4176
J. Org. Chem. 1997, 62, 4176-4179
Preparation of Organometallic Complexed Sugars: Hetero Diels-Alder Reactivity of Tricarbonyl(formyltrimethylenemethane)iron Paul J. Kleindl and William A. Donaldson* Department of Chemistry, Marquette University, P.O. Box 1881, Milwaukee, Wisconsin 53201-1881 Received February 10, 1997
There has been considerable recent interest in the preparation of biologically important molecules which are “tagged” with a metal carbonyl group. Such compounds have been examined for use in carbonyl metallo immunoassays (CMIA) using FT-IR spectroscopy.1 While the majority of these “tagged” molecules are within the steroidal family, the preparation of organometallic nucleotides,2 leukotrienes,3 and carbohydrates4 have also been reported. σ-Bonded manganese and iron carbonyl complexes of carbohydrates have been prepared by displacement of 1-glucosyl halides or 6-deoxy-6-haloglucosides. Due to the lability of the metal-carbon σ bond, the majority of these metallo-sugar complexes are reported to be unstable. As part of our broader interest in developing methodology for the application of (TMM)Fe(CO)3 complexes [(TMM) ) trimethylenemethane] in organic synthesis,5 we have investigated the hetero Diels-Alder reaction6 of tricarbonyl(formyl-TMM)iron (1)7 and further elaboration into 4,6-dideoxypyranoside derivatives. The reaction of racemic 1 with 1-methoxy-3-[(trimethylsilyl)oxy]-1,3-butadiene (2), in the presence of BF3‚Et2O, followed by treatment with trifluoroacetic acid gave the dihydropyrone complex 3 as a single diastereomer (52%, eq 1).8 Since cyclocondensation of 1 with 2 in the
(1) (a) Jaouen, G.; Vessie`res. A.; Top, S.; Ismail, A. A.; Butler, I. S. J. Am. Chem. Soc. 1985, 107, 4778-80. (b) Jaouen, G.; Vessie`res. A. Pure Appl. Chem. 1985, 57, 1865-74. (2) (a) Dalla Riva Toma, J. M.; Bergstrom, D. E. J. Org. Chem. 1994, 59, 2418-22. (b) Bergstrom, D. E.; Schmaltz, T. Nucleosides Nucleotides 1989, 8, 1057-9. (c) Bergstrom, D. E.; Beal, P.; Lind, R. Nucleosides Nucleotides 1989, 8, 1061-3. (3) (a) Pinsard, P.; Lellouche, J.-P.; Beaucourt, J.-P.; Gre´e, R. Tetrahedron Lett. 1990, 31, 1141-4. (b) Franck-Neumann, M.; Colson, J.-P. Synlett 1991, 891-4. (4) (a) DeShong, P.; Slough, G. A.; Elango, V.; Trainor, G. L. J. Am. Chem. Soc. 1985, 107, 7788-90. (b) DeShong, P.; Slough, G. A.; Elango, V. Carbohydrate Res. 1987, 171, 342-5. (c) Trainor, G. L. J. Organomet. Chem. 1985, 282, C43-5. (d) Trainor, G. L.; Smart, B. E. J. Org. Chem. 1983, 48, 2447-8. (e) Baer, H. R.; Hanna, H. R. Carbohydrate Res. 1982, 102, 169-83. (f) Adams, M. J.; Hall, L. D. Can. J. Chem. 1980, 58, 1188-97. (5) (a) Donaldson, W. A.; Hossain, M. A.; Cushnie, C. D. J. Org. Chem. 1995, 60, 1611-8. (b) Donaldson, W. A.; Hossain, M. A. Tetrahedron Lett. 1992, 33, 4107-10. (c) Donaldson, W. A.; Hossain, M. A. Tetrahedron Lett. 1991, 32, 7047-50. (6) (a) Danishefsky, S.; Kerwin, J. F., Jr.; Kobayshi, S. J. Am. Chem. Soc. 1982, 104, 358-60. (b) Daniskefsky, S. J. Aldrichimica Acta 1986, 19, 59-69. Boger, D. L.; Weinreb, S. M. Hetero Diels-Alder Methodology in Organic Synthesis; Academic Press: New York, 1987.
S0022-3263(97)00234-X CCC: $14.00
Figure 1.
Scheme 1
presence of BF3‚Et2O occurred in a diastereospecific fashion, the use of other Lewis acid catalysts was not attempted. The relative stereochemistry of 3 was assigned as indicated on the basis of single crystal X-ray diffraction analysis.9 Dihydropyrone 3 arises via attack of 2, in the s-trans conformer, on the face of the aldehyde which is opposite to the sterically bulky Fe(CO)3 group. This present diastereoselectivity is consistent with that observed for addition of nucleophiles to 1.7,10 This high selectivity for this cyclocondensation (>25:1) is superior to that observed for the cyclocondensation of (dienal)Fe(CO)3 complexes (4) with 2 (
