Synthesis of Lithium α-tert-Butylsulfonyl Carbanion Salts
7794; Angew. Chem. Int. Ed. 2007, 46, 7648–7650; c) S. Naka-
mura, N. Hirata, R. Yamada, T. Kita, N. Shibata, T. Toru,
Chem. Eur. J. 2008, 14, 5519–5527.
W. K. Lee, Y. S. Park, P. Beak, Acc. Chem. Res. 2009, 42, 224–
234.
(S)-12, (R)-12, (S)-13, (R)-13, (S)-14, (R)-14, (S)-6, (R)-6, (S)-16,
(R)-17, (R)-7, (R)-18, (R)-19, (S)-17, (S)-7, rac-21, (S)-22, (S)-21,
(S)-20, rac-20, (R)-20, (S)-23, (R)-24, (R)-8, (R)-25, (S)-25, (S)-28,
(R)-29, (R)-9, (R)-31, (S)-31, (S)-32, (R)-32, (S)-10, (R)-10, rac-33,
(R)-30, (S)-30, (S)-32, (R)-32, 49, 50, rac-10, rac-6, rac-7, (S)-40,
rac-40, (2S,3S)-47, (2S,3R)-47, (1R,2S)-44, (1S,2S)-47, (3R,4S)-46,
and (3S,4S)-46; scheme describing the synthesis of rac-6–9, 59, and
50; experimental procedures for the synthesis and reactions of the
salts (M)-1, (P)-1, (M)-2, (P)-2, rac-2, (P)-3, (M)-3, rac-4, and (P)-
5; tables containing the racemization data for (P)-1 and (M)-2,
tables containing the crystal data and experimental details of the
structure determination of (R)-9, (S)-10, rac-33, (R)-34, (R)-35, (S)-
40, (S)-42, (S,R)-44, and (S,S)-44.
[7]
[8]
C. Wolf, Dynamic Stereochemistry of Chiral Compounds, Prin-
ciples and Applications, RSC, Cambridge, 2008.
For short communications, see ref.[3a,3c]
[9]
[10]
The enantioselective conversion of the sulfone via the α-sulfo-
nyl carbanion into the substituted sulfone may be regarded as
an example of what has been termed “memory of chirality”,
see ref.[11a] However, the use of this term has been criticized,
see: F. Cozzi, J. S. Siegel, Org. Biomol. Chem. 2005, 3, 4296–
4298.
a) T. Kawabata, K. Fuji, Top. Stereochem. 2003, 23, 175–205;
b) H. Zhao, D. C. Hsu, P. R. Carlier, Synthesis 2005, 1, 1–16;
c) T. Kawabata, J. Chen, H. Suzuki, K. Fuji, Synthesis 2005,
1368–1377; d) A. G. Brewster, J. Jayatissa, M. B. Mitchell, A.
Schofield, R. J. Stoodley, Tetrahedron Lett. 2002, 43, 3919–
3922; e) M. A. Bonache, G. Gerona-Navarro, M. Martin-Mart-
inez, M. T. Garcia-Lopez, P. Lopez, C. Cativiela, R. Gonzalez-
Muniz, Synlett 2003, 1007–1011; f) J. Clayden, C. C. Stimson,
M. Keenan, Synlett 2005, 1716–1720; g) P. C.-H. Lam, P. R.
Carlier, J. Org. Chem. 2005, 70, 1530–1538.
R. W. Baker, M. A. Foulkes, J. A. Taylor, J. Chem. Soc. Perkin
Trans. 1 1998, 1047–1057.
a) P. J. DeChristopher, J. P. Adamek, G. D. Lyon, S. A. Klein,
R. J. Baumgarten, J. Org. Chem. 1974, 39, 3525–3532; b) P.
Müller, M. P. Nguyen-Thi, Helv. Chim. Acta 1980, 63, 2168–
2172.
J. Dupont, A. S. Gruber, G. S. Fonseca, A. L. Monteiro, G.
Ebling, Organometallics 2001, 20, 171–176.
K. Laumen, M. P. Schneider, J. Chem. Soc., Chem. Commun.
1988, 598–600.
[11]
Acknowledgments
This research was supported by the Deutsche Forschungsgemein-
schaft (DFG), Volkswagen Foundation, and Fonds der Chemischen
Industrie. We thank D. Wolters for his help with the graphics.
[1] R. Scholz, G. Hellmann, S. Rohs, G. Raabe, J. Runsink, D.
Özdemir, O. Luche, T. Heß, A. W. Giesen, J. Atodiresei, H. J.
Lindner, H.-J. Gais, Eur. J. Org. Chem. 2010, 4559–4587, pre-
ceding contribution.
[12]
[13]
[2] a) N. S. Simpkins, Chem. Ind. 1988, 387–389; b) P. J. Cox, N. S.
Simpkins, Tetrahedron: Asymmetry 1991, 2, 1–26; c) H.-J. Gais,
in: Organosulfur Chemistry in Asymmetric Snythesis (Eds.: T.
Toru, C. Bolm), Wiley-VCH, Weinheim, 2008, pp. 375–398.
[3] a) H.-J. Gais, G. Hellmann, H. Günther, F. Lopez, H. J.
Lindner, S. Braun, Angew. Chem. 1989, 101, 1061–1064; Angew.
Chem. Int. Ed. Engl. 1989, 28, 1025–1028; b) H.-J. Gais, G.
Hellmann, H. J. Lindner, Angew. Chem. 1990, 102, 96–99; An-
gew. Chem. Int. Ed. Engl. 1990, 29, 100–103; c) H.-J. Gais, G.
Hellmann, J. Am. Chem. Soc. 1992, 114, 4439–4440; d) G.
Raabe, H.-J. Gais, J. Fleischhauer, J. Am. Chem. Soc. 1996, 118,
4622–4630.
[4] For clarity lithium α-sulfonyl carbanion salts are represented
throughout this paper only by the structural formula of their
monomers. Although the monomers may have only one O–Li
bond they are depicted with two bonds of this type; see ref.[1]
According to NMR spectroscopic and cryoscopic analysis of
the racemic salts the monomers are in equilibrium with the
dimers, both of which are O–Li CIPs with similar basic struc-
tural features; see ref.[1] The monomer/dimer ratio of the race-
mic and enantiopure salts may differ, however, because of the
lack of achiral dimers in the latter case.
[5] a) H. J. Reich, R. P. Dykstra, Angew. Chem. 1993, 105, 1489–
1491; Angew. Chem. Int. Ed. Engl. 1993, 32, 1469–1470; b) H. J.
Reich, R. P. Dykstra, J. Am. Chem. Soc. 1993, 115, 7041–7042;
c) R. E. Gawley, Curr. Org. Chem. 1997, 1, 71–94; d) T. Toru,
S. Nakamura, Top. Organomet. Chem. 2003, 5, 177–216; e) A.
Basu, S. Thayumanavan, Angew. Chem. 2002, 114, 740–763;
Angew. Chem. Int. Ed. 2002, 41, 716–738; f) J. Clayden, in:
Organolithiums: Selectivity for Synthesis (Eds.: J. E. Baldwin,
R. M. Williams), Elsevier, Oxford, 2002; g) P. Beak, T. A. John-
son, D. D. Kim, S. H. Lim, Top. Organomet. Chem. 2003, 5,
139–176; h) D. Hoppe, F. Marr, M. Brueggemann, Top. Or-
ganomet. Chem. 2003, 5, 61–137; i) R. W. Hoffmann, Chem.
Soc. Rev. 2003, 32, 225–230; j) R. E. Gawley, in: Chemistry of
Organolithium Compounds (Eds.: Z. Rappoport, I. Marek),
Wiley, Chichester, 2004, vol. 2, pp. 997–1053; k) D. Hoppe, G.
Christoph, in: Chemistry of Organolithium Compounds (Eds.:
Z. Rappoport, I. Marek), Wiley, Chichester, 2004, vol. 2, pp.
1055–1164.
[14]
[15]
[16]
[17]
[18]
[19]
H. L. Holland, F. M. Brown, B. Munoz, R. W. Ninniss, J.
Chem. Soc. Perkin Trans. 2 1988, 1557–1563.
R. M. Coates, J. P. Chen, Tetrahedron Lett. 1969, 10, 2705–
2708.
T. Shibata, K. Iwahashi, T. Kawasaki, K. Soai, Tetrahedron:
Asymmetry 2007, 18, 1759–1762.
a) S. Winstein, B. K. Morse, J. Am. Chem. Soc. 1952, 74, 1133–
1139; b) M. Falorni, L. Lardicci, C. Rosini, G. Giacomelli, J.
Org. Chem. 1986, 51, 2030–2033; c) F. Toda, K. Tanaka, K.
Koshiro, Tetrahedron: Asymmetry 1991, 2, 873–874.
H. E. Zieger, D. A. Bright, H. Haubenstock, J. Org. Chem.
1986, 51, 1180–1184.
C. L. Arcus, P. A. Hallgarten, J. Chem. Soc. 1956, 2987–2991.
CCDC-767751 [for (R)-9], -767753 [for (S)-10], -767752 (rac-
33), -767750 [(R)-34], -767748 [for (R)-35], -767749 [for (S)-
40], -767754 [for (S)-42], -767756 [for (S,S)-44], and -767755
[for (S,R)-44] contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.ac.uk/data_request/cif.
a) R. J. Kurland, M. B. Rubin, W. B. Wise, J. Chem. Phys. 1964,
40, 2426–2427; b) G. Binsch, Top. Stereochem. 1968, 3, 97–192.
M. Õki, The Chemistry of Rotational Isomers, Springer, Heidel-
berg, 1993.
O. Takahashi, Y. Gondoh, K. Saito, Y. Kohno, H. Suezawa, T.
Yoshida, S. Ishihara, M. Nishio, New J. Chem. 2003, 27, 1639–
1643.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery Jr., T.
Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N.
Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P.
Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts,
R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pom-
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[6] a) T. Akiyama, M. Shimizu, T. Mukaiyama, Chem. Lett. 1984,
611–614; b) S. Nakamura, N. Hirata, T. Kita, R. Yamada, D.
Nakane, N. Shibata, T. Toru, Angew. Chem. 2007, 119, 7792–
Eur. J. Org. Chem. 2010, 4588–4616
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4615