Two different pathways of stereoinformation transfer: Asymmetric substitutions in the (-)-sparteine mediated reactions of laterally lithiated N,N-diisopropyl-o-ethylbenzamide and N-pivaloyl-o-ethylaniline

Journal of the American Chemical Society

Volumn 119, Issue 35, 1997, Pages 8209-8216

  Thayumanavan, S ^a   Basu, Amit ^a   Beak, Peter ^a  

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

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; SPARTEINE;

ARTICLE; CHEMICAL MODIFICATION; DIASTEREOISOMER; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY; THERMODYNAMICS;

EID: 0030768599     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970930r     Document Type: Article

References (68)

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23. Experimental details are provided as Supporting Information.
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25. (a) The reaction of 3·1 with phenyldimethylsilyl chloride to obtain 12 was not optimized for enantioselectivities. Therefore, even though the enrichment appears to be different than for trimethylsilyl chloride, the reaction is assumed to have the same sense of facial selectivity as 10.
26. (b) The lithiation had to be carried out in MTBE:pentane, because 2 could not be lithiated in pentane in the absence of (-)-sparteine. The reaction in Table 3 was carried out in pentane, and the difference in the enantiomeric ratios is attributed to the solvent difference.
27. The S-enantiomers of the products 5-7 can also be obtained in moderate selectivities by the reaction of methyl chloride with appropriately substituted, laterally lithiated intermediate in the presence of (-)-sparteine. 6a
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31. The enantioenrichment of the product is not taken into account, since the organolithium intermediate is configurationally labile and enantiode-termination occurs after deprotonation. The details of the calculations are provided as Supporting Information.
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40. Lithio-destannylations with retention of configuration at the carbon bearing tin are usually observed, see: Still, W. C.; Sreekumar, C. J. Am. Chem. Soc. 1980, 102, 1201. Sawyer, J. S.; Macdonald, T. L.; McGarvey, G. J. J. Am. Chem. Soc. 1984, 106, 3376. However, Clayden has recently reported a case of partial inversion: Clayden, J.; Pink, J. H., Tetrahedron Lett. 1997, 29, 552.
41. Lithio-destannylations with retention of configuration at the carbon bearing tin are usually observed, see: Still, W. C.; Sreekumar, C. J. Am. Chem. Soc. 1980, 102, 1201. Sawyer, J. S.; Macdonald, T. L.; McGarvey, G. J. J. Am. Chem. Soc. 1984, 106, 3376. However, Clayden has recently reported a case of partial inversion: Clayden, J.; Pink, J. H., Tetrahedron Lett. 1997, 29, 552.
42. Lithio-destannylations with retention of configuration at the carbon bearing tin are usually observed, see: Still, W. C.; Sreekumar, C. J. Am. Chem. Soc. 1980, 102, 1201. Sawyer, J. S.; Macdonald, T. L.; McGarvey, G. J. J. Am. Chem. Soc. 1984, 106, 3376. However, Clayden has recently reported a case of partial inversion: Clayden, J.; Pink, J. H., Tetrahedron Lett. 1997, 29, 552.
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47. The absolute configurations to the organostannanes are inferred by comparison of CSP-HPLC chromatographic profiles and signs of optical rotation which correspond to organosilanes. These assignments and those to the organolithium intermediates are provisional and used to show the suggested pathways of invertive substitutions of 14·1 and specific retentive substitution of 3·1 with tosylate and related nucleophiles.
48. When the test is conducted by carrying out the electrophilic substitution at -25°C, reaction with 0.1 equiv of TMSCl affords (R)-15 with 98:2 er, while reaction with excess TMSCl provides (A)-15 with 92:8 er.
49. The use of electrophiles other than TMSCl in the test with 14-1 afforded identical enantiomeric ratios in reactions with excess and deficient electrophile. This may be attributed to indistinguishable rates of reaction of each diastereomeric complex with the electrophile.
50. Similar results were observed when allyl chloride was used as the electrophile.
51. A potential concern is that the diastereomeric ratio of the product was determined by equilibration of the acidic benzylic position. This was shown to be unlikely by the failure of the products to equilibrate under the reaction conditions. Lee, S.; Beak, P. Unpublished results.
52. (a) Bunn, B. J.; Simpkins, N. S. J. Org. Chem. 1993, 58, 533.
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57. When the reaction is stopped before the addition of butyl tosylate, a significant amount of (R)-6 is obtained. This confirms that allyl chloride has reacted with the organolithium to provide lithium chloride in solution prior to the addition of butyl tosylate.
58. Reaction of 3·1 with carbonyl electrophiles results in much poorer enantioenrichment than products derived from alkylation.
59. While coincidental equivalence of transtion state energies remains a possibility for reactions of 3·1, the observation of different enantioselectivities with different electrophiles suggests that this is not the case.
60. In an alternate possibility, either enantiomer of the products can be obtained through a retentive substitution reaction in a dynamic kinetic resolution. In this case, the reactive diastereomeric complex would be different for different electrophiles.
61. The ion pair formation with the sulfonates can be accommodated either by allowing the carbonyl group of the benzamide or one of the nitrogens of (-)-sparteine to move out of ligation with lithium.
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