Chiral allyl cations are captured by furan with 100% stereoselectivity: Synthesis of enantiopure 2-alkoxy-8-oxabicyclo[3.2.1]oct-6-en-3-ones by low- temperature [4+3] cycloaddition

Chemistry - A European Journal

Volumn 6, Issue 4, 2000, Pages 684-691

  Stark, Christian B W ^a   Pierau, Sabine ^b   Wartchow, Rudolf ^a   Hoffmann, H M R ^a  

^a LEIBNIZ UNIVERSITY HANNOVER   (Germany)

^b Department of Obstetrics Gynecology   (United States)

Author keywords

Acerals; Asymmetric synthesis; Chiral auxiliaries; Dilution effects; Ion Pairs; Mediumsized rings

Indexed keywords

ACETAL DERIVATIVE; ALLYL COMPOUND; CATION; FURAN DERIVATIVE;

ARTICLE; CHIRALITY; CYCLIZATION; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0034681560     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(20000218)6:4<684::AID-CHEM684>3.0.CO;2-Z     Document Type: Article

References (48)

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11. For example, S. Hatakeyama, H. Numata, K. Osanai, S. Takano, J. Chem. Soc. Chem. Commun. 1989, 1893. Synthesis of enantiopure triphyllenol in caryophyllene chemistry: C. E. Sowa, U. Eggert, H. M. R Hoffmann, Tetrahedron 1993, 49, 4183; U. Vogt, U. Eggert, A. M. Z. Slawin, D. J. Williams, H. M. R. Hoffmann, Angew. Chem. 1990, 102, 1530; Angew. Chem. Int. Ed. Engl. 1990, 29, 1456.
12. For example, S. Hatakeyama, H. Numata, K. Osanai, S. Takano, J. Chem. Soc. Chem. Commun. 1989, 1893. Synthesis of enantiopure triphyllenol in caryophyllene chemistry: C. E. Sowa, U. Eggert, H. M. R Hoffmann, Tetrahedron 1993, 49, 4183; U. Vogt, U. Eggert, A. M. Z. Slawin, D. J. Williams, H. M. R. Hoffmann, Angew. Chem. 1990, 102, 1530; Angew. Chem. Int. Ed. Engl. 1990, 29, 1456.
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14. Reviews: A. Alexakis, P. Mangeney, Tetrahedron: Asymmetry 1990, 1, 477. See also S. E. Denmark, N. G. Almstead, J. Am. Chem. Soc. 1991, 113, 8089, For some early work see P. A. Bartlett, W. S. Johnson, J. D. Elliott, J. Am. Chem. Soc. 1983, 105, 2088; P. V. Fish, W. S. Johnson, G. S. Jones, F. S. Tham, R. K. Kullnig, J. Org. Chem. 1994, 59, 6150; D. Seebach, R. Imwinkelried, T. Weber in Modern Synthetic Methods, Vol. 4 (Ed.: R. Scheffold), Springer, Heidelberg, 1986, p. 191; H.-J. Altenbach, Nachr. Chem. Tech. Lab. 1988, 36, 1212.
15. Reviews: A. Alexakis, P. Mangeney, Tetrahedron: Asymmetry 1990, 1, 477. See also S. E. Denmark, N. G. Almstead, J. Am. Chem. Soc. 1991, 113, 8089, For some early work see P. A. Bartlett, W. S. Johnson, J. D. Elliott, J. Am. Chem. Soc. 1983, 105, 2088; P. V. Fish, W. S. Johnson, G. S. Jones, F. S. Tham, R. K. Kullnig, J. Org. Chem. 1994, 59, 6150; D. Seebach, R. Imwinkelried, T. Weber in Modern Synthetic Methods, Vol. 4 (Ed.: R. Scheffold), Springer, Heidelberg, 1986, p. 191; H.-J. Altenbach, Nachr. Chem. Tech. Lab. 1988, 36, 1212.
16. Reviews: A. Alexakis, P. Mangeney, Tetrahedron: Asymmetry 1990, 1, 477. See also S. E. Denmark, N. G. Almstead, J. Am. Chem. Soc. 1991, 113, 8089, For some early work see P. A. Bartlett, W. S. Johnson, J. D. Elliott, J. Am. Chem. Soc. 1983, 105, 2088; P. V. Fish, W. S. Johnson, G. S. Jones, F. S. Tham, R. K. Kullnig, J. Org. Chem. 1994, 59, 6150; D. Seebach, R. Imwinkelried, T. Weber in Modern Synthetic Methods, Vol. 4 (Ed.: R. Scheffold), Springer, Heidelberg, 1986, p. 191; H.-J. Altenbach, Nachr. Chem. Tech. Lab. 1988, 36, 1212.
17. Reviews: A. Alexakis, P. Mangeney, Tetrahedron: Asymmetry 1990, 1, 477. See also S. E. Denmark, N. G. Almstead, J. Am. Chem. Soc. 1991, 113, 8089, For some early work see P. A. Bartlett, W. S. Johnson, J. D. Elliott, J. Am. Chem. Soc. 1983, 105, 2088; P. V. Fish, W. S. Johnson, G. S. Jones, F. S. Tham, R. K. Kullnig, J. Org. Chem. 1994, 59, 6150; D. Seebach, R. Imwinkelried, T. Weber in Modern Synthetic Methods, Vol. 4 (Ed.: R. Scheffold), Springer, Heidelberg, 1986, p. 191; H.-J. Altenbach, Nachr. Chem. Tech. Lab. 1988, 36, 1212.
18. Reviews: A. Alexakis, P. Mangeney, Tetrahedron: Asymmetry 1990, 1, 477. See also S. E. Denmark, N. G. Almstead, J. Am. Chem. Soc. 1991, 113, 8089, For some early work see P. A. Bartlett, W. S. Johnson, J. D. Elliott, J. Am. Chem. Soc. 1983, 105, 2088; P. V. Fish, W. S. Johnson, G. S. Jones, F. S. Tham, R. K. Kullnig, J. Org. Chem. 1994, 59, 6150; D. Seebach, R. Imwinkelried, T. Weber in Modern Synthetic Methods, Vol. 4 (Ed.: R. Scheffold), Springer, Heidelberg, 1986, p. 191; H.-J. Altenbach, Nachr. Chem. Tech. Lab. 1988, 36, 1212.
19. See also: M. Harmata, D. E. Jones, J. Org. Chem. 1997, 62, 1578.
20. M. Lautens, R. Aspiotis, J. Colucci, J. Am. Chem. Soc. 1996, 118, 10930; H. M. L. Davies, G. Ahmed, M. R. Churchill, J. Am. Chem. Soc. 1996, 118, 10774; M. A. Walters, H. R. Arcand, J. Org. Chem. 1996, 61, 1478; A. S. Kende, H. Huang, Tetrahedron Lett. 1997, 38, 3353; S. Y. Cho, J. C. Lee, J. K. Cha, J. Org. Chem. 1999, 64, 3394; M. Harmata, D. E. Jones, M. Kahraman, U. Sharma, C, L. Barnes, Tetrahedron Lett. 1999, 40, 1831.
21. M. Lautens, R. Aspiotis, J. Colucci, J. Am. Chem. Soc. 1996, 118, 10930; H. M. L. Davies, G. Ahmed, M. R. Churchill, J. Am. Chem. Soc. 1996, 118, 10774; M. A. Walters, H. R. Arcand, J. Org. Chem. 1996, 61, 1478; A. S. Kende, H. Huang, Tetrahedron Lett. 1997, 38, 3353; S. Y. Cho, J. C. Lee, J. K. Cha, J. Org. Chem. 1999, 64, 3394; M. Harmata, D. E. Jones, M. Kahraman, U. Sharma, C, L. Barnes, Tetrahedron Lett. 1999, 40, 1831.
22. M. Lautens, R. Aspiotis, J. Colucci, J. Am. Chem. Soc. 1996, 118, 10930; H. M. L. Davies, G. Ahmed, M. R. Churchill, J. Am. Chem. Soc. 1996, 118, 10774; M. A. Walters, H. R. Arcand, J. Org. Chem. 1996, 61, 1478; A. S. Kende, H. Huang, Tetrahedron Lett. 1997, 38, 3353; S. Y. Cho, J. C. Lee, J. K. Cha, J. Org. Chem. 1999, 64, 3394; M. Harmata, D. E. Jones, M. Kahraman, U. Sharma, C, L. Barnes, Tetrahedron Lett. 1999, 40, 1831.
23. M. Lautens, R. Aspiotis, J. Colucci, J. Am. Chem. Soc. 1996, 118, 10930; H. M. L. Davies, G. Ahmed, M. R. Churchill, J. Am. Chem. Soc. 1996, 118, 10774; M. A. Walters, H. R. Arcand, J. Org. Chem. 1996, 61, 1478; A. S. Kende, H. Huang, Tetrahedron Lett. 1997, 38, 3353; S. Y. Cho, J. C. Lee, J. K. Cha, J. Org. Chem. 1999, 64, 3394; M. Harmata, D. E. Jones, M. Kahraman, U. Sharma, C, L. Barnes, Tetrahedron Lett. 1999, 40, 1831.
24. M. Lautens, R. Aspiotis, J. Colucci, J. Am. Chem. Soc. 1996, 118, 10930; H. M. L. Davies, G. Ahmed, M. R. Churchill, J. Am. Chem. Soc. 1996, 118, 10774; M. A. Walters, H. R. Arcand, J. Org. Chem. 1996, 61, 1478; A. S. Kende, H. Huang, Tetrahedron Lett. 1997, 38, 3353; S. Y. Cho, J. C. Lee, J. K. Cha, J. Org. Chem. 1999, 64, 3394; M. Harmata, D. E. Jones, M. Kahraman, U. Sharma, C, L. Barnes, Tetrahedron Lett. 1999, 40, 1831.
25. M. Lautens, R. Aspiotis, J. Colucci, J. Am. Chem. Soc. 1996, 118, 10930; H. M. L. Davies, G. Ahmed, M. R. Churchill, J. Am. Chem. Soc. 1996, 118, 10774; M. A. Walters, H. R. Arcand, J. Org. Chem. 1996, 61, 1478; A. S. Kende, H. Huang, Tetrahedron Lett. 1997, 38, 3353; S. Y. Cho, J. C. Lee, J. K. Cha, J. Org. Chem. 1999, 64, 3394; M. Harmata, D. E. Jones, M. Kahraman, U. Sharma, C, L. Barnes, Tetrahedron Lett. 1999, 40, 1831.
26. Cyclic allylic cations of the cyclohexenyl type are conformationally constrained and enter into [4+3] cycloadditions with complete stereoselectivity, giving enantiopure cycloadducts: H. M. R. Hoffmann, D. Wagner, R. Wartchow, Chem. Ber. 1990, 123, 2131; H. M. R. Hoffmann in Encyclopedia of Reagents for Organic Synthesis, Vol. 7 (Ed.: L. A. Paquette), Wiley, 1995, p.4591.
27. Cyclic allylic cations of the cyclohexenyl type are conformationally constrained and enter into [4+3] cycloadditions with complete stereoselectivity, giving enantiopure cycloadducts: H. M. R. Hoffmann, D. Wagner, R. Wartchow, Chem. Ber. 1990, 123, 2131; H. M. R. Hoffmann in Encyclopedia of Reagents for Organic Synthesis, Vol. 7 (Ed.: L. A. Paquette), Wiley, 1995, p.4591.
28. C. B. W. Stark, U. Eggert, H. M. R. Hoffmann, Angew. Chem. 1998, 110, 1337; Angew. Chem. Int. Ed. 1998, 37, 1266.
29. C. B. W. Stark, U. Eggert, H. M. R. Hoffmann, Angew. Chem. 1998, 110, 1337; Angew. Chem. Int. Ed. 1998, 37, 1266.
30. These experiments are carried out in our undergraduate laboratories on a 0.2 mmol up to 100 mmol scale and are reproduced without difficulty. For example, 17 g of cycloadduct 3a was isolated per batch.
31. Determined by shift NMR experiments and analysis of the Mosher ester of the corresponding α-hydroxy ketones.
32. T. H. Chan, M. A. Brook, T. Chaly, Synthesis 1983, 203; cf. also ref. [15].
33. In the case of cycloadduct S. the methoxy-substituted cycloadduct was formed in 18% yield, in the case of 10, not at all. Silyl enol ethers derived from α,α-di(benzyloxy)ketones and α,α-di(1-phenylethoxy)-ketones gave lower yields.
34. S. Pierau, H. M. R. Hoffmann, Synlett 1999, 213.
35. H. M. R. Hoffmann, Angew. Chem. 1984, 95, 29; Angew. Chem. Int. Ed. Engl. 1984, 23, 1, 15. The terms compact and extended are not synonymous with endo and exo. The transition state of the six-centre Diels-Alder reaction is uniquely boat-like (cf., frozen boat-like cyclohexene moiety in norbornene, obtainable from eyclopentadiene and ethylene). endo and exo refer to the configuration of substituents on the periphery of the newly formed six-membered ring. Compact and extended describe alternative 7-carbon pericyclic geometries. These alternative geometries do not exist in concerted, lower order cycloadditions such as Diels-Alder and 1,3-dipolar reactions.
36. H. M. R. Hoffmann, Angew. Chem. 1984, 95, 29; Angew. Chem. Int. Ed. Engl. 1984, 23, 1, 15. The terms compact and extended are not synonymous with endo and exo. The transition state of the six-centre Diels-Alder reaction is uniquely boat-like (cf., frozen boat-like cyclohexene moiety in norbornene, obtainable from eyclopentadiene and ethylene). endo and exo refer to the configuration of substituents on the periphery of the newly formed six-membered ring. Compact and extended describe alternative 7-carbon pericyclic geometries. These alternative geometries do not exist in concerted, lower order cycloadditions such as Diels-Alder and 1,3-dipolar reactions.
37. 1-(4́-Bromophenyl)ethoxide is an undesirable leaving group, and the α-methoxy-α-1-(4′-methoxyphenyl)ethoxyketo acetal is too sensitive.
38. D. Bianchi, E. Battistel, A. Bosetti, P. Cesti, Z. Fekete. Tetrahedron: Asymmetry 1993, 4, 777. Lipase PS was kindly supplied by Amano, plc.
39. Isolated as a diastereomeric mixture with respect to carbon C1. The mixture was not separated since the configuration at C1 is lost on generation of the postulated 1-alkoxy-2-silyloxyallyl cation intermediate (Scheme 1).
40. GC suggested that a minor amount (< 10%) of E-configured silyl enol ether (E)-13b had also been formed, inseparable from Z-configuraled 13b. The presumed (E)-13b entered into cycloaddition less readily. Allowing for the presence of precursor (E)-13b, the yield of cycloadduct 14b is essentially quantitative.
41. Other types of dictation involving, for example, chelated lithium. sodium and zinc oxyallyl are feasible and are being studied.
42. U. Eggert, I. Rose, C. B. W. Stark, unpublished results.
43. For the selective preparation of trans-C-glycosides from these cycloadducts see: O. Gaertzen, A. M. Misske, P. Wolbers, H. M. R. Hoffmann, Synlett 1999, 1041; see also O. Gaertzen, A.M. Misske, P. Wolbers, H. M. R. Hoffmann, Tetrahedron Lett 1999, 40, 6359; for cis-C-glycosides: R. Dunkel, M. Mentzel, Ph. D. thesis, University of Hannover, in preparation.
44. For the selective preparation of trans-C-glycosides from these cycloadducts see: O. Gaertzen, A. M. Misske, P. Wolbers, H. M. R. Hoffmann, Synlett 1999, 1041; see also O. Gaertzen, A.M. Misske, P. Wolbers, H. M. R. Hoffmann, Tetrahedron Lett 1999, 40, 6359; for cis-C-glycosides: R. Dunkel, M. Mentzel, Ph. D. thesis, University of Hannover, in preparation.
45. For the selective preparation of trans-C-glycosides from these cycloadducts see: O. Gaertzen, A. M. Misske, P. Wolbers, H. M. R. Hoffmann, Synlett 1999, 1041; see also O. Gaertzen, A.M. Misske, P. Wolbers, H. M. R. Hoffmann, Tetrahedron Lett 1999, 40, 6359; for cis-C-glycosides: R. Dunkel, M. Mentzel, Ph. D. thesis, University of Hannover, in preparation.
46. C. B. W. Stark, Ph. D. thesis, University of Hannover, in preparation.
47. a) K. Schank, A. Weber, Chem. Ber. 1972, 105, 2188;
48. b) J. Fried, K. S. Petrakis, Synthesis 1983, 891.