A catalytic approach to (R)-(+)-muscopyridine with integrated "self-clearance"

Angewandte Chemie - International Edition

Volumn 42, Issue 3, 2003, Pages 308-311

  Fürstner, Alois ^a   Leitner, Andreas ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

Cross coupling; Iron; Macrocycles; Metathesis; Ruthenium

Indexed keywords

MIXTURES; REACTION KINETICS;

METAL-CATALYZED REACTIONS;

CATALYSIS;

ALKALOID; ALKANE; ALKENE; MUSCOPYRIDINE; PYRIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; COMPLEX FORMATION; MATHEMATICAL ANALYSIS; REACTION ANALYSIS; TEMPERATURE DEPENDENCE; THIN LAYER CHROMATOGRAPHY;

ALKALOIDS; CATALYSIS; PYRIDINES; STEREOISOMERISM;

EID: 0037455149     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200390103     Document Type: Article

References (51)

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28. Ruthenium-based metathesis catalysts are easily poisoned by amines. This problem can be circumvented by protonating the basic sites, see, for example: a) G. C. Fu, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1993, 115, 9856-9857; b) A. Fürstner, J. Grabowski, C. W. Lehmann, J. Org. Chem. 1999, 64, 8275-8280.
29. A. Fürstner, O. Guth, A. Düffels, G. Seidel, M. Liebl, B. Gabor, R. Mynott, Chem. Eur. J. 2001, 7, 4811-4820.
30. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
31. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
32. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
33. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
34. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
35. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
36. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
37. For previous applications of this catalyst see: a) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Wilton-Ely, Chem. Commun. 1999, 601-602; b) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742; c) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68; d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672; e) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C.W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069; f) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206; Angew. Chem. Int. Ed. 2002, 41, 2097-2101; g) A. Fürstner, M. Schlecle, Adv. Synth. Catal. 2002, 344, 657-665.
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45. In contrast, macrocyclic alkenes are not inert to the more active "second-generation" ruthenium catalysts. While in the present case this leads to undesirable polymerization, it is possible to use this ability to advantage: a) A. B. Smith, C. M. Adams, S. A. Kozmin, J. Am. Chem. Soc. 2001, 123, 990-991; b) A. Fürstner, O. R. Thiel, L. Ackermann, Org. Lett. 2001, 3, 449-451; c) C. W. Lee, R.H. Grubbs, Org. Lett. 2000, 2, 2145-2147; d) A. Fürstner, O. R. Thiel, N. Kindler, B. Bartkowska, J. Org. Chem. 2000, 65, 7990-7995.
46. In contrast, macrocyclic alkenes are not inert to the more active "second-generation" ruthenium catalysts. While in the present case this leads to undesirable polymerization, it is possible to use this ability to advantage: a) A. B. Smith, C. M. Adams, S. A. Kozmin, J. Am. Chem. Soc. 2001, 123, 990-991; b) A. Fürstner, O. R. Thiel, L. Ackermann, Org. Lett. 2001, 3, 449-451; c) C. W. Lee, R.H. Grubbs, Org. Lett. 2000, 2, 2145-2147; d) A. Fürstner, O. R. Thiel, N. Kindler, B. Bartkowska, J. Org. Chem. 2000, 65, 7990-7995.
47. In contrast, macrocyclic alkenes are not inert to the more active "second-generation" ruthenium catalysts. While in the present case this leads to undesirable polymerization, it is possible to use this ability to advantage: a) A. B. Smith, C. M. Adams, S. A. Kozmin, J. Am. Chem. Soc. 2001, 123, 990-991; b) A. Fürstner, O. R. Thiel, L. Ackermann, Org. Lett. 2001, 3, 449-451; c) C. W. Lee, R.H. Grubbs, Org. Lett. 2000, 2, 2145-2147; d) A. Fürstner, O. R. Thiel, N. Kindler, B. Bartkowska, J. Org. Chem. 2000, 65, 7990-7995.
48. In contrast, macrocyclic alkenes are not inert to the more active "second-generation" ruthenium catalysts. While in the present case this leads to undesirable polymerization, it is possible to use this ability to advantage: a) A. B. Smith, C. M. Adams, S. A. Kozmin, J. Am. Chem. Soc. 2001, 123, 990-991; b) A. Fürstner, O. R. Thiel, L. Ackermann, Org. Lett. 2001, 3, 449-451; c) C. W. Lee, R.H. Grubbs, Org. Lett. 2000, 2, 2145-2147; d) A. Fürstner, O. R. Thiel, N. Kindler, B. Bartkowska, J. Org. Chem. 2000, 65, 7990-7995.
49. For previous examples of tandem RCM/hydrogenation catalysis by ruthenium-carbene complexes see: a) A. Fürstner, K. Langemann, N. Kindler Studiengesellschaft Kohle mbH. US Patent 5, 936, 100 1999 (priority December 16, 1996); b) J. Louie, C. W. Bielawski, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 11312-11313.
50. For previous examples of tandem RCM/hydrogenation catalysis by ruthenium-carbene complexes see: a) A. Fürstner, K. Langemann, N. Kindler Studiengesellschaft Kohle mbH. US Patent 5, 936, 100 1999 (priority December 16, 1996); b) J. Louie, C. W. Bielawski, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 11312-11313.
51. Insertion of Mg into commercial 6-bromo-1-hexene is accompanied by partial cyclization to give (cyclopentylmethyl)magnesium bromide in addition to the desired 5-hexenylmagnesium bromide, see D. Lal, D. Griller, S. Husband, K. U. Ingold, J. Am. Chem. Soc. 1974, 96. 6355-6357. The side products resulting thereof are easily eliminated by flash chromatography and the yield of 14 refers to analytically pure product.