Chiral Heterocylic Carbenes in Asymmetric Homogeneous Catalysis†
Prof. Dr. Wolfgang A. Herrmann
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Search for more papers by this authorCorresponding Author
Lukas J. Goossen
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]Search for more papers by this authorChristian Köcher
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Search for more papers by this authorDr. Georg R. J. Artus
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Search for more papers by this authorProf. Dr. Wolfgang A. Herrmann
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Search for more papers by this authorCorresponding Author
Lukas J. Goossen
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]Search for more papers by this authorChristian Köcher
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Search for more papers by this authorDr. Georg R. J. Artus
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-85747 Garching (Germany), Fax: Int. code +(89)289-13473, e-mail: [email protected]
Search for more papers by this authorHeterocyclic Carbenes, Part 9. This work received generous support from the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie (PhD scholarship to L.J.G.), the Bayerische Forschungsstiftung (Bayerischer For-schungsverbund Katalyse, FORKAT), and the Volkswagenstiftung. Part 8: W. A. Herrmann, M. Elison, O. Runte, G. R. J. Artus, J. Organomet. Chem. 1995, 501, C1–C4.
Graphical Abstract
The ee values of the hydrosilylation of acetophenone with the rhodium catalyst 1 are only small; nevertheless, the robustness of the catalyst is impressive: The chiral carbene ligand, which is readily available and can be easily varied, remains bound to the metal in solution to over 100°C. Thus, no excess of ligand is necessary in the catalytic reactions.
References
- 1 W. A. Herrmann, M. Elison, J. Fischer, C. Köcher, G. R. J. Artus, Angew. Chem. 1995, 107, 2602–2605; Angew. Chem. Int. Ed. Engl. 1995, 34, 2371–2374.
- 2 W. A. Herrmann, M. Elison, J. Fischer, C. Köcher, DE4447068 (Hoechst AG), 1994; EP0719758, 1996 DE4447067 (Hoechst AG), 1994 EP0719753, 1996 DE47066 (Hoechst AG), 1994 EP0721953, 1996,.
- 3 A. A. Griednev, I. M. Mihaltseva, Synth. Commun. 1994, 24, 1547–1555.
- 4 W. A. Herrmann, L. J. Goossen, G. R. J. Artus, Organometallics, in print.
- 5 W. A. Herrmann, C. Köcher, L. J. Goossen, G. R. J. Artus, Chem. Eur. J. 1996, 2, 1627–1636.
- 6 (S,S)-2a: 13C NMR (100 MHz, THF/CD,3NO2): δ = 211.2 (C:), 144.3 (phenyl-CR), 127.1 (p-phenyl-CH), 126.6(phenyl-CH), 117.8 (NCH), 59.5 (NCH), 22.3 (CH3), (S,S)-2b: 13C NMR (400 MHz,CDCl3): δ = 210.5 (C:), 134.4, 131.8, 129.3, 129.0, 126.9, 126.3, 125.9, 124.4, 124.3 (naphthyl), 118.7 (NC), 56.4 (NCH), 22.2 (CH3).
- 7(a) K. Öfele,
W. A. Herrmann,
D. Mihalios,
M. Elison,
E. Herdtweck,
E. Scherer,
J. Mink,
J. Organomet. Chem.
1993,
459, 177–184;
(b)
M. Regitz,
Angew. Chem.
1996,
122, 791–794;
10.1002/ange.19961080706 Google ScholarAngew. Chem. Int. Ed. Engl. 1996, 35, 725–728.
- 8
Crystal structure analysis of 4b (C32H24N2O5W), Mr = 700.39, yellow plate 0.05 × 0.15 × 0.15 mm3, monoclinic, space group P21, a = 12.481(2), b = 12.349(1), c = 19.073(2) Å, b = 100.14(1)°, V = 2893.8 Å3, Z = 4, ρcalcd = 1.61 g cm−3, μ = 41.2 cm−1, T = −100.0(3)°C, measured with IPDS (STOE) with MoKα radiation, 240 pictures in the range 0° < φ < 360°, Δφ = 1.5°, 5 min exposure, distance between detector and crystal 80 mm, range 1.42° <θ <24.2°; 32746 reflections measured, 7 beyond the dynamic region, O overlapping, 2690 systematic absences or reflections with negative intensity, 8569 independent; Rmerge = 0.06, Lorentzian polarization and empirical absorption corrections performed with IPDS-Software, 7699 reflections with I>1.0 σ(I) used for refinement, 720 parameters, 10.7 reflections per parameter, Flack parameter −0.02(1), Chebychev polynomial weighting, hydrogen atoms calculated, residual electron density 1.71 eÅ−3 and −2.28 eÅ−3, GOF = 0.814, R = Σ(||Fo|-|Fc||)/Σ|Fo| = 0.035, R = w = [Σw(|Fo|- |Fc|)2/ΣwF
]1/2 = 0.040. Several physically doubtful thermal displacement parameters were obtained from refinement of 4b. Unsatisfactorily corrected absorption effects cannot be excluded as a reason. However, there is some evidence that 4b is contaminated with a small amount of 4a. The resulting unresolvable disorder in the crystal of 4b may well cause meaningless displacement parameters. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-179-122. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: int. code+(1223)336-033; e-mail: [email protected]).
- 9 Transition Metal Carbene Complexes (Eds.: U. Schubert, H. Fischer, P. Hofmann, K. Weiss, K.-H. Dötz, F. R. Kreissl), VCH, Weinheim 1983, p. 137–143.
- 10 3a: 1H NMR (400 MHz, CDCl3): δ = 7.4–7.2 (overlapping multipletts, 10H, phenyl-H), 6.75 (s, 2H, HC), 6.08 (q, 3J(H,H) = 7 Hz, 2H, NCH), 1.73 (d, 3J(H,H) = 7 Hz, 6H, CH3); 13C NMR (100 MHz, CDCl3): δ = 197.8 (CO), 189.2(CN2), 141.0, 128.6, 127.7, 126.7 (Ph-C), 118.4(NC), 58.5(NCH), 20.8 (CH3);IR(THF)ṽ;(CO) = 2050, 1968 cm−1. 4a:1H NMR (400 MHz,C6D6): δ = 7.14–7.29 (m, 10H, Ph-H); 6.48 (q, 3J(H,H) = 3 Hz, 2H, NCH), 6.28 (s, 2H, HC), 1.55 (d, 3J(H,H) = 6.5 Hz, 6H, CH3); 13C NMR (100 MHz, C6D6): δ = 200.9 (trans-CO), 198.5 (cis-CO), 180.3 (CN2), 141.2 (p-PhC), 129.4(PhC), 128.6 (PhCR), 127.1 (PhC), 120.4(CH), 60.9(CH),21.7(CH3); IR (THF) δ = 2060, 1927 cm−1.
- 11 5b: 1H NMR (400 MHz, CDCl3): δ = 8.97 (d, 3J(H,H) = 9 Hz, 1H, naphthyl-H), 8.58 (d, 3J(H,H) = 9 Hz, 1H, naphthyl-H), 8.0–7.0 (m, 12H, naphthyl-H), 7.22 (q, 3J(H,H) = 7 Hz, 2H, NCH), 7.01 (m, 2H, HC), 4.8 (m, 2H, cod-CH), 4.19 (m, 1H, cod-CH), 3.39 (m, 1H, cod-CH), 2.5–1.0 (m, 8H, cod-CH2), 2.03 (d, 3J(H,H) = 7 Hz, 3H, CH3), 1.84 (d, 3J(H,H) = 7 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): δ = 183.5 (d,1J(103Rh,C) = 51 Hz, CN2), 141.0, 136.4, 133.8, 131.0, 130.1, 129.0, 128.8, 128.5, 127.7, 127.2, 126.7, 126.1, 125.3, 125.1, 124.9, 123.8, 123.7, 121.4 (naphthyl-C), 119.3 (NCH), 118.6 (NCH), 98.4 (d, 1J(103Rh,C) = 7 Hz, cod-CH), 97.6 (d, 1J(103Rh,C) = 7 Hz, cod-CH), 70.0 (d, 1J(103Rh,C) = 5 Hz, cod-CH), 66.5 (d, 1J(103Rh,C) = 5 Hz, cod-CH), 57.2 (NCH), 55.2 (NCH), 32.5, 32.0 (cod-CH2), 29.2 (CH3), 27.2 (CH3), 23.1 22.8 (cod-CH2).
- 12 T. H. Johnson, K. C. Klein, S. Thomen, J. Mol. Catal. 1981, 12, 37–40.
- 13
I. Ojima,
K. Hirai
in Asymmetric Synthesis,
Vol. 5
(Ed. J. D. Morrison),
Academic Press,
1985,
p. 103–113.
10.1016/B978-0-08-092493-9.50009-8 Google Scholar
- 14 H. Brunner, Methoden der Organischen Chemie (Houben–Weyl), 4th ed. 1952 –, Vol. E 21, Thieme, Stuttgart, 1995, p. 4074–4081.
