1,13 and 1,14 asymmetric induction: Remote control

Tetrahedron Letters

Volumn 38, Issue 20, 1997, Pages 3491-3494

  Magnus, Nicholas ^a   Magnus, Philip ^a  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHELATE; POLYAMINE; SULFONE;

ARTICLE; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; IN VITRO STUDY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030952194     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00704-1     Document Type: Article

References (23)

1. Linnane, P.; Magnus, N.; Magnus, P. Nature 1997, Vol 385, 799. For example, for 1, the n = 1 series did not show any notable stereoselectivity, whereas the n = 2 series exhibited dramatic diastereoselective enhancements. The ratio of the erythro-isomers 2A and 2A′ is (2.2:1) in THF, and changes to 9:1 when HMPA (2.2 eq) is present. The amounts of threo-isomers 2B and 2B′ was reduced such that the 2AA′:2BB′ ratio changes from 2.7:1 in THF to 10:1 with HMPA (2.2 eq) additive. These effects disappear in the next homologous series n = 3, but are restored when n = 4; 2A:2A′ (4.5:1) (HMPA, 2.2 eq) and 2A/A′:2B/B′ (5.5:1) (HMPA, 2.2 eq). Conditions:-a) THF (0.1M in substrate)/2.2 equiv n-BuLi/0.5h/5.0 equiv PhCHO/-70°C. b) THF (0.1M in substrate)/2.2 equiv n-BuLi/0.5h/2.2 equiv HMPA/0.5K/5.0 equiv PhCHO/-70°C.
2. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
3. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
4. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
5. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
6. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
7. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
8. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
9. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
10. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
11. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
12. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
13. For examples of "Long-Range Asymmetric Induction" (LAI) reactions see:-Magnus, P.; Frost, C.; Linnane, P.; Spyvee, M. Tetrahedron Lett. 1996, 37, 9139. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1990, 31, 6239. McNeill, A. H.; Thomas, E. J. Tetrahedron Lett. 1992, 33, 1369. Hallett, D. J.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1995, 657 and references therein. Paetow, M.; Ahrens, H.; Hoppe, D. Tetrahedron Lett. 1992, 33, 5323. Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2517. Mears, R. J.; Whiting, A. Tetrahedron Lett. 1993, 34, 8155. Molander, G. A.; Bobbitt, K. L. J. Am. Chem. Soc. 1993, 115, 7518. Molander, G. A.; Haar, Jr. J. P. J. Am. Chem. Soc. 1993, 115, 40. Zhang, H-C.; Harris, B. D.; Maryanoff, C. A.; Maryanoff, B. E. Tetrahedron Lett. 1996, 37, 7897. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984. Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788.
14. 2/0°C, 100%. b) Dess-Martin periodane.
15. 1H NMR) to the newly formed stereogenic centers, we do not know their absolute stereochemistry. Even given the information in reference 1, it would be premature to hazard an educated guess based on the bicyclic chelate model.
16. Truce, W. E.; Klingler, T. C. J. Org. Chem. 1970, 35, 1834. Caturia, F.; Nájera, C. Tetrahedron Lett. 1996, 37, 4787.
17. Truce, W. E.; Klingler, T. C. J. Org. Chem. 1970, 35, 1834. Caturia, F.; Nájera, C. Tetrahedron Lett. 1996, 37, 4787.
18. Seebach, D.; Bossler, H.; Gründler, H.; Shoda, S.; Wenger, R. Helv. 1991, 74, 197.
19. Lehn, J-M, "Supramolecular Chemistry", VCH Weinheim, 1995.
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23. If we use racemic 6 (n = 3) in the dianion/PhCHO reaction, we obtained two diastereomers 7 in the same ratio (ca. 1.5:1 ) as in the enantiomerically enriched series. This can be viewed as circumstantial evidence for an intramolecular chelate, rather than an aggregate.