Chiral benzyllithium compounds: High configurative stability of (R)- and (S)-1-lithioindan-1-yl N,N-diisopropylcarbamate and unexpected stereochemical course of the substitution reactions

European Journal of Organic Chemistry

Volumn , Issue 12, 1999, Pages 3519-3524

  Derwing, Christoph ^a   Frank, Holger ^a   Hoppe, Dieter ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

Chiral benzyllithium compounds; Lithiation; Semiempirical calculations; Stereochemistry of electrophilic substitution

Indexed keywords

CARBAMIC ACID DERIVATIVE; LITHIUM DERIVATIVE; ORGANOTIN COMPOUND;

ARTICLE; CHEMICAL REACTION; CHIRALITY; CRYSTAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE; PROTON TRANSPORT; STEREOCHEMISTRY;

EID: 0032708681     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1099-0690(199912)1999:12<3519::AID-EJOC3519>3.0.CO;2-N     Document Type: Article

References (40)

1. For a similar study see: F. Hammerschmidt, A. Hanninger, B. Peric, H. Völlenkle, A. Werner, Eur. J. Org. Chem. 1999, 3511-3518, preceding paper.
2. C. Derwing, part of diploma thesis, University of Münster, 1993, and of the dissertation. University of Münster, 1995.
3. Reviews: [3a] D. Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376-2410; Angew. Chem. Int. Ed. Engl. 1997, 36, 2282-2316.
4. Reviews: [3a] D. Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376-2410; Angew. Chem. Int. Ed. Engl. 1997, 36, 2282-2316.
5. [3b] P. Beak, A. Basu, D. J. Gallagher, Y. S. Park, S. Thayumanavan. Acc. Chem. Res. 1996, 29, 552-560.
6. [4a] D. Hoppe, A. Carstens, T. Krämer, Angew. Chem. 1990, 102, 1455-1456; Angew. Chem. Int. Ed. Engl. 1990, 29, 1424-1425.
7. [4a] D. Hoppe, A. Carstens, T. Krämer, Angew. Chem. 1990, 102, 1455-1456; Angew. Chem. Int. Ed. Engl. 1990, 29, 1424-1425.
8. [4b] A. Carstens, D. Hoppe, Tetrahedron 1994, 50, 6097-6108.
9. [4c] For a correction and for a more suitable carbamate protecting group: C. Derwing, D. Hoppe, Synthesis 1996, 149-154.
10. [5a] F. Hammerschmidt, A. Hanninger, Chem. Ber. 1995. 128, 1069-1077.
11. [5b] F. Hammerschmidt, S. Schmidt, Chem. Ber. 1996, 129, 1503-1508.
12. [5c] F. Hammerschmidt, A. Hanninger, Chem. Ber. 1995, 128, 823-830.
13. [6a] Y. S. Park P. Beak, J. Org. Chem. 1997, 62, 1574-575.
14. [6b] Y. S. Park, M. L. Loys, P. Beak, J. Am. Chem. Soc. 1996, 118, 3757-3758.
15. J D. Hoppe, B. Kaiser, O. Stratmann, R. Fröhlich, Angew. Chem. 1997. 109, 2872-2874; Angew. Chem. Int. Ed. Engl. 1997, 36, 2784-2786.
16. J D. Hoppe, B. Kaiser, O. Stratmann, R. Fröhlich, Angew. Chem. 1997. 109, 2872-2874; Angew. Chem. Int. Ed. Engl. 1997, 36, 2784-2786.
17. K. Laumen, M. P. Schneider, J. Chem. Soc., Chem. Commun. 1988, 598-600.
18. A few experiments were performed using (S)-5 under identical conditions.
19. Hammerschmidt (ref.[1]) observed a large influence of the leaving group at the tin reagent. In our study, only the chlorides were utilized.
20. [11a] P. N. Rylander, Hydrogenation Methods, Academic Press, London, 1985.
21. [11b] E. W. Garbisch Jr., L. Schreader, J. J. Frankel, J. Am. Chem. Soc. 1967, 89, 4233-4235.
22. [11c] J. H. Brewster, W. E. Braden, Jr., Chem. Ind. 1964, 1759.
23. [11d] S. Mitsui, Y. Senda, K. Konno, Chem. Ind. 1963, 1354.
24. J. H. Brewster, J. G. Butta, J. Am. Chem. Soc: 1966, 88, 2233-2240.
25. [13a] K. Tomooka, N. Komine, T. Sasaki, H. Shimizu, T. Nakai, Tetrahedron Lett. 1998, 39, 9715-9718 and references cited therein.
26. [13b] M. Oestreich, D. Hoppe, Tetrahedron Lett. 1999, 40, 1881-1884.
27. The method of Nakai (ref.[13a]), employing a large excess of DIBAL-H, provided low yields.
28. M. Marsch, K. Harms, O. Zschage, D. Hoppe, G. Boche, Angew. Chem. 1991, 103, 338-339; Angew. Chem. Int. Ed. Engl. 1991, 30, 321-323.
29. M. Marsch, K. Harms, O. Zschage, D. Hoppe, G. Boche, Angew. Chem. 1991, 103, 338-339; Angew. Chem. Int. Ed. Engl. 1991, 30, 321-323.
30. See, for instance: G. Boche, M. Marsch, J. Harbach, K. Harms, B. Ledig, F. Schubert, J. C. W. Lohrenz, H. Ahlbrecht, Chem. Ber. 1993, 126, 1887-1894.
31. MOPAC93, QCPE, Bloomington, Indiana, USA: Keywords: PM3, EF, GNORM = 0.01; Lithium PM3-parametrization: E. Anders, R. Koch, P. Freunscht, J. Comp. Client. 1993, 14, 1301-1312.
32. This simplification at the carbamate moiety, in our opinion, will have no significant influence on the difference in enthalpy of formation between the two structures. As shown recently for the transition states of the deprotonation of alkyl carbamates with sec-butyllithium, mediated by chiral diamines, a much bulkier substituent at the carbamate is necessary to have any influence, see: E.-U. Würthwein, K. Behrens, D. Hoppe, Chem. Eur. J. 1999, 5, 3459-3463.
33. 3-hybridized pyramidal unit.
34. For related calculations on hydroxymethyllithium see: G. Boche, A. Opel, M. Marsch, K. Harms, F. Haller, J. C. W. Lohrenz, C. Tümmler, W. Koch, Chem. Ber. 1992, 125, 2265-2273.
35. This has been performed by fixing the dieder angle between ArC/C/OCb [option 0 (= zero, i.e. not optimizing) in the Z matrix] stepwise up to 180°. which finally gives an ideal trigonal planar structure.
36. After releasing the angle of 180° between ArC/C/OCb, the calculations deliver the same ground-state conformations with the same enthalpy of formations again.
37. ≠ of 3.1 kcal/mol calculated for -78°C.
38. Details of the quantum-chemical calculations (MOPAC93 archive entries) are available from H. F. upon request.
39. 3).
40. K. Laumen, D. Breitgoff, M. P. Schneider, J. Chem. Soc., Chem. Commun. 1988, 1459-1461.