[3,3]-Sigmatropic Rearrangements in the Enantioselective Synthesis of (-)-Methylenolactocin

Abstract

A Pd(II)-catalyzed [3,3]-sigmatropic rearrangement is used to transfer chirality from an enantio-enriched alk-3-ene-1,2-diol to a C ₂ -symmetrical alk-2-ene-1,4-diol which, in turn, can be converted into a precursor of (-)-methylenolactocin through an additional [3,3]-sigmatropic rearrangement (either Johnson orthoester or Ireland-Claisen rearrangement).

Key words

rearrangement - diols - asymmetric synthesis - dihidroxylations

References

• 1a Pichon M. Figadère B. Tetrahedron: Asymmetry  1996,  7:  927 
• 1b Whitesell JK. Chem. Rev.  1989,  89:  1581 
• 1c Chong JM. Clarke IS. Koch I. Olbach PC. Taylor NJ. Tetrahedron: Asymmetry  1995,  6:  409 
• 1d Kim MJ. Lee IS. Synlett  1993,  767 
• 2a Otten S. Fröhlich R. Hanfe G. Tetrahedron: Asymmetry  1998,  9:  189 
• 2b Julienne K. Metzner P. Henryon V. Greiner A. J. Org. Chem.  1998,  63:  4532 
• 3a Burk MJ. Feaster JE. Harlow RL. Tetrahedron: Asymmetry  1991,  2:  569 
• 3b Burk MJ. Harper TGP. Kalberg CS. J. Am. Chem. Soc.  1995,  117:  4423 ; and references cited therein
• 3c Wiesaner C. Kratky C. Weissensteiner W. Tetrahedron: Asymmetry  1996,  7:  397 
• 4a Amador M. Ariza X. Garcia J. Sevilla S. Org. Lett.  2002,  4:  4511 
• 4b Ariza X. Garcia J. López M. Montserrat L. Synlett  2001,  120 
• For an overview on the desymmetrization of meso and other prochiral compounds in asymmetric synthesis, see:
• 5a Willis MC. J. Chem. Soc., Perkin Trans. 1  1999,  1765 
• 5b Magnunson SR. Tetrahedron  1995,  51:  2167 
• 5c Hoveyda AH. Evans DA. Fu GC. Chem. Rev.  1993,  93:  1307 
• 6 Park BK. Nakagawa M. Hirota A. Nakayama M. J. Antibiot.  1988,  41:  751 
• 7a Saicic RN. Zard SZ. Chem. Commun.  1996,  1631 
• 7b Ghatak A. Sarkar S. Ghosh S. Tetrahedron  1997,  53:  17335 
• 7c Mandal PK. Maiti G. Roy SC. J. Org. Chem.  1998,  63:  2829 
• 7d Loh T.-P. Lye P.-L. Tetrahedron Lett.  2001,  42:  3511 
• 8a Zhu G. Lu X. J. Org. Chem.  1995,  60:  1087 
• 8b Zhu G. Lu X. Tetrahedron: Asymmetry  1995,  6:  885 
• 8c Mawson SD. Weavers RT. Tetrahedron  1995,  51:  11257 
• 8d Chandrasekharam M. Liu R.-S. J. Org. Chem.  1998,  63:  9122 
• 8e Kongsaeree P. Meepowpan P. Thebtaranonth Y. Tetrahedron: Asymmetry  2001,  12:  1913 
• 9a de Azevedo MBM. Murta MM. Greene AE. J. Org. Chem.  1992,  57:  4567 
• 9b Murta MM. de Azevedo MBM. Greene AE. Synth. Commun.  1993,  23:  495 
• 10a Vaupel A. Knochel P. Tetrahedron Lett.  1995,  36:  231 
• 10b Takahata H. Uchida Y. Momose T. J. Org. Chem.  1995,  60:  5628 
• 10c Drioli S. Felluga F. Forzato C. Nitti P. Pitacco G. Chem. Commun.  1996,  1289 
• 10d Sibi MP. Deshpande PK. La Loggia AJ. Synlett  1996,  343 
• 10e Vaupel A. Knochel P. J. Org. Chem.  1996,  61:  5743 
• 10f Masaki Y. Arasaki H. Itoh A. Tetrahedron Lett.  1999,  40:  4829 
• 10g Chhor RB. Nosse B. Sörgel S. Böhm C. Seitz M. Reiser O. Chem.-Eur. J.  2003,  9:  260 
• In this connection it should be pointed out that the reduction of related alk-2-ene-1,4-diones gives lower stereoselectivities:
• 11a Bach J. Berenguer R. Garcia J. López M. Manzanal J. Vilarrasa J. Tetrahedron  1998,  54:  14947 
• 11b Bach J. Berenguer R. Garcia J. Loscertales T. Manzanal J. Vilarrasa J. Tetrahedron Lett.  1997,  38:  1091 
• 12 For a review, see: Corey EJ. Helal CJ. Angew. Chem. Int. Ed.  1998,  37:  1986 
• 13 Chabaud B. Sharpless KB. J. Org. Chem.  1979,  44:  4202 
• 14a Amador M. Ariza X. Garcia J. Ortiz J. Tetrahedron Lett.  2002,  43:  2691 
• 14b Diez RS. Adger B. Carreira EM. Tetrahedron  2002,  58:  8341 
• 15 An attempt to obtain (S,S)-5 by double addition of acetylene to hexanal under similar conditions also failed, see: Sasaki H. Boyall D. Carreira EM. Helv. Chim. Acta  2001,  84:  964 
• 16a In this case the main process seems to be the concomitant aldehyde aldol self-condensation: Anand NK. Carreira EM. J. Am. Chem. Soc.  2001,  123:  9687 
• 16b Frantz DE. Fässler R. Tomooka CS. Carreira EM. Acc. Chem. Res.  2000,  33:  373 
• 17a Zweifel G. Miller RL. J. Am. Chem. Soc.  1970,  92:  6678 
• 17b Farthing CN. Kocovsky P. J. Am. Chem. Soc.  1998,  120:  6661 
• 18a Xu D. Crispino GA. Sharpless KB. J. Am. Chem. Soc.  1992,  114:  7570 
• 18b For a review on catalytic asymmetric dihydroxylation, see: Kolb HC. VanNieuwenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 
• For some reviews on allylic rearrangements catalyzed by Pd(II), see:
• 19a Tsuji J. Palladium Reagents and Catalysts. Innovations in Organic Synthesis   Wiley; New York: 1995.  p.399 
• 19b Overman LE. Angew. Chem., Int. Ed. Engl.  1984,  23:  579 
• 21a Henry PM. J. Chem. Soc., Chem. Commun.  1971,  328 
• 21b Henry PM. J. Am. Chem. Soc.  1972,  94:  5200 
• For recent stereoselective applications, see:
• 22a Trost BM. Lee CB. J. Am. Chem. Soc.  2001,  123:  3687 
• 22b Saito S. Kuroda A. Matsunaga H. Ikeda S. Tetrahedron  1996,  52:  13919 
• 23 For a detailed review on [3,3]-sigmatropic rearrangements, see: Frauenrath H. In Houben-Weyl, Methods of Organic Chemistry   Vol. E21:  Helmchen G. Hoffmann RW. Mulzer J. Schaumann E. Thieme; Stuttgart: 1995.  p.3301 
• 24a Pereira S. Srebnik M. Aldrichimica Acta  1993,  26:  17 
• 24b Chai Y. Hong S.-P. Lindsay HA. McFarland C. McIntosh MC. Tetrahedron  2002,  58:  2905 
• 25 Carlsen PHJ. Katsuki T. Martin VS. Sharpless KB. J. Org. Chem.  1981,  46:  3936 
• 26 Mathre J. Jones TK. Xavier LC. Blacklock TJ. Reamer RA. Mohan JJ. Jones ET. Hoogsteen K. Baum MW. Grabowski EJ. J. Org. Chem.  1991,  56:  751 
• 27 Bach J. Berenguer R. Garcia J. López M. Manzanal J. Vilarrasa J. J. Org. Chem.  1996,  61:  9021 
• 28 Bicking JB. Robb CM. Smith RL. Cragoe EJ. Kuehl FA. Mandel LR. J. Med. Chem.  1977,  20:  35 
• 29 Knothe G. Bagby MO. Weisleder D. J. Am. Oil Chem. Soc.  1995,  72:  1021 

20

In order to assess the stereochemical purity of the product, an analytical sample of diacetate (S,S)-4, was hydrolyzed (NaOMe/MeOH) to diol (S,S)-3. The analysis of the corresponding Mosher diester revealed a 98% ee. Since the analysis of the Mosher diester derived from (S,S)-13 was unclear (signal overlap in ¹⁹F NMR and HPLC), we assumed that its optical purity should be ≥98% ee on the basis of that found for (S,S)-3. Absolute configuration of diol 3 revealed it to be identical to that obtained from reduction of diketone 5.