Abstract
Secondary and tertiary α-methylbenzyllithium compounds were prepared by deprotonation of the corresponding carbon acids. Carbanions with a 2,4,6-triisopropylbenzoyloxy substitutent are configurationally stable in toluene/20% diethyl ether and react with electrophiles with retention (protonation, acylation with methyl chloroformate and dimethyl carbonate) or inversion (trimethyltin chloride). Secondary and tertiary carbanions with a dialkylphosphoryloxy substituent isomerise as soon as they are formed to α-hydroxyphenyl-methylphosphonates with retention of configuration (phosphate-phosphonate rearrangement).
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References
D. J. Cram; Fundamentals of Carbanion Chemistry, Organic Chemistry, A Series of Monographs, ed. by A. T. Blomquist, Academic Press, 1965. A. Krief, Tetrahedron 36, 2531 (1980).
W. C. Still, C. Sreekumar, J. Am. Chem. Soc. 102, 1201 (1980).
D. Hoppe, F. Hintze, P. Tebben, M. Paetow, H. Ahrens, J. Schwerdtfeger, P. Sommerfeld, J. Haller, W. Guarnieri, S. Kolczewski, T. Hense, I. Hoppe, Pure Appl. Chem. 66, 1479 (1994).
R. E. Gawley, Q. Zhang, Tetrahedron 50, 6077 (1994).
R. W. Hoffmann, T. Rühl, J. Harbach, Liebigs Ann. Chem. 1992, 725.
T. Ruhland, R. Dress, R. W. Hoffmann, Angew. Chem. 105, 1487 (1993).
T. Ruhland, R. Dress, R. W. Hoffmann, Angew. Chem. Int. Ed. Engl. 32, 1467 (1993).
H. J. Reich, R. R. Dykstra, Angew. Chem. 105, 1489 (1993).
H. J. Reich, R. R. Dykstra, Angew. Chem. Int. Ed. Engl. 32, 1469 (1993).
W. Zarges, M. Marsch, K. Harms, G. Boche, Chem. Ber. 122, 2303 (1989).
W. Zarges, M. Marsch, K. Harms, F. Haller, G. Frenking, G. Boche, Chem. Ber. 124, 861 (1991).
G. Vanermen, S. Toppet, M. V. Beylen, Chem. Soc. Perkin Trans II, 1989, 707. H. Ahlbrecht, J. Harbach, R. W. Hoffmann, T. Ruhland, Liebigs Ann. Chem. 1995, 211.
J. P. Gilday, J. C. Gallucci, L. A. Paquette, J. Org. Chem. 54, 1399 (1989).
A. Wright, R. West, J. Am. Chem. Soc. 96, 3227 (1974).
F. Hammerschmidt, A. Hanninger, Chem. Ber. 128, 823 (1995).
A. Carstens, D. Hoppe, Tetrahedron 50, 6097 (1994).
P. Beak, L. G. Carter, J. Org. Chem. 46, 2363 (1981).
F. Hammerschmidt, A. Hanninger, Chem. Ber. 128, 1069 (1995).
N. G. Rondan, K. N. Houk, P. Beak, W. J. Zajdel, J. Chandrasekhar, P. v. R. Schleyer, J. Org. Chem. 46, 4108 (1981).
E. L. Eliel, J. P. Freeman, J. Am. Chem. Soc. 74, 923 (1952).
E. D. Jemmis, J. Chandrasekhar, P. v. R. Schleyer, J. Am. Chem. Soc. 101, 527 (1979).
F. Hammerschmidt, H. Völlenkle, Liebigs Ann. Chem. 1986, 2053.
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Hammerschmidt, F., Hanninger, A. (1997). Configurational Stability and Reactions of Benzylic Carbanions with an Acyloxy or Dialkylphosphoryloxy Substituent. In: Fleischhacker, W., Schönfeld, T. (eds) Pioneering Ideas for the Physical and Chemical Sciences. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-0268-9_12
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