Chiral n-Butyllithium Compounds
FULL PAPER
E. G. Corley, M. F. Huntington, E. J. J. Grabowski, J. F. Remenar,
D. B. Collum, J. Am. Chem. Soc. 1998, 120, 2028–2038; e) D. Hoff-
mann, D. B. Collum, J. Am. Chem. Soc. 1998, 120, 5810–5811; For
studies on n-butyllithium aggregates by means of diffusion-ordered
NMR spectroscopy (DOSY) see: f) I. Keresztes, P. G. Williard, J.
Am. Chem. Soc. 2000, 122, 10228–10229.
Acknowledgements
We are grateful to the Fonds der Chemischen Industrie for financial sup-
port as well as for a Dozenten-Stipendium to B. G. We also thank the
Deutsche Forschungsgemeinschaft (DFG) for support (GO-930/7–1, GO-
930/5–1). We are grateful to Bayer AG, BASF AG, Wacker AG, Degussa
AG, Raschig GmbH, Symrise GmbH, Solvay GmbH, and OMG AG for
generous gifts of laboratory equipment and chemicals. Prof. P. Hofmann
generously supported this work at the University of Heidelberg.
[6] P. I. Arvidsson, P. Ahlberg, G. Hilmersson, Chem. Eur. J. 1999, 5,
1348–1354.
[7] With biphenlybisfenchol (BIFOL), a chelating, C2-symmetric fen-
chol-based diol is available: B. Goldfuss, F. Rominger, Tetrahedron
2000, 56, 881–884.
[8] a) M. Steigelmann, Y. Nisar, F. Rominger, B. Goldfuss, Chem. Eur.
J. 2002, 8, 5211–5218; b) B. Goldfuss, M. Steigelmann, S. I. Khan,
K. N. Houk, J. Org. Chem. 2000, 65, 77–82; c) B. Goldfuss, M. Stei-
gelmann, J. Mol. Model. 2000, 6, 166–170; d) B. Goldfuss, M. Stei-
gelmann, F. Rominger, Eur. J. Org. Chem. 2000, 1785–1792.
[9] For fenchylphosphinites (FENOPs) in Pd-catalysed allylic substitu-
tions see: a) B. Goldfuss, T. Lçschmann, F. Rominger, Chem. Eur. J.
2004, 10, 5422–5431; For a fenchol-based phosphorane see: b) B.
Goldfuss, T. Lçschmann, F. Rominger, Chem. Eur. J. 2001, 7, 2028–
2033; corrigendum Chem. Eur. J. 2001, 7, 2284.
[10] a) “Enantioselective Addition of Organolithiums to C=O and
Ethers”, B. Goldfuss, Top. Organomet. Chem. 2003, 5, 21–36; b) B.
Goldfuss, M. Steigelmann, F. Rominger, H. Urtel, Chem. Eur. J.
2001, 7, 4456–4464; c) B. Goldfuss, M. Steigelmann, F. Rominger,
Angew. Chem. 2000, 112, 4299–4302; Angew. Chem. Int. Ed. 2000,
39, 4133–4136; d) B. Goldfuss, S. I. Khan, K. N. Houk, Organome-
tallics 1999, 18, 2927–2929.
[1] a) D. M. Hodgson, Organolithiums in Enantioselective Synthesis,
Topics in Organometallic Chemistry, Vol. 5, Springer, Heidelberg,
2003; b) J. Clayden, Organolithiums: Selectivity for Synthesis, Tetra-
hedron Organic Chemistry Series, Vol. 23, Pergamon, Amsterdam,
2002; c) M. Hanack, Houben-Weyl, Methoden der Organischen
Chemie, Vol. E 19d, Carbanionen, Thieme, Stuttgart, 1993.
[2] a) T. F. Briggs, M. D. Winemiller, B. Xiang, D. B. Collum, J. Org.
Chem. 2001, 66, 6291–6298; b) P. I. Arvidsson, O. Davidsson, G. Hil-
mersson, Tetrahedron: Asymmetry 1999, 10, 3, 527–534; c) N. Bre-
mand, I. Marek, J. F. Normant, Tetrahedron Lett. 1999, 40, 3383–
3386; d) A. Corruble, J.-Y. Valnot, J. Maddaluno, P. Duhamel, Tetra-
hedron: Asymmetry 1997, 8, 10, 1519–1523.
[3] a) A. Deiters, D. Hoppe, J. Org. Chem. 2001, 66, 2842–2849; b) E.-
U. Wꢀrthwein, K. Behrens, D. Hoppe, Chem. Eur. J. 1999, 5, 3459–
3463; c) D. Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376–2410;
Angew. Chem. Int. Ed. Engl. 1997, 36, 2282–2316; d) P. Beak, A.
Basu, D. J. Gallagher, Y. S. Park, S. Thayumanavan, Acc. Chem. Res.
1996, 29, 552–560; e) D. Enders, U. Reinhold, Tetrahedron: Asym-
metry 1997, 8, 1895–1946; f) S. E. Denmark, O. J.-C. Nicaise, Chem.
Commun. 1996, 999–1004; g) C. Fehr, Angew. Chem. 1996, 108,
2726–2748; Angew. Chem. Int. Ed. Engl. 1996, 35, 2566–2587; h) E.
Juaristi, A. K. Beck, J. Hansen, T. Matt, T. Mukhopadhyay, M.
Simson, D. Seebach, Synthesis 1993, 1271–1290; i) D. Seebach,
Angew. Chem. 1988, 100, 1685–1715; Angew. Chem. Int. Ed. Engl.
1988, 27, 1624–1654; j) D. Seebach, Proc. Robert A. Welch Found.
Conf. Chem. Res. 1984, 27, 93–145.
[4] a) J. G. Donkervoort, J. L. Vicario, E. Rijnberg, J. T. B. H. Jastrzeb-
ski, H. Kooijman, A. L. Spek, G. van Koten, J. Organomet. Chem.
1998, 550, 463–467; b) D. J. Pippel, G. A. Weisenburger, S. R.
Wilson, P. Beak, Angew. Chem. 1998, 110, 2600–2602; Angew.
Chem. Int. Ed. Engl. 1998, 37, 2522–2524; c) P. G. Williard, C. Sun,
J. Am. Chem. Soc. 1997, 119, 11693–11694; d) I. Hoppe, M.
Marsch, K. Harms, G. Boche, D. Hoppe, Angew. Chem. 1995, 107,
2328–2330; Angew. Chem. Int. Ed. Engl. 1995, 34, 2158–2160.
[5] a) G. Hilmersson, B. Malmros, Chem. Eur. J. 2001, 7, 337–341; b) X.
Sun, M. D. Winemiller, B. Xiang, D. B. Collum, J. Am. Chem. Soc.
2001, 123, 8039–8046; c) F. Xu, R. A. Reamer, R. Tillyer, J. M.
Cummins, E. J. J. Grabowski, P. J. Reider, D. B. Collum, J. C. Huff-
man, J. Am. Chem. Soc. 2000, 122, 11212–11218; d) A. Thompson,
[11] The X-ray crystal structure of (2-Li)2 reveals a distorted, trigonal
pyramidal environment of the lithium cations: B. Goldfuss, F. Ei-
sentrꢁger, Aust. J. Chem. 2000, 53, 209–212.
[12] For electrostatic interactions of “naked” lithium ions with neutral
thienyl groups, acetylene units and cyclopropyl groups see, respec-
tively: a) B. Goldfuss, P. von R. Schleyer, F. Hampel, Organometal-
lics 1997, 16, 5032–5041; b) B. Goldfuss, P. von R. Schleyer, F.
Hampel, J. Am. Chem. Soc. 1997, 119, 1072–1080; c) B. Goldfuss, P.
von R. Schleyer, F. Hampel, J. Am. Chem. Soc. 1996, 118, 12183–
12189.
1
[13] For H,6Li-HOESY NMR spectroscopy experiments see: a) B. Gold-
fuss, P. von R. Schleyer, S. Handschuh, Hampel, W. Bauer, Organo-
metallics 1997, 16, 5999–6003; b) A. Fuerstner, G. Seidel, H.-E.
Mons, R. Mynott, Eur. J. Inorg. Chem. 1998, 11, 1771–1774; c) D.
Hoffmann, W. Bauer, P. von R. Schleyer, J. Chem. Soc. Chem.
Commun. 1990, 3, 208–211; d) W. Bauer, P. von R. Schleyer, Magn.
1
Reson. Chem. 1988, 26, 827–833; For H,7Li-HOESY NMR spectro-
scopy experiments see: e) W. Bauer, Magn. Reson. Chem. 1996, 34,
532–537.
Received: February 14, 2005
Published online: April 28, 2005
Chem. Eur. J. 2005, 11, 4019 – 4023
ꢂ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4023