Control of the enantiochemistry of electrophilic substitutions of N-pivaloyl-α-lithio-o-ethylaniline: Stereoinformation transfer based on the method of organolithium formation

Journal of the American Chemical Society

Volumn 118, Issue 6, 1996, Pages 1575-1576

  Basu, Amit ^a   Beak, Peter ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANILINE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029920726     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja951895w     Document Type: Article

References (34)

1. (a) Thayumanavan, S.; Lee, S.; Liu, C.; Beak, P. J. Am. Chem. Soc. 1994, 116, 9755.
2. (b) Beak, P.; Du, H. J. Am. Chem. Soc. 1993, 115, 2516.
3. (c) Beak, P.; Kerrick, S. T.; Wu, S.; Chu, J. J. Am. Chem. Soc. 1994, 116, 3231.
4. (a) Hoppe, I.; Marsch, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2158.
5. (b) Kaiser, B.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 323.
6. (c) Zschage, O.; Hoppe, D. Tetrahedron 1992, 48, 5657.
7. (d) Hoppe, D.; Hintze, F.; Tebben, P.; Paetow, M.; Ahrens, H.; Schwerdtfeger, J.; Sommerfeld, P.; Haller, J.; Guarnieri, W.; Kolczewski,. S.; Hense, T.; Hoppe, I. Pure Appl. Chem. 1994, 66, 1479.
8. 2O to THF as the solvent for the (-)-sparteine-mediated lithiation/substitution of Boc-N-methyl benzyl amine. Schlosser, M.; Limat, D. J. Am. Chem. Soc. 1995, 117, 12342.
9. Lautens, M.; Gajda, C.; Chiu, P. J. Chem. Soc., Chem. Commun. 1993, 1193. Denmark, S. E.; Nakajima, N.; Nicaise, O. J.-C. J. Am. Chem. Soc. 1994, 116, 8797. Klein, S.; Marek, I.; Poisson, J.-F.; Normant, J.-F. J. Am. Chem. Soc. 1995, 117, 8853. Muci, A.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc. 1995, 117, 9075.
10. Lautens, M.; Gajda, C.; Chiu, P. J. Chem. Soc., Chem. Commun. 1993, 1193. Denmark, S. E.; Nakajima, N.; Nicaise, O. J.-C. J. Am. Chem. Soc. 1994, 116, 8797. Klein, S.; Marek, I.; Poisson, J.-F.; Normant, J.-F. J. Am. Chem. Soc. 1995, 117, 8853. Muci, A.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc. 1995, 117, 9075.
11. Lautens, M.; Gajda, C.; Chiu, P. J. Chem. Soc., Chem. Commun. 1993, 1193. Denmark, S. E.; Nakajima, N.; Nicaise, O. J.-C. J. Am. Chem. Soc. 1994, 116, 8797. Klein, S.; Marek, I.; Poisson, J.-F.; Normant, J.-F. J. Am. Chem. Soc. 1995, 117, 8853. Muci, A.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc. 1995, 117, 9075.
12. Lautens, M.; Gajda, C.; Chiu, P. J. Chem. Soc., Chem. Commun. 1993, 1193. Denmark, S. E.; Nakajima, N.; Nicaise, O. J.-C. J. Am. Chem. Soc. 1994, 116, 8797. Klein, S.; Marek, I.; Poisson, J.-F.; Normant, J.-F. J. Am. Chem. Soc. 1995, 117, 8853. Muci, A.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc. 1995, 117, 9075.
13. For studies on the effect of temperature on the configurational stability of related organolithium species, see: Gawley, R. E.; Zhang, Q. Tetrahedron 1994, 56, 6077. Elworthy, T. R.; Meyers, A. I. Tetrahedron 1994, 56, 6089. Burchat, A. F.; Chong, J. M.; Park, S. B. Tetrahedron Lett. 1993, 34, 51, Kawabata, T.; Wirth, T.; Yahiro, K.; Suzuki, H.; Fuji, K. J. Am. Chem. Soc. 1994, 116, 10809.
14. For studies on the effect of temperature on the configurational stability of related organolithium species, see: Gawley, R. E.; Zhang, Q. Tetrahedron 1994, 56, 6077. Elworthy, T. R.; Meyers, A. I. Tetrahedron 1994, 56, 6089. Burchat, A. F.; Chong, J. M.; Park, S. B. Tetrahedron Lett. 1993, 34, 51, Kawabata, T.; Wirth, T.; Yahiro, K.; Suzuki, H.; Fuji, K. J. Am. Chem. Soc. 1994, 116, 10809.
15. For studies on the effect of temperature on the configurational stability of related organolithium species, see: Gawley, R. E.; Zhang, Q. Tetrahedron 1994, 56, 6077. Elworthy, T. R.; Meyers, A. I. Tetrahedron 1994, 56, 6089. Burchat, A. F.; Chong, J. M.; Park, S. B. Tetrahedron Lett. 1993, 34, 51, Kawabata, T.; Wirth, T.; Yahiro, K.; Suzuki, H.; Fuji, K. J. Am. Chem. Soc. 1994, 116, 10809.
16. For studies on the effect of temperature on the configurational stability of related organolithium species, see: Gawley, R. E.; Zhang, Q. Tetrahedron 1994, 56, 6077. Elworthy, T. R.; Meyers, A. I. Tetrahedron 1994, 56, 6089. Burchat, A. F.; Chong, J. M.; Park, S. B. Tetrahedron Lett. 1993, 34, 51, Kawabata, T.; Wirth, T.; Yahiro, K.; Suzuki, H.; Fuji, K. J. Am. Chem. Soc. 1994, 116, 10809.
17. The two most common methods are deprotonation and tin/lithium exchange (lithiodestannylation).
18. For a review of the directed lateral lithation, see: Clark, R. D.; Jahangir, A. Org. React. 1995, 47, 1.
19. 13C NMR, and mass spectral analysis.
20. The organosilane 4 was subject to a Tamao-Fleming oxidation to afford the hydroxy amide. The oxidation has been shown to proceed with retention of configuration, even at a benzylic position, Fleming, I.; Henning, R.; Parker, D. C.; Plant, H. E.; Sanderson, P. E. J. J. Chem. Soc., Perkin Trans. 1 1995, 317. Oppolzer, W.; Mills, R. J.; Pachinger, W.; Stevenson, T. Helv. Chim. Acta 1986, 69, 1542. This was correlated with a sample of the enantioenriched alcohol independently prepared from commercially available (S)-(-)-2-bromo-α-methylbenzyl alcohol. The MOM-protected bromo alcohol was electrophilically aminated using Trost's azidomethyl phenyl sulfide methodology. Subsequent hydrolysis of the triazoline and acylation of the resultant aniline, followed by deprotection of the MOM ether, afforded (5)-14 in 86% ee. Trost, B. M.; Pearson, W. H. J. Am. Chem. Soc. 1981, 103, 2483. The absolute configuration of 11 was determined through independent chemical synthesis from (R)-3-phenylbutyric acid. The sequence involves reduction of the acid to the alcohol and activation as the tosylate, followed by a one-carbon homologation with methylmagnesium bromide in the presence of the Tamura-Kochi catalyst. Nitration of the alkane, followed by reduction and pivaloylation, affords the desired product. See supporting information for full experimental details.
21. The organosilane 4 was subject to a Tamao-Fleming oxidation to afford the hydroxy amide. The oxidation has been shown to proceed with retention of configuration, even at a benzylic position, Fleming, I.; Henning, R.; Parker, D. C.; Plant, H. E.; Sanderson, P. E. J. J. Chem. Soc., Perkin Trans. 1 1995, 317. Oppolzer, W.; Mills, R. J.; Pachinger, W.; Stevenson, T. Helv. Chim. Acta 1986, 69, 1542. This was correlated with a sample of the enantioenriched alcohol independently prepared from commercially available (S)-(-)-2-bromo-α-methylbenzyl alcohol. The MOM-protected bromo alcohol was electrophilically aminated using Trost's azidomethyl phenyl sulfide methodology. Subsequent hydrolysis of the triazoline and acylation of the resultant aniline, followed by deprotection of the MOM ether, afforded (5)-14 in 86% ee. Trost, B. M.; Pearson, W. H. J. Am. Chem. Soc. 1981, 103, 2483. The absolute configuration of 11 was determined through independent chemical synthesis from (R)-3-phenylbutyric acid. The sequence involves reduction of the acid to the alcohol and activation as the tosylate, followed by a one-carbon homologation with methylmagnesium bromide in the presence of the Tamura-Kochi catalyst. Nitration of the alkane, followed by reduction and pivaloylation, affords the desired product. See supporting information for full experimental details.
22. The organosilane 4 was subject to a Tamao-Fleming oxidation to afford the hydroxy amide. The oxidation has been shown to proceed with retention of configuration, even at a benzylic position, Fleming, I.; Henning, R.; Parker, D. C.; Plant, H. E.; Sanderson, P. E. J. J. Chem. Soc., Perkin Trans. 1 1995, 317. Oppolzer, W.; Mills, R. J.; Pachinger, W.; Stevenson, T. Helv. Chim. Acta 1986, 69, 1542. This was correlated with a sample of the enantioenriched alcohol independently prepared from commercially available (S)-(-)-2-bromo-α-methylbenzyl alcohol. The MOM-protected bromo alcohol was electrophilically aminated using Trost's azidomethyl phenyl sulfide methodology. Subsequent hydrolysis of the triazoline and acylation of the resultant aniline, followed by deprotection of the MOM ether, afforded (5)-14 in 86% ee. Trost, B. M.; Pearson, W. H. J. Am. Chem. Soc. 1981, 103, 2483. The absolute configuration of 11 was determined through independent chemical synthesis from (R)-3-phenylbutyric acid. The sequence involves reduction of the acid to the alcohol and activation as the tosylate, followed by a one-carbon homologation with methylmagnesium bromide in the presence of the Tamura-Kochi catalyst. Nitration of the alkane, followed by reduction and pivaloylation, affords the desired product. See supporting information for full experimental details.
23. Pirkle, W. H., Welch, C. J., Lamm, B. J. Org. Chem. 1992, 57, 3854.
24. 3SnH, afforded (S)-9 in 82% ee. Dolan, S. C.; MacMillan, J. J. Chem. Soc., Chem. Commun. 1985, 1588.
25. 2O, a subsequent solvent study revealed that MTBE afforded higher yields with little effect on the enantioselectivities.
26. (a) Still, W. C.; Sreekumar, C. J. Am. Chem. Soc. 1980, 102, 1201.
27. (b) Aggarwal, V. K. Angew. Chem., Int. Ed. Engl. 1994, 33, 175 and references cited therein.
28. Asymmetric induction at a stereocenter capable of epimerizing under the reaction conditions is an example of dynamic kinetic resolution. See: Novori, R.; Tokunaga, M.; Kitamura, M. Bull. Chem. Soc. Jpn. 1995, 68, 36.
29. The diastereoselectivity of the addition of benzaldehyde to a metalated isoquinoloyloxazoline has been reported to be higher at -65°C than at -78°C. Zhang, P.; Gawley, R. E. Tetrahedron Lett. 1992, 33, 2945. A related effect has been reported for the enantioselective amidocuprate-mediated conjugate addition to enones. Rossiter, B. E.; Miao, G.; Swingle, N. M.; Eguchi, M.; Hernandez, A. E.; Patterson, R. G. Tetrahedron: Asymmetry 1992, 3, 231. The work of Schlosser and Limat (ref 2d) also shows a time-dependent enantioselectivity, consistent with the formation of diastereomeric complexes with (-)-sparteine.
30. The diastereoselectivity of the addition of benzaldehyde to a metalated isoquinoloyloxazoline has been reported to be higher at -65°C than at -78°C. Zhang, P.; Gawley, R. E. Tetrahedron Lett. 1992, 33, 2945. A related effect has been reported for the enantioselective amidocuprate-mediated conjugate addition to enones. Rossiter, B. E.; Miao, G.; Swingle, N. M.; Eguchi, M.; Hernandez, A. E.; Patterson, R. G. Tetrahedron: Asymmetry 1992, 3, 231. The work of Schlosser and Limat (ref 2d) also shows a time-dependent enantioselectivity, consistent with the formation of diastereomeric complexes with (-)-sparteine.
31. As far as we know, there is no known case of a lithiodestannylation that proceeds with inversion of configuration at the tin-bearing carbon. On the other hand, there are sporadic reports in the literature of electrophilic substitutions that proceed with inversion of configuration, most notably recent reports by both Hoppe and Gawley. Carstens, A.; Hoppe, D. Tetrahedron 1994, 6097. Gawley, R. E.; Zhang, Q. J. Org. Chem. 1995, 60, 5763.
32. As far as we know, there is no known case of a lithiodestannylation that proceeds with inversion of configuration at the tin-bearing carbon. On the other hand, there are sporadic reports in the literature of electrophilic substitutions that proceed with inversion of configuration, most notably recent reports by both Hoppe and Gawley. Carstens, A.; Hoppe, D. Tetrahedron 1994, 6097. Gawley, R. E.; Zhang, Q. J. Org. Chem. 1995, 60, 5763.
33. If (rac)-5 is transmetalated at -78°C in the presence of (-)-sparteine, trapping with TMSCl affords (rac)-3. This indicates that there is no kinetic resolution during the transmetalation step, consistent with the formation of two nonequilibrating diastereomeric complexes in equal ratios. However, if (rac)-5 is transmetalated at -78°C in the presence of (-)-sparteine and allowed to stir at -25°C for 2 h prior to cooling to -78°C and trapping with TMSCl, (R)-3 is obtained with 85% ee.
34. (17 For a discussion of the effectiveness of TMEDA as a bidentate ligand for lithium, see: Collum, D. B. Acc. Chem. Res. 1992, 25, 448.