Summary
α-Bromo-alkyllithium compounds such as (18) have been generated by diastereoselective bromine/lithium exchange from the dibromoalkanes (17). On trapping with electrophiles, diastereomer ratios of up to 94:6 have been attained. The α-bromo-alkyllithium compounds have been found to be configurationally stable at -110°C. In contrast, the α-phenylselenoalkyllithium compounds (24) epimerise rapidly at -78°C. Nevertheless diastereomer ratios of up to 93:7 may be realized upon quenching with electrophiles. The configurational stabi- * lity of these and related α-heterosubstituted organolithium have been rapidly assessed by a test based on kinetic resolution.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
D. Hoppe, F. Hintze, P. Tebben, Angew. Chem. 102 (1990) 1457; Angew. Chem. Int. Ed. End. 29 (1990), 1422.
W. C. Still, C. Sreekumar, J. Am. Chem. Soc. 102 (1980) 1201.
R. H. Ritter, T. Cohen, J. Am. Chem. Soc. 108 (1986) 3718.
P. G. McDougal, B. D. Condon, M. D. Laffosse, jr., A. M. Lauro, D. VanDerveer, Tetrahedron Lett. 29 (1988) 2547.
G. P. Lutz, A. P. Wallin, S. T. Kerrick, P. Beak, J. Org. Chem. 56 (1991) 4938.
H. J. Reich, M. D. Bowe, J. Am. Chem. Soc. 112 (1990) 8994.
A. Krief, G. Evrard, E. Badaoui, V. De Beys, R. Dieden, Tetrahedron Lett. 30 (1989) 5635.
R. W. Hoffmann, M. Julius, K. Oltmann, Tetrahedron Lett. 31 (1990) 7419.
W. H. Pearson, A. C. Lindbeck, J. Am. Chem. Soc. 113 (1991) 8546.
S. T. Kerrick, P. Beak, J. Am. Chem. Soc. 113 (1991) 9708.
G. Köbrich, Angew. Chem. 79 (1967) 15; Angew. Chem. Int. Ed. Engl. 6 (1967), 41.
D. Seyferth, R. L. Lambert, jr., J. Organomet. Chem. 55 (1973) C 53.
G. Köbrich, W. Goyert, Tetrahedron 24 (1968) 4327.
P. M. Warner, S.-C. Chang, N. J. Koszewski, Tetra hedron Lett. 26 (1985) 5371.
A. Schmidt, G. Köbrich, R. W. Hoffmann, Chem. Ber. 124 (1991) 1253.
J. Villieras, B. Kirschleger, R. Tarhouni, M. Rambaud, Bull. Soc. Chim. Fr. 1986 470.
R. W. Hoffmann, J. Lanz, R. Metternich, G. Tarara, D. Hoppe, Angew. Chem. 99 (1987) 1196; Angew. Chem.. Int. Ed. Engl. 26 (1987), 1145.
R. Hirsch, R. W. Hoffmann, Chem. Ber. 125 (1992) 975.
M. T. Reetz, Angew. Chem. 103 (1991) 1559: Angew. Chem. Int. Ed. Engl. 30 (1991), 1531.
R. W. Hoffmann, T. Ruhland, M. Bewersdorf, J. Chem. Soc., Chem. Commun. 1991 195.
F. Chemla, unpublished results. Marburg 1991.
J. M. Chong, S. B. Park, J. Org. Chem. 57 (1992) 2220.
M. Krüger, Diplomarbeit Univ. Marburg. 1988.
T. Ruhland, Diplomarbeit Univ. Marburg. 1989.
R. W. Hoffmann, M. Bewersdorf, M. Krüger, W. Mikolaiski, R. Stürmer, Chem. Ber. 124 (1991) 1243.
R. Tripathy, R. W. Franck, K. D. Onan, J. Am. Chem. Soc. 110 (1988) 3257.
R. W. Hoffmann, M. Bewersdorf, Chem. Ber. 124 (1991) 1259.
D. Seyferth, R. L. Lambert, jr., M. Massol, J. Organomet. Chem. 88 (1975) 255.
R. W. Hoffinann, M. Julius, Liebigs Ann. Chem. 1991 811.
W. Mikolaiski, Dissertation Univ. Marburg, 1990.
R. W. Hoffmann, K. Brumm, M. Bewersdorf, W. Mikolaiski, A. Kusche, Chem. Ber. 1992 submitted.
R. W. Hoffmann, M. Bewersdorf, Tetrahedron Lett. 31 (1990) 67.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1993 Friedr. Vieweg & Sohn Verlagsgesellschaft mbH, Braunschweig/Wiesbaden
About this chapter
Cite this chapter
Hoffmann, R.W. (1993). Configurationally Stable and Configurationally Labile Chiral α-Substituted Organolithium Compounds in Stereoselective Transformations. In: Enders, D., Gais, HJ., Keim, W. (eds) Organic Synthesis via Organometallics (OSM 4). Vieweg+Teubner Verlag. https://doi.org/10.1007/978-3-322-84062-2_7
Download citation
DOI: https://doi.org/10.1007/978-3-322-84062-2_7
Publisher Name: Vieweg+Teubner Verlag
Print ISBN: 978-3-528-06481-5
Online ISBN: 978-3-322-84062-2
eBook Packages: Springer Book Archive