Synthesis of Enantiopure 1-Alkoxyallenes and their 3-Alkylated Derivatives

Abstract

A series of enantiopure 1-alkoxyallenes 1a-1f was prepared starting from propargyl bromide and the corresponding optically active alcohols via propargyl ethers 3a-3f as intermediates. In addition, disubstituted enantiopure allene derivatives 5a-5c were synthesized by isomerization of the corresponding alkynes 4a-4c. Allene derivative 5a was also prepared via an alternative route with 1-trimethylsilylallene derivative 6a as crucial intermediate.

Key words

alkynes - allenes - isomerization - carbohydrates - asymmetric synthesis

References and Notes

• 1 General review: Zimmer R. Synthesis  1993,  165 
• For recent synthetic work, see:
• 2a Pirrung MC. Zhang J. Morehead AT. Tetrahedron Lett.  1994,  35:  6229 
• 2b Gröschl D. Niedermann H.-P. Meier H. Chem. Ber.  1994,  127:  955 
• 2c Hojo M. Aihara H. Ito H. Hosomi A. Tetrahedron Lett.  1996,  37:  9241 
• For typical applications, see:
• 3a Unger C. Zimmer R. Reissig H.-U. Würthwein E.-U. Chem. Ber.  1991,  124:  2279 
• 3b Zimmer R. Reissig H.-U. Homann K. J. Prakt. Chem.  1995,  337:  521 
• 3c Angermann J. Homann K. Reissig H.-U. Zimmer R. Synlett  1995,  1014 
• 3d Zimmer R. Hiller F. Reissig H.-U. Heterocycles  1999,  50:  393 
• 3e Zimmer R. Homann K. Angermann J. Reissig H.-U. Synthesis  1999,  1223 
• 4 Hoff S. Brandsma L. Arens JF. Recl. Trav. Chim. Pays-Bas  1968,  87:  916 
• 5a Hormuth S. Reissig H.-U. Dorsch D. Angew. Chem., Int. Ed. Engl.  1993,  32:  1449 
• 5b Hormuth S. Reissig H.-U. Dorsch D. Angew. Chem.  1993,  105:  1513 
• 5c Hormuth S. Schade W. Reissig H.-U. Liebigs Ann. Chem.  1996,  2001 
• 6 Reissig H.-U. Hormuth S. Schade W. Okala Amombo M. Watanabe T. Pulz R. Hausherr A. Zimmer R. J. Heterocycl. Chem.  2000,  37:  597 
• 7a Arnold T. Orschel B. Reissig H.-U. Angew. Chem., Int. Ed. Engl.  1992,  31:  1033 
• 7b Arnold T. Orschel B. Reissig H.-U. Angew. Chem.  1992,  104:  1084 
• 8a Rochet P. Vatèle J.-M. Goré J. Synlett  1993,  105 
• 8b Rochet P. Vatèle J.-M. Goré J. Synthesis  1994,  795 
• 9a Recently several 3-O-allenyl-substituted furanoses have been synthesized and their conformations were studied by NMR spectroscopy: Lysek R. Krajewski P. Urbanczyk-Lipkowska Z. Furman B. Kaluza Z. Kozerski L. Chmielewski M. J. Chem. Soc., Perkin Trans. 2  2000,  61 
• 9b Other applications: Harrington PE. Tius MA. Org. Lett.  2000,  2:  2447 
• 10a Tius MA. Hu H. Kawakami JK. Busch-Petersen J. J. Org. Chem.  1998,  63:  5971 
• 10b Verkrujisse HD. Verboom W. Van Rijn PE. Brandsma L. J. Organomet. Chem.  1982,  232:  C1 
• 12 This route is based on transformations as described by: Clinet J.-C. Linstrumelle G. Tetrahedron Lett.  1980,  21:  3987 
• 15 Kofron WG. Baclawski LM. J. Org. Chem.  1976,  41:  1879 
• 16 Singh PP. Gharia MM. Dasgupta P. Scrivastara HC. Tetrahedron Lett.  1977,  439 
• 17 Fayet C. Gelas J. Carbohydr. Res.  1986,  155:  99 
• 18 Banks MR. Cadogan JIG. Gosney I. Gould RO. Hodgson PKG. McDougall D. Tetrahedron  1998,  54:  9765 
• 19 Copeland C. McAdam DP. Stick RV. Aust. J. Chem.  1983,  36:  1239 
• 20 Hockett RC. Miller RE. Scattergood A. J. Am. Chem. Soc.  1949,  71:  3072 

11

The predominating configuration has been established by subsequent transformation into a literature known amino acid derivative and comparison of optical rotations: Hausherr, A.; Reissig, H.-U. unpublished results.

13

Deprotonation of 4a with n-BuLi in the presence of 1.2 equivalents of (-)-sparteine followed by aqueous workup furnished 5a as a 50:50 mixture of diastereomers. Thus, addition of this chiral complexing agent does not seem to exert a noticeable influence on the diastereoselectivity of this process.

14

Hausherr, A.; Reissig, H.-U. manuscript in preparation.