int. Ed. 2005, 44: 1343
- 10e 
             
            Pan Q.Zou B.Wang Y.Ma D. Org. Lett. 2004, 6: 1009
- 10f 
             
            Northrup AB.MacMillan DWC. Science 2004, 305: 1752
- 10g 
             
            Suri JT.Ramachary DB.Barbas CF. Org. Lett. 2005, 7: 1383
- For selected examples of aldol reactions catalyzed by proline derivatives, see:
- 11a 
             
            Mase N.Tanaka F.Barbas CF. Angew. Chem. Int. Ed. 2004, 43: 2420
- 11b 
             
            Sakthivel K.Notz W.Bui T.Barbas CF. J. Am. Chem. Soc. 2001, 123: 5260
- 11c 
             
            Nakadai M.Saito S.Yamamoto H. Tetrahedron 2002, 58: 8167
- 11d 
             
            Tang Z.Jiang F.Yu L.-T.Cui X.Gong L.-Z.Mi A.-Q.Jiang Y.-Z.Wu Y.-D. J. Am. Chem. Soc. 2003, 125: 5262
- 11e 
             
            Mangion IK.Northrup AB.MacMillan DWC. Angew. Chem. Int. Ed. 2004, 43: 6722
- 11f 
             
            Krattiger P.Kovasy R.Revell JD.Ivan S.Wennemers H. Org. Lett. 2005, 7: 1101
- 11g 
             
            Torii H.Nakadai M.Ishihara K.Saito S.Yamamoto H. Angew. Chem. Int. Ed. 2004, 43: 1983
- 11h 
             
            Cobb AJA.Shaw DM.Longbottom DA.Ley SV. Org. Biomol. Chem. 2005, 3: 84
- 11i 
             
            Wang W.Li H.Wang J. Tetrahedron Lett. 2005, 46: 5077
- 11j 
             
            Hayashi Y.Sumiya T.Takahashi J.Gotoh H.Urushima T.Shoji M. Angew. Chem. Int. Ed. 2006, 45: 958
- 11k 
             
            Dziedzic P.Zou W.Hafren J.Córdova A. Org. Biomol. Chem. 2006, 4: 38
- 11l 
             
            Chimni SS.Mahajan D.Babu VVS. Tetrahedron Lett. 2005, 46: 5617
- 11m 
             
            Bellis E.Vasilatou K.Kokotos G. Synthesis 2005, 2407
- 11n 
             
            Chen J.-R.Lu H.-H.Li X.-Y.Cheng L.Wan J.Xiao W.-J. Org. Lett. 2005, 7: 4543
- 12a 
             
            Zhang S.-L.Duan W.-H.Wang W. Adv. Synth. Catal. 2006, 348: 1228 ; and other examples using l-proline-catalyzed aldol reactions in natural product synthesis for total synthesis
- 12b 
             
            Mangion IK.MacMillan DWC. J. Am. Chem. Soc. 2005, 127: 3696
- 12c 
             
            Pihko PM.Erkkila A. Tetrahedron Lett. 2003, 44: 7607
- 13 
             
            Molander GA.McKie JA. J. Org. Chem. 1993, 58: 7216
- 14 
             
            Akita H.Chen CY.Kato K. Tetrahedron 1998, 54: 11011
 
    