A Study of the Stereodirecting Effect by an Allylic Nitrogen Substituent on Dihydroxylation Reactions of Cyclic Double Bonds[1]

Joon Seok Oh; Yoo Seong Hong; Young Gyu Kim

Journal of Industrial and Engineering Chemistry, Vol.3, No.4, 326-334, December, 1997

Joon Seok Oh, Yoo Seong Hong, and Young Gyu Kim

Department of Chemical Technology, Seoul National University, Seoul 151-742, Korea

Stereoselective introduction of a vicinal amino alcohol group is an essential step for the preparation of biologically active natural products such as the side chain of Taxol, an anticancer agent, and phytosphingosine, one of the important cell membrane components. The goal can be efficiently achieved by the osmium-catalyzed dihydroxylation reaction of chiral allylic amines that are easily prepared from readily dvailable α-amino acids. In order to understand the stereodirecting effect by an allylic amino substitutent, diastereoselectivity in dihydroxylation reactions of 1-aminosubstituted 2-cyclohexenes using osmium tetroxide (OsO₄) was systematically investigated in various solvents for the first time. A good to excellent anti selectivity (from 10:1 to >20:1) was obtained with an azido substituent (3-azidocyclohexene), which did not show dependence on solvent polarity. No significant change in the diastereofacial selectivity was also noted by changing the water content in THF. However, the facial selectivity for the anti isomer in monoprotected N-Boc amines decreased with a decrease in the solvent polarity. The best selectivity (5.9:1) for the anti diol isomer was produced in DMF and no selectivity in CH₂Cl₂. Cyclohexenes with diprotected allylic amines did always show the exclusive anti selectivity irrespective of the solvent polarity. Dependence of diastereoselectivity by the monoprotected amino susbstitutents on the solvent polarity could be attributed to the hydrogen bonding effect. The steric effect appears to be responsible for the exclusive selectivity in N,N-disubstituted amino cyclohexenes.

[References]

Excerpted in Part from the M.E. Thesis of Y.S. Hong, Seoul National University, Feb. (1997)
Presented in Part at the Fall '97 Conference of the Korean Society of Industrial and Engineering chemistry, The University of Suwon, Hwasung-Gun, Kyonggi-Do, October 31-November 1, No. 1PB-29 (1997)
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Sibi MP, Lu J, Edwards J, J. Org. Chem., 62, 5864 (1997)
Yokomatsu T, Yuasa Y, Shibuya S, Heterocycles, 33, 1051 (1992)
Cardillo G, Tomasini C, Chem. Soc. Rev., 25, 117 (1996)
Veeresha G, Datta A, Tetrahedron Lett., 38, 5223 (1997)
Nicolaou KC, Dai WN, Guy RK, Angew. Chem.-Int. Edit., 33, 15 (1994)
Hepperle M, Georg GI, Drugs Fut., 19, 573 (1994)
Gennari C, Carcano M, Donghi M, Mongelli N, Vanotti E, Vulpetti A, J. Org. Chem., 62, 4746 (1997)
Wild R, Schmidt RR, Tetrahedron: Asymmetry, 5, 2195 (1994)
Li YL, Mao XH, Wu YL, J. Chem. Soc.-Perkin Trans. 1, 1559 (1995)
Shimizu M, Wakioka I, Fujisawa T, Tetrahedron Lett., 38, 6027 (1997)
Coppola GM, Schuster HF, Asymmetric Synthesis: Construction of Chiral Molecules Using Amino Acids, Wiley, New York (1987)
Williams RM, Synthesis of Optically Active α-Amino Acids, Pergamon, Oxford (1989)
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Cha JK, Kim NS, Chem. Rev., 95(6), 1761 (1995)
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[Related Articles]

[1] Excerpted in Part from the M.E. Thesis of Y.S. Hong, Seoul National University, Feb. (1997)

[2] Presented in Part at the Fall '97 Conference of the Korean Society of Industrial and Engineering chemistry, The University of Suwon, Hwasung-Gun, Kyonggi-Do, October 31-November 1, No. 1PB-29 (1997)

[3] Hauser FM, Ellenberger SR, Chem. Rev., 86, 35 (1986)

[4] Thomas GJ, Synthesis of Anthracyclines Related to Daunomycin in Recent Progress in the Chemical Synthesis of Antibiotics, G. Lukacs and M. Ohno (eds.), p. 467, Springer-Verlag, Berlin (1990)

[5] Sibi MP, Lu J, Edwards J, J. Org. Chem., 62, 5864 (1997)

[6] Yokomatsu T, Yuasa Y, Shibuya S, Heterocycles, 33, 1051 (1992)

[7] Cardillo G, Tomasini C, Chem. Soc. Rev., 25, 117 (1996)

[8] Veeresha G, Datta A, Tetrahedron Lett., 38, 5223 (1997)

[9] Nicolaou KC, Dai WN, Guy RK, Angew. Chem.-Int. Edit., 33, 15 (1994)

[10] Hepperle M, Georg GI, Drugs Fut., 19, 573 (1994)

[11] Gennari C, Carcano M, Donghi M, Mongelli N, Vanotti E, Vulpetti A, J. Org. Chem., 62, 4746 (1997)

[12] Wild R, Schmidt RR, Tetrahedron: Asymmetry, 5, 2195 (1994)

[13] Li YL, Mao XH, Wu YL, J. Chem. Soc.-Perkin Trans. 1, 1559 (1995)

[14] Shimizu M, Wakioka I, Fujisawa T, Tetrahedron Lett., 38, 6027 (1997)

[15] Coppola GM, Schuster HF, Asymmetric Synthesis: Construction of Chiral Molecules Using Amino Acids, Wiley, New York (1987)

[16] Williams RM, Synthesis of Optically Active α-Amino Acids, Pergamon, Oxford (1989)

[17] Maryanoff BE, Reitz AB, Chem. Rev., 89, 863 (1989)

[18] Vedejs E, Peterson MJ, Top. Stereochem., 21, 1 (1994)

[19] Cha JK, Christ WJ, Kishi Y, Tetrahedron, 40, 2247 (1984)

[20] Cha JK, Kim NS, Chem. Rev., 95(6), 1761 (1995)

[21] Kolb HC, Vannieuwenhze MS, Sharpless KB, Chem. Rev., 94(8), 2483 (1994)

[22] Hoffman RW, Chem. Rev., 89, 89 (1989)

[23] Hoveyda AH, Evans DA, Fu GC, Chem. Rev., 93, 1307 (1993)

[24] Donohoe TJ, Garg R, Moore PR, Tetrahedron Lett., 37, 3407 (1996)

[25] Donohoe TJ, Moore PR, Beddoes RL, J. Chem. Soc.-Perkin Trans. 1, 43 (1997)

[26] Donohoe TJ, Moore PR, Waring MJ, Tetrahedron Lett., 38, 5027 (1997)

[27] Lindstrm UM, Franckowiak R, Pinault N, Somfai P, Tetrahedron Lett., 38, 2027 (1997)

[28] Sharpless et al. Reported in reference 3c (p. 2512) three examples of the dihydroxylation reactions with stoichiometric amount of O_sO₄ in toluene at room temperature; that is, the syn to anti ratio of N-tosyl-, N-triflyl- and N-methyl-N-triflyl-2-cyclohexenylamine was 1:2.5, 1.1:1, and 0:1, respectively, which was used to support the proposed hydrogen bonding interaction between O_sO₄ and the allylic substituent.

[29] Poli G, Tetrahedron Lett., 30, 7385 (1989)

[30] Hirama M, Oishi T, Ito S, J. Chem. Soc.-Chem. Commun., 665 (1989)

[31] Burdisso M, Gandolfi R, Rastelli A, Tetrahedron Lett., 32, 2659 (1991)

[32] Krysan DJ, Rockway TW, Haight AR, Tetrahedron: Asymmetry, 5, 625 (1994)

[33] Targett NM, Kilcoyne JP, Green B, J. Org. Chem., 44, 4962 (1979)

[34] Pelletier SW, Chokshi HP, Desai HK, J. Nat. Prod., 49, 892 (1986)

[35] Coll JC, Bowden BF, J. Nat. Prod., 49, 934 (1986)

[36] Leonard J, Lygo B, Procter G, Advanced Practical Organic Chemistry 2nd ed., Chap. 11, pp. 215 ~ 216, Blackie Academic & Professional, London (1995)

[37] Koziara A, Osowska-Parewicka K, Zawadzki S, Zwierzak A, Synthesis, 202 (1988)

[38] Lehmkuhl H, Rabet F, Haushild K, Synthesis, 184 (1977)

[39] Johnson AW, Ylides and Imines of Phosphorus, Chap. 13, pp. 403-483, Wiley, New York (1993)

[40] Murahashi SI, Taniguchi Y, Imada Y, Tanigawa Y, J. Org. Chem., 54, 5864 (1989)

[41] Murahashi SI, Imada Y, Tanigawa Y, Taniguchi Y, Tetrahedron Lett., 27, 227 (1986)

[42] VanRheenen V, Kelly RC, Cha DY, Tetrahedron Lett., 1973 (1976)

[43] Schroder M, Chem. Rev., 80, 187 (1980)

[44] Leo A, Hansch C, Elkins D, Chem. Rev., 71, 525 (1971)

[45] Laane C, Boeren S, Vos K, Veeger C, Biotechnol. Bioeng., 30, 81 (1987)

[46] Reichardt C, Solvents and Solvent Effects in Organic Chemistry 2nd ed., Chap. 7, p. 339, VCH, Weinheim (1988)

[47] Reetz MT, Angew. Chem.-Int. Edit., 30, 1531 (1991)

[48] Saito S, Inaba M, Moriwake T, Tetrahedron Lett., 30, 837 (1989)