(-)-Sparteine-mediated α-lithiation of N-Boc-N-(p-methoxyphenyl)benzylamine: Enantioselective syntheses of (S) and (R) mono-and disubstituted N-Boc-benzylamines

Journal of the American Chemical Society

Volumn 118, Issue 15, 1996, Pages 3757-3758

  Park, Yong Sun ^a   Boys, Mark L ^a,b   Beak, Peter ^a  

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

^b PFIZER INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZYLAMINE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; ENANTIOMER; REACTION ANALYSIS;

EID: 0029891973     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9538804     Document Type: Article

References (30)

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2. (b) Hoppe, D.; Hintze, F.; Tebben, P.; Paetow, M.; Haller, J.; Guarnieri, W.; Kolczewski, S.; Hense, T.; Hoppe, I. Pure Appl. Chem. 1994, 66, 1479.
3. (c) Klein, S.; Marek, I.; Poisson, J. F.; Normant, J. F. J. Am. Chem. Soc. 1995, 117, 8853.
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5. (e) Tsukazaki, M.; Tinkl, A.; Roglans, A.; Chapell, B. J., Taylor, N. J.; Snieckus, V. J. Am. Chem. Soc. 1996, 118, 685.
6. Beak, P.; Kerrick, S. T.; Wu, S.; Chu, J. J. Am. Chem. Soc. 1994, 116, 3231 and references cited therein.
7. 4b in the enantiomeric excesses for the lithiation - substitution of N-Boc-N-methylbenzylamine with s-BuLi/(-)-sparteine and methyl iodide. In THF, two regioisomers were produced in 85% yield in a ratio of 1.3:1. The major isomer, (N)-N-Boc-N-methyl-α-methylbenzylamine, from the lithiation - substitution at the benzylic position was obtained with -36% ee, and the minor product as N-Boc-N-ethylbenzylamine from lithiation - substitution at the N-methyl group. In toluene, only (S)-N-Boc-N-methyl-α-methyl-benzylamine was obtained with 92% ee. Park, Y. S.; Beak, P. Unpublished Results.
8. 4b in the enantiomeric excesses for the lithiation - substitution of N-Boc-N-methylbenzylamine with s-BuLi/(-)-sparteine and methyl iodide. In THF, two regioisomers were produced in 85% yield in a ratio of 1.3:1. The major isomer, (N)-N-Boc-N-methyl-α-methylbenzylamine, from the lithiation - substitution at the benzylic position was obtained with -36% ee, and the minor product as N-Boc-N-ethylbenzylamine from lithiation - substitution at the N-methyl group. In toluene, only (S)-N-Boc-N-methyl-α-methyl-benzylamine was obtained with 92% ee. Park, Y. S.; Beak, P. Unpublished Results.
9. 4b in the enantiomeric excesses for the lithiation - substitution of N-Boc-N-methylbenzylamine with s-BuLi/(-)-sparteine and methyl iodide. In THF, two regioisomers were produced in 85% yield in a ratio of 1.3:1. The major isomer, (N)-N-Boc-N-methyl-α-methylbenzylamine, from the lithiation - substitution at the benzylic position was obtained with -36% ee, and the minor product as N-Boc-N-ethylbenzylamine from lithiation - substitution at the N-methyl group. In toluene, only (S)-N-Boc-N-methyl-α-methyl-benzylamine was obtained with 92% ee. Park, Y. S.; Beak, P. Unpublished Results.
10. 4b in the enantiomeric excesses for the lithiation - substitution of N-Boc-N-methylbenzylamine with s-BuLi/(-)-sparteine and methyl iodide. In THF, two regioisomers were produced in 85% yield in a ratio of 1.3:1. The major isomer, (N)-N-Boc-N-methyl-α-methylbenzylamine, from the lithiation - substitution at the benzylic position was obtained with -36% ee, and the minor product as N-Boc-N-ethylbenzylamine from lithiation - substitution at the N-methyl group. In toluene, only (S)-N-Boc-N-methyl-α-methyl-benzylamine was obtained with 92% ee. Park, Y. S.; Beak, P. Unpublished Results.
11. For applications and comparisons to alternative methodology, see: Elworthy, T. R.; Meyers, A. I. Tetrahedron 1994, 50, 6089. Gawley, R. E.; Zhang. O J. Org. Chem. 1995, 60, 5763.
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13. During the reviewing process, the reaction of 1 with s-BuLi followed by addition to imines was reported to give a racemic product with high diastereoselectivity, while addition to benzaldehyde showed little diastereoselectivity. Kise, N.; Kashiwagi, K.; Watanabe, M.; Yoshida, J. J. Org. Chem. 1996, 61, 428.
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19. 11 (Matrix Presented)
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22. 14 for the crystalline complex of N-methyl-N-pivaloyl-α-lithiobenzylamine/(-)-sparteine, the reaction with electrophiles would proceed with retention.
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