Asymmetric Synthesis of Orthogonally Protected (2S,4R)- and (2S,4S)-4-Hydroxyornithine

Abstract

Synthesis of orthogonally protected (2S, 4R)- and (2S, 4S)-4-hydroxyornithine was reported featuring an asymmetric alkylation of N-(diphenylmethylene)glycine tert-butyl ester (6) by (5S)-N-benzyloxycarbonyl-5-iodomethyl oxazolidine (7). Double stereoselection was examined using chiral ammonium salts as phase transfer catalysts and a substrate-directed chiral induction is documented.

Key words

amino acid - asymmetric alkylation - double stereo­selection - glycine template - 4-hydroxyornithine - phase transfer catalyst

References

• 1a Ezaki M. Iwami M. Yamashita M. Hashimoto S. Komori T. Umehara K. Mine Y. Kohsaka M. Aoiki H. Imanaka H. J. Antibiot.  1985,  38:  1453 
• 1b Uchida I. Shigematsu N. Ezaki M. Hashimoto M. J. Antibiot.  1985,  38:  1462 
• 1c Uchida I. Ezaki M. Shigematsu N. Hashimoto M. J. Org. Chem.  1985,  50:  1341 
• 1d Kannan R. Williams DH. J. Org. Chem.  1987,  52:  5435 
• 1e Hempel JC. Brown FK. J. Am. Chem. Soc.  1989,  111:  7323 
• 1f Brown FK. Hempel JC. Dixon JS. Amato S. Mueller L. Jeffs PW. J. Am. Chem. Soc.  1989,  111:  7328 
• 2a Pruess DL. Kellett M. J. Antibiot.  1983,  36:  208 
• 2b Evans RH. Ax H. Jacoby A. Williams TH. Jenkis E. Scannell JP. J. Antibiot.  1983,  36:  213 
• 2c Müller J.-C. Toome V. Pruess DL. Blount JF. Weigele M. J. Antibiot.  1983,  36:  217 
• 3a Koiso Y. Natori M. Iwasaki S. Sato S. Sonoda R. Fujita Y. Yaegashi H. Sato Z. Tetrahedron Lett.  1992,  33:  4157 
• 3b Koiso Y. Morisaki N. Yamashita Y. Mitsui Y. Shirai R. Hashimoto Y. Iwasaki S. J. Antibiot.  1998,  51:  418 
• 3c Koiso Y. Li Y. Iwasaki S. Hanaoka K. Kobayashi T. Sonoda R. Fujita Y. Yaegashi H. Sato Z. J. Antibiot.  1994,  47:  765 
• 3d Morisaki N. Mitsui Y. Yamashita Y. Koiso Y. Shirai R. Hashimoto Y. Iwasaki S. J. Antibiot.  1998,  51:  423 
• 4a Talbot G. Gaudry R. Berlinguet L. Can. J. Chem.  1956,  34:  911 
• 4b Mizusaki K. Makisumi S. Bull. Chem. Soc. Jpn.  1981,  54:  470 
• 4c Hausler J. Liebigs Ann. Chem.  1992,  1231 
• 4d Jacob M. Roumestant ML. Viallefont P. Martinez J. Synlett  1997,  691 
• 5a De Bernardo S. Tengi JP. Sasso GJ. Weigele M. J. Org. Chem.  1985,  50:  3457 
• 5b Girard A. Greck C. Genêt JP. Tetrahedron Lett.  1998,  39:  4259 
• 5c Mues H. Kazmaier U. Synthesis  2001,  487 
• 6 Schmidt U. Meyer R. Leitenberger V. Stäbler F. Lieberknecht A. Synthesis  1991,  409 
• 7 Jackson RFW. Rettie AB. Wood A. Wythes MJ. J. Chem. Soc., Perkin Trans. 1  1994,  1719 
• 8 Rudolph J. Hannig F. Theis H. Wischnat R. Org. Lett.  2001,  3:  3153 
• 9 Hutton CA. White JM. Tetrahedron Lett.  1997,  38:  1643 
• 10 Corey EJ. Xu F. Noe MC. J. Am. Chem. Soc.  1997,  119:  12414 
• 11 Lygo B. Wainwright PG. Tetrahedron Lett.  1997,  38:  8595 
• 12a Ooi T. Kameda M. Maruoka K. J. Am. Chem. Soc.  1999,  121:  6519 
• 12b Ooi T. Takeuchi M. Kameda M. Maruoka K. J. Am. Chem. Soc.  2000,  122:  5228 
• 12c Kita T. Georgieva A. Hashimoto Y. Nakata T. Nagasawa K. Angew. Chem. Int. Ed.  2002,  41:  2832 
• 13 O’Donnell MJ. Aldrichimica Acta  2001,  34:  3 
• 14a Lygo B. Crosby J. Peterson JA. Tetrahedron Lett.  1999,  40:  1385 
• 14b Lygo B. Tetrahedron Lett.  1999,  40:  1389 
• 15 Boisnard S. Carbonnelle A.-C. Zhu J. Org. Lett.  2001,  3:  2061 
• 16 Carbonnelle A.-C. Zhu J. Org. Lett.  2000,  2:  3477 
• 17 Substrate-directed transformation, see: Hoveyda AH. Evans DA. Fu GC. Chem. Rev.  1993,  93:  1307 
• Double asymmetric induction:
• 18a Horeau A. Kagan HB. Vigneron JP. Bull. Soc. Chim. Fr.  1968,  3795 
• 18b Masamune S. Choy W. Petersen JS. Sita LR. Angew. Chem., Int. Ed. Engl.  1985,  24:  1 
• 20 Estiarte MA. Diez A. Rubiralta M. Jackson RFW. Tetrahedron  2001,  57:  157 
• Double stereoselection using matched and mismatched chiral ammonium catalyst in the alkylation of a Gly-l-Phe derivative has been documented very recently, see:
• 22a Ooi T. Tayama E. Maruoka K. Angew. Chem. Int. Ed.  2003,  42:  579 
• 22b For an earlier example of an achiral quarternary ammonium salt catalyzed alkylation of a dipeptide, see: O’Donnell MJ. Zhou C. Scott WL. J. Am. Chem. Soc.  1996,  118:  6070 
• 23a Morikawa K. Sharpless KB. Tetrahedron Lett.  1993,  34:  5575 
• 23b Guzman-Perez A. Corey EJ. Tetrahedron Lett.  1997,  34:  5941 

19

We thank one of the reviews for pointing out this control experiment. This result was not unexpected, but it didn’t allow us to conclude whether the observed stereoselectivity in the presence of chiral ammonium salt was intrinsic to our substrate or was the consequence of the lack of the catalyst assistance.

21

Compound 17. R_f = 0.5 (eluent: ethyl acetate/heptane = 1/4); IR (CHCl₃) 3444, 3024, 2982, 1712, 1507 cm^-1; ¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.44 (s, 9 H) Hz, 1.46 (s, 9 H), 1.65-1.82 (m, 1 H), 1.93-1.98 (m, 1 H), 3.08-3.17 (ddd, 1 H, J ₁ = 13.3 Hz, J ₂ = 7.8 Hz, J ₃ = 6 Hz), 3.36-3.42 (m, 1 H), 3.91 (m, 1 H), 4.22 (m, 1 H), 5.10 (s, 2 H), 5.26 (m,1 H), 5,39 (m, 1 H), 7,35 (m, 5 H); ¹³C NMR (75 MHz, CDCl₃) δ 28.0, 28.3, 38.0, 46.8, 52.1, 66.9, 69.1, 82.3, 82.5, 128.1, 128.2, 128.5, 136.4, 156, 157.1, 171.6; MS (ESI) m/z 461 (M + Na); [α]_D = +9.3 (c 0.9 CHCl₃). Compound 18. R_f = 0.41 (eluant: ethyl acetate/heptane = 1/1); IR (CHCl₃) 3445, 1783, 1717 cm^-1; ¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.45 (s, 1 H), 2.32 (m, 1 H), 2.46-2.53 (m, 1 H), 3.30 (dt, 1 H, J ₁ = 15 Hz, J ₂ = 6.3 Hz), 3.52-3.56 (m, 1 H), 4.23 (br d, 1 H, J = 6.8 Hz), 4.75 (br s, 1 H), 5.12-5.18 (m, 4 H), 7.36 (m, 5 H); ¹³C NMR (75 MHz, CDCl₃) δ 28.2, 31.4, 44.6, 49.5, 67.1, 77.2, 80.7, 128.1, 128.2, 128.6, 136.2, 155.3, 156.7, 175.1; MS (EI) m/z 387 (M + Na), 403 (M + K); [α]_D = -18.1 (c 0.57 CHCl₃); [α]_D = -22.4 (c 0.5 CHCl₃). [20]