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Synlett 2003(2): 0211-0214
DOI: 10.1055/s-2003-36799
LETTER
© Georg Thieme Verlag Stuttgart · New York

A First Asymmetric Diamination of Olefins

Kilian Muñiz*a, Martin Niegerb
a Kekulé-Institut für Organische Chemie und Biochemie, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
Fax: +49(228)735813; e-Mail: kilian.muniz@uni-bonn.de;
b Institut für Anorganische Chemie, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
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Publication History

Received 13 November 2002
Publication Date:
22 January 2003 (online)

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Abstract

An asymmetric diamination of olefins employing stable imidoosmium(VIII) complexes is described for the first time. The reaction is based on the use of chiral acrylic esters and related substrates with enantiopure menthol and 8-phenyl menthol as chiral auxiliaries and gives rise to osmaimidazolidines with good to excellent diastereomeric ratios (up to 95:5). Removal of the osmium centre and the chiral auxiliary leads to novel enantiopure 1,2,3-trisubstituted compounds.

Key words

diamines - asymmetric synthesis - imido complexes - osmium - diastereoselectivity

    References

  • 1a Gómez Aranda V. Barluenga J. Aznar F. Synthesis  1974,  504 
    Article in Thieme ConnectGoogle Scholar
  • 1b Aznar F. PhD Thesis   Zaragoza; Spain: 1975. 
    Article in Thieme ConnectGoogle Scholar
  • 2 Bäckvall J.-E. Tetrahedron Lett.  1975,  2225 
    CrossrefGoogle Scholar
  • 3 Chong AO. Oshima K. Sharpless KB. J. Am. Chem. Soc.  1977,  99:  3420 
    CrossrefGoogle Scholar
  • 4a Barluenga J. Alonso-Cires L. Asensio G. Synthesis  1979,  962 
    Google Scholar
  • 4b Barluenga J. Aznar F. de Mattos MCS. Kover WB. García-Granda S. Pérez-Carreño E. J. Org. Chem.  1991,  56:  2930 
    Google Scholar
  • 5 Schofield MH. Kee TP. Anhaus JT. Schrock RR. Johnson KH. Davis WM. Inorg. Chem.  1991,  30:  3595 
    CrossrefGoogle Scholar
  • Catalytic racemic diamination of functionalised olefins:
  • 6a Jeong JU. Tao B. Sagasser I. Henniges H. Sharpless KB. J. Am. Chem. Soc.  1998,  120:  6844 
    CrossrefGoogle Scholar
  • 6b Li G. Wei H.-X. Kim SH. Carducci M. Angew. Chem. Int. Ed.  2001,  40:  4277 
    CrossrefGoogle Scholar
  • 6c Wei H.-X. Kim SH. Li G. J. Org. Chem.  2002,  67:  4777 
    CrossrefGoogle Scholar
  • 7a Lucet D. Le Gall T. Mioskowski C. Angew. Chem. Int. Ed.  1998,  37:  2580 
    CrossrefPubMedGoogle Scholar
  • 7b Noyori R. Ohkuma T. Angew. Chem. Int. Ed.  2001,  40:  40 
    CrossrefPubMedGoogle Scholar
  • 8a Nugent WA. Harlow RL. McKinney RJ. J. Am. Chem. Soc.  1979,  101:  7265 
    CrossrefGoogle Scholar
  • 8b Danopoulos AA. Wilkinson G. Hussain-Bates B. Hursthouse MB. J. Chem. Soc., Dalton Trans.  1991,  269 
    CrossrefGoogle Scholar
  • 9a Kolb HC. VanNieuwenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 
    CrossrefGoogle Scholar
  • 9b Kolb HC. Sharpless KB. In Transition Metals For Organic Chemistry: Building Blocks and Fine Chemicals   Vol. II:  Beller M. Bolm C. Wiley-VCH; Weinheim: 1998.  p.219 
    CrossrefGoogle Scholar
  • 9c Kolb HC. Sharpless KB. In Transition Metals For Organic Chemistry: Building Blocks and Fine Chemicals   Vol. II:  Beller M. Bolm C. Wiley-VCH; Weinheim: 1998.  p.243 
    CrossrefGoogle Scholar
  • 9d Bolm C. Hildebrand JP. Muñiz K. In Catalytic Asymmetric Synthesis   Ojima I. Wiley-VCH; Weinheim: 2000.  p.299 
    CrossrefGoogle Scholar
  • 9e For stoichiometric asymmetric aminohydroxylation reactions, see also: Rubenstein H. Svendsen JS. Acta Chem. Scand.  1994,  48:  439 
    CrossrefGoogle Scholar
  • 12 Data for crystal structure analysis were measured on a Nonius KappaCCD diffractometer. 4a: hexagonal, P6(1) (No.169), a = 17.7617 (2), c = 18.3872 (2) Å, V = 5023.60 (10) Å3, Z = 6, µ = 3.847 mm-1, T = 123K, 46712 reflections, 5872 unique reflections (2θmax = 50°), R1 = 0.0273 [I> 2sigma(I)], wR2 = 0.0613 (all data), 373 parameters and 44 restraints. Empirical absorption correction was applied. Crystallographic data (excluding structure factors) for the structure reported have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-192700. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax:+44 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk)
  • For example:
  • 13a Barluenga J. Montserrat JM. Flórez J. García-Granda S. Martín E. Angew. Chem., Int. Ed. Engl.  1994,  33:  1392 
    CrossrefGoogle Scholar
  • 13b Oppolzer W. Robbiani C. Bättig K. Helv. Chim. Acta  1980,  63:  2015 
    CrossrefGoogle Scholar
  • 13c d’Angelo J. Maddaluno J. J. Am. Chem. Soc.  1986,  108:  8112 
    CrossrefGoogle Scholar
  • 16 Rubin AE. Sharpless KB. Angew. Chem., Int. Ed. Engl.  1997,  36:  2637 
    CrossrefGoogle Scholar
  • 19a Nakamura Y. Hirai M. Tamotsu K. Yonezawa Y. Shin C.-G. Bull. Chem. Soc. Jpn.  1995,  68:  1369 
    CrossrefGoogle Scholar
  • 19b Synthesis via aminohydroxylation: Han H. Yoon J. Janda KD. J. Org. Chem.  1998,  63:  2045 
    CrossrefGoogle Scholar
  • 20 Corey EJ. DaSilva JP. Virgil S. Yuen P.-W. Connell RD. J. Am. Chem. Soc.  1989,  111:  9243 
    CrossrefGoogle Scholar
10

Details on the full characterisation of new compounds, further substrates including studies on functional group tolerance, and X-ray structures of various racemic compounds will be given in a full account.

11

Typical experimental procedure for the diamination of olefins: (-)-8-Phenylmenthyl cinnamate (181 mg, 0.5 mmol) was added to a solution of bis(N-t-butylimido)dioxo-osmium(VIII) (183 mg, 0.5 mmol) in 5 mL of freshly distilled THF. The resulting orange solution was stirred at r.t. for 11 h during which it turned dark red. The solvent was removed under reduced pressure to leave a red-brown oil which was passed through a small pad of silica gel (hexanes-ethyl acetate, 4:1). The pure mixture of the two diastereomers (248 mg, 0.34 mmol, 68% yield) was separated by semipreparative HPLC (Knauer Eurospher 100CN, t-BuOCH3-n-hexane, 15:85, 14 mL/min, 254 nm). Retention times: 12.9 min for 4b and 15.6 min for 4a. Selected data for the major diastereomer 4a: 1H NMR (300 MHz, benzene-d 6, 25 °C): δ = 0.79 (d, J = 6.4 Hz, 3 H), 0.80-0.95 (m, 4 H), 1.08 (s, 3 H), 1.18 (s, 9 H), 1.19 (s, 9 H), 1.22 (s, 3 H), 1.43-1.55 (m, 1 H), 1.60-1.71 (m, 1 H), 2.05-2.20 (m, 2 H), 3.64 (s, 1 H), 4.77 (dt, J = 4.1, 10.7 Hz, 1 H), 4.90 (s, 1 H), 6.85-6.93 (m, 1 H), 7.01-7.28 (m, 9 H). 13C NMR (75 MHz, benzene-d 6, 25 °C): δ = 21.9, 23.8, 26.7, 29.4, 30.2, 30.9, 31.3, 34.81, 39.5, 41.8, 50.2, 66.8, 67.4, 76.4, 81.3, 84.1, 125.4, 125.7, 127.2, 127.7, 127.9, 128.3, 128.6, 171.2. MS (EI, 70 eV): m/z (%): 728 (2) [M+], 469 (17), 413 (11), 279 (39), 146 (100). HRMS: calcd for C33H49N2O4 188Os: 724.3173, found: 724.3166.

14

At present we refrain from any mechanistic discussion. Both a [2+2] or [3+2] mechanism [9] might be operating. Experimental and theoretical investigations addressing this question are underway.

15

Apparently, this way of amide formation is not a general reaction. While it worked well for the present purpose, preliminary reactions indicated that it is not suitable for conventional N-alkylated α-amino esters. In these cases, the reaction proceeds very sluggishly and with complete racemization (K. Muñiz, unpublished results).

17

Typical experimental procedure for LiAlH 4 reduction: Osmaimidazolidine 4b (365 mg, 0.5 mmol) was dissolved in absolute THF (4 mL), LiAlH4 (57 mg, 1.5 mmol) was added in one portion and the resulting mixture was stirred for 2 hours at r.t. It was treated with methanol and water, extracted with ethyl acetate, dried over MgSO4 and filtered over celite. The solvent was removed under reduced pressure to leave the desired compound 9 as a colourless oil (131 mg, 0.47 mmol, 94% yield). Selected data for 9: [α]D 22 = -22 (CH2Cl2, c = 0.1). 1H NMR (300 MHz, DMSO-d 6, 25 °C): δ = 0.93 (s, 9 H), 0.97 (s, 9 H), 3.16 (dd, J = 2.6, 10.7 Hz, 1 H), 3.19-3.42 (m, 5 H), 3.80 (d, J = 7.0 Hz, 1 H), 7.19-7.47 (m, 5 H). 13C NMR (75 MHz, DMSO-d 6, 25 °C): δ = 29.9, 30.0, 49.9, 50.4, 57.58, 58.8, 61.5, 125.9, 127.4, 128.0, 147.0. MS (EI, 70 eV): m/z (%): 278 (3) [M+], 259 (11), 222 (37), 201 (66), 166 (49), 77 (100), 65 (95). Elemental analysis: calcd for C17H30N2O: C 73.33; H 10.86; N 10.06; found: C 73.62; H 11.01; N 9.89.

18

Typical experimental procedure for Os removal: Osmaimidazolidine 10b (177 mg, 0.35 mmol) was dissolved in absolute ethanol (3 mL), sodium borohydride (30 mg, 0.79 mmol) was added in small portions and the resulting mixture was stirred for 60 min at r.t. It was filtered over celite and the solvent was removed under reduced pressure to leave the desired compound 11b as a colourless oil (89 mg, 0.31 mmol, 89% yield). Selected data for 11b: [α]D 22 = -89 (CH2Cl2, c = 0.1). 1H NMR (300 MHz, CDCl3, 25 °C): δ = 0.87 (d, J = 7.3 Hz, 3 H), 1.16 (s, 9 H), 1.26 (s, 9 H), 1.43 (s, 9 H), 2.91 (dq, J = 7.3, 9.4 Hz, 1 H), 3.47 (d, J = 9.4 Hz, 1 H), 7.52 (br s, 1 H). 13C NMR (75 MHz, CDCl3, 25 °C):
δ = 22.7, 28.4, 29.7, 29.7, 51.8, 51.8, 52.9, 56.9, 59.3, 171.5. MS (EI, 70 eV): m/z (%): 285 (6) [M+], 228 (17), 174 (66), 125 (49), 73 (100). Elemental analysis: calcd for C16H35N3O: C 67.32; H 12,36; N 14.72; found: C 66. 95; H 12.22; N 15.01.