A new variant of the Claisen rearrangement from malonate-derived allylic trimethylsilyl ketene acetals: Efficient, highly enantio- and diastereoselective syntheses of (+)-methyl dihydroepijasmonate and (+)-methyl epijasmonate

Angewandte Chemie - International Edition

Volumn 39, Issue 3, 2000, Pages 569-573

  Fehr, Charles ^a   Galindo, José ^a  

^a Analysis and Perception Department   (Switzerland)

Author keywords

Asymmetric synthesis; Enzyme catalysis; Fragrances; Lewis acids; Rearrangements

Indexed keywords

ACETAL DERIVATIVE; JASMONIC ACID; KETENE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0034603016     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000204)39:3<569::AID-ANIE569>3.0.CO;2-8     Document Type: Article

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63. a) G. Helmchen, A. Goeke, G. Lauer, M. Urmann, J. Fries, Angew. Chem. 1990, 102, 1079; Angew. Chem. Int. Ed. Engl. 1990, 29, 1024; K. Weinges, U. Lernhardt, Liebigs Ann. Chem. 1990, 751; T. Kitahara, T. Nishi, K. Mori, Tetrahedron 1991, 47, 6999; H. Stadtmüller, P. Knochel, Synlett 1995, 463, H. Stadtmüller, A. Vaupel, C. E. Tucker, T. Stüdemann, P. Knochel, Chem. Eur. J. 1996, 2, 1204; G. J. Roth, S. Kirschbaum, H. J. Bestmann, Synlett 1997, 618; J. S. U. H. S. Park, S. Gupta, J. K. Cha, Synth. Commun. 1997, 27, 2931; T. K. Sarkar, B. Mukherjee, S. K. Ghosh, Tetrahedron 1998, 54, 3243;
64. a) G. Helmchen, A. Goeke, G. Lauer, M. Urmann, J. Fries, Angew. Chem. 1990, 102, 1079; Angew. Chem. Int. Ed. Engl. 1990, 29, 1024; K. Weinges, U. Lernhardt, Liebigs Ann. Chem. 1990, 751; T. Kitahara, T. Nishi, K. Mori, Tetrahedron 1991, 47, 6999; H. Stadtmüller, P. Knochel, Synlett 1995, 463, H. Stadtmüller, A. Vaupel, C. E. Tucker, T. Stüdemann, P. Knochel, Chem. Eur. J. 1996, 2, 1204; G. J. Roth, S. Kirschbaum, H. J. Bestmann, Synlett 1997, 618; J. S. U. H. S. Park, S. Gupta, J. K. Cha, Synth. Commun. 1997, 27, 2931; T. K. Sarkar, B. Mukherjee, S. K. Ghosh, Tetrahedron 1998, 54, 3243;
65. a) G. Helmchen, A. Goeke, G. Lauer, M. Urmann, J. Fries, Angew. Chem. 1990, 102, 1079; Angew. Chem. Int. Ed. Engl. 1990, 29, 1024; K. Weinges, U. Lernhardt, Liebigs Ann. Chem. 1990, 751; T. Kitahara, T. Nishi, K. Mori, Tetrahedron 1991, 47, 6999; H. Stadtmüller, P. Knochel, Synlett 1995, 463, H. Stadtmüller, A. Vaupel, C. E. Tucker, T. Stüdemann, P. Knochel, Chem. Eur. J. 1996, 2, 1204; G. J. Roth, S. Kirschbaum, H. J. Bestmann, Synlett 1997, 618; J. S. U. H. S. Park, S. Gupta, J. K. Cha, Synth. Commun. 1997, 27, 2931; T. K. Sarkar, B. Mukherjee, S. K. Ghosh, Tetrahedron 1998, 54, 3243;
66. a) G. Helmchen, A. Goeke, G. Lauer, M. Urmann, J. Fries, Angew. Chem. 1990, 102, 1079; Angew. Chem. Int. Ed. Engl. 1990, 29, 1024; K. Weinges, U. Lernhardt, Liebigs Ann. Chem. 1990, 751; T. Kitahara, T. Nishi, K. Mori, Tetrahedron 1991, 47, 6999; H. Stadtmüller, P. Knochel, Synlett 1995, 463, H. Stadtmüller, A. Vaupel, C. E. Tucker, T. Stüdemann, P. Knochel, Chem. Eur. J. 1996, 2, 1204; G. J. Roth, S. Kirschbaum, H. J. Bestmann, Synlett 1997, 618; J. S. U. H. S. Park, S. Gupta, J. K. Cha, Synth. Commun. 1997, 27, 2931; T. K. Sarkar, B. Mukherjee, S. K. Ghosh, Tetrahedron 1998, 54, 3243;
67. a) G. Helmchen, A. Goeke, G. Lauer, M. Urmann, J. Fries, Angew. Chem. 1990, 102, 1079; Angew. Chem. Int. Ed. Engl. 1990, 29, 1024; K. Weinges, U. Lernhardt, Liebigs Ann. Chem. 1990, 751; T. Kitahara, T. Nishi, K. Mori, Tetrahedron 1991, 47, 6999; H. Stadtmüller, P. Knochel, Synlett 1995, 463, H. Stadtmüller, A. Vaupel, C. E. Tucker, T. Stüdemann, P. Knochel, Chem. Eur. J. 1996, 2, 1204; G. J. Roth, S. Kirschbaum, H. J. Bestmann, Synlett 1997, 618; J. S. U. H. S. Park, S. Gupta, J. K. Cha, Synth. Commun. 1997, 27, 2931; T. K. Sarkar, B. Mukherjee, S. K. Ghosh, Tetrahedron 1998, 54, 3243;
68. a) G. Helmchen, A. Goeke, G. Lauer, M. Urmann, J. Fries, Angew. Chem. 1990, 102, 1079; Angew. Chem. Int. Ed. Engl. 1990, 29, 1024; K. Weinges, U. Lernhardt, Liebigs Ann. Chem. 1990, 751; T. Kitahara, T. Nishi, K. Mori, Tetrahedron 1991, 47, 6999; H. Stadtmüller, P. Knochel, Synlett 1995, 463, H. Stadtmüller, A. Vaupel, C. E. Tucker, T. Stüdemann, P. Knochel, Chem. Eur. J. 1996, 2, 1204; G. J. Roth, S. Kirschbaum, H. J. Bestmann, Synlett 1997, 618; J. S. U. H. S. Park, S. Gupta, J. K. Cha, Synth. Commun. 1997, 27, 2931; T. K. Sarkar, B. Mukherjee, S. K. Ghosh, Tetrahedron 1998, 54, 3243;
69. a) G. Helmchen, A. Goeke, G. Lauer, M. Urmann, J. Fries, Angew. Chem. 1990, 102, 1079; Angew. Chem. Int. Ed. Engl. 1990, 29, 1024; K. Weinges, U. Lernhardt, Liebigs Ann. Chem. 1990, 751; T. Kitahara, T. Nishi, K. Mori, Tetrahedron 1991, 47, 6999; H. Stadtmüller, P. Knochel, Synlett 1995, 463, H. Stadtmüller, A. Vaupel, C. E. Tucker, T. Stüdemann, P. Knochel, Chem. Eur. J. 1996, 2, 1204; G. J. Roth, S. Kirschbaum, H. J. Bestmann, Synlett 1997, 618; J. S. U. H. S. Park, S. Gupta, J. K. Cha, Synth. Commun. 1997, 27, 2931; T. K. Sarkar, B. Mukherjee, S. K. Ghosh, Tetrahedron 1998, 54, 3243;
70. b) see also: F.-P. Montforts, I. Gesing-Zibulak, W. Grammenos, M. Schneider, K. Laumen, Helv. Chim. Acta 1989, 72, 1852; C. Borm, E. Winterfeldt, Liebigs Ann. 1996, 1209, and references therein.
71. b) see also: F.-P. Montforts, I. Gesing-Zibulak, W. Grammenos, M. Schneider, K. Laumen, Helv. Chim. Acta 1989, 72, 1852; C. Borm, E. Winterfeldt, Liebigs Ann. 1996, 1209, and references therein.
72. V. Rautenstrauch, J.-J. Riedhauser (Firmenich). EP-B 715615 1998 (prior. 23.06.1994).
73. C. Fehr. Angew. Chem. 1998, 110, 2509; Angew. Chem. Int. Ed. 1998, 37, 2407.
74. C. Fehr. Angew. Chem. 1998, 110, 2509; Angew. Chem. Int. Ed. 1998, 37, 2407.
75. a) Review: B, Rickborn, Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, New York, 1991, p. 733; b) R. Sudha, K. Malola Narasimhan, V. Geetha Saraswathi, S. Sankararaman, J. Org. Chem. 1996, 61, 1877; c) H. Sasai, T. Arai, E. Emori, M. Shibasaki, J. Org. Chem. 1995, 60, 465; d) H. B. Henbest, T. I. Wrigley, J. Chem. Soc. 1957, 4765.
76. a) Review: B, Rickborn, Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, New York, 1991, p. 733; b) R. Sudha, K. Malola Narasimhan, V. Geetha Saraswathi, S. Sankararaman, J. Org. Chem. 1996, 61, 1877; c) H. Sasai, T. Arai, E. Emori, M. Shibasaki, J. Org. Chem. 1995, 60, 465; d) H. B. Henbest, T. I. Wrigley, J. Chem. Soc. 1957, 4765.
77. a) Review: B, Rickborn, Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, New York, 1991, p. 733; b) R. Sudha, K. Malola Narasimhan, V. Geetha Saraswathi, S. Sankararaman, J. Org. Chem. 1996, 61, 1877; c) H. Sasai, T. Arai, E. Emori, M. Shibasaki, J. Org. Chem. 1995, 60, 465; d) H. B. Henbest, T. I. Wrigley, J. Chem. Soc. 1957, 4765.
78. a) Review: B, Rickborn, Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, New York, 1991, p. 733; b) R. Sudha, K. Malola Narasimhan, V. Geetha Saraswathi, S. Sankararaman, J. Org. Chem. 1996, 61, 1877; c) H. Sasai, T. Arai, E. Emori, M. Shibasaki, J. Org. Chem. 1995, 60, 465; d) H. B. Henbest, T. I. Wrigley, J. Chem. Soc. 1957, 4765.
79. For the hydroboration of racemic (2)-10a, which is also syn-selective (70:30), leading predominantly to the trans-disubstituted system, see; T. Kitahara, K. Hamaguchi, Y. Warita, Y. Takagi, K. Mori, Agric. Biol. Chem. 1986, 50, 1867.
80. 2, 10 C), as concomitant acid-catalyzed lactonization of the anti-epoxide 18a to 20a (10% formed) is much faster than that of 17a to 19a (1% formed).
81. 2O, followed by silylation of the unconverted alcohol with N,O-bis(trimethylsilyl)acetamide (BSA) in toluene at 100 C for 5 min and chiral GC analysis (Megadex 5). Normal GC analysis did not always give reproducible results (thermal instability of 11a).
82. 2 as solvent.