4
5
D. J. Cram and H. Steinberg, J. Am. Chem. Soc., 1951, 73, 5691–5704;
C. J. Brown and A. C. Farthing, Nature, 1949, 164, 915–916.
A. A. Aly, H. Hopf, P. G. Jones and I. Dix, Tetrahedron, 2006, 62,
4
2
498–4505; M. L. Birsa, P. G. Jones and H. Hopf, Eur. J. Org. Chem.,
005, 3263–3270; T. Furo, T. Mori, T. Wada and Y. Inoue, J. Am.
Chem. Soc., 2005, 127, 8242–8243; Modern Cyclophane Chemistry, ed.
R. Gleiter and H. Hopf, Wiley-VCH, Weinheim, 2004; K. A. Lyssenko,
A. A. Korlyukov and M. Y. Antipin, Mendeleev Commun., 2005, 90–
9
2; L. Minuti, A. Taticchi, A. Marrocchi, S. Landi and E. Gacs-Baitz,
Tetrahedron Lett., 2005, 46, 5735–5737; L. Bondarenko, S. Hentschel,
H. Greiving, J. Grunenberg, H. Hopf, I. Dix, P. G. Jones and L. Ernst,
Chem.–Eur. J., 2007, 13, 3950–3963; H. Hinrichs, A. J. Boydston, P. G.
Jones, K. Hess, R. Herges, M. M. Haley and H. Hopf, Chem.–Eur. J.,
2
006, 12, 7103–7115.
6
7
K. Schlotter, F. Boeckler, H. Hubner and P. Gmeiner, J. Med.
Chem., 2006, 49, 3628–3635; B. Ortner, H. Hubner and P. Gmeiner,
Tetrahedron: Asymmetry, 2001, 12, 3205–3208; B. Ortner, R. Waibel
and P. Gmeiner, Angew. Chem., Int. Ed., 2001, 40, 1283–1285.
K. M. El-Shaieb, A. F. E. Mourad and H. Hopf, Arkivoc, 2006, 193–
2
Scheme 11 ‘Templated’ synthesis of [2.2]paracyclophane.
00.
To the best of our knowledge, all current routes to enantiomer-
ically pure [2.2]paracyclophanes are based on the resolution of
either an intermediate or the final product. Whilst it will be a
challenge, it should be possible to apply current asymmetric tech-
nology to the development of a non-resolution based synthesis.
8 S. Amthor and C. Lambert, J. Phys. Chem. A, 2006, 110, 3495–3504; P. J.
Ball, T. R. Shtoyko, J. A. K. Bauer, W. J. Oldham and W. B. Connick,
Inorg. Chem., 2004, 43, 622–632; G. C. Bazan, J. Org. Chem., 2007, 72,
8
615–8635; Y. Morisaki and Y. Chujo, Angew. Chem., Int. Ed., 2006,
5, 6430–6437; L. Valentini, F. Mengoni, A. Taticchi, A. Marrocchi
4
and J. M. Kenny, J. Mater. Chem., 2006, 16, 1622–1625; L. Valentini,
F. Mengoni, A. Taticchi, A. Marrocchi, S. Landi, L. Minuti and J. M.
Kenny, New J. Chem., 2006, 30, 939–943.
9
S. E. Gibson and J. D. Knight, Org. Biomol. Chem., 2003, 1, 1256–1269.
Outlook
1
0 V. Rozenberg, E. Sergeeva and H. Hopf, in Modern Cyclophane
Chemistry, ed. R. Gleiter, and H. Hopf, Wiley-VCH, Weinheim, 2004,
pp. 435–462.
Over 50 years after their discovery, [2.2]paracyclophane and its
derivatives have still to realise their full potential. Arguably,
the impediment to furthering this field is the lack of attractive
methods for the preparation of enantiomerically pure derivatives.
Hopefully, this article has highlighted a number of approaches
that could ameliorate this shortcoming. We have laid the foun-
dations for a strategy that will permit the synthesis of a wide
range of [2.2]paracyclophane derivatives from common sulfoxide
precursors. Whilst it is clear that present methodology has
limitations, it is hopefully only a matter of time before the optimum
sulfoxide is found that enables us to bring this project to fruition.
The article also conveys the belief that more efficient processes
for the synthesis of enantiomerically pure [2.2]paracyclophane
derivatives exist. Whilst these reactions will be more challenging,
they will be more rewarding and could open a new chapter in
1
1
1
1 P. J. Pye, K. Rossen, R. A. Reamer, R. P. Volante and P. J. Reider,
Tetrahedron Lett., 1998, 39, 4441–4444.
2 K. Rossen, P. J. Pye, A. Maliakal and R. P. Volante, J. Org. Chem.,
1
997, 62, 6462–6463.
3 P. J. Pye, K. Rossen, R. A. Reamer, N. N. Tsou, R. P. Volante and P. J.
Reider, J. Am. Chem. Soc., 1997, 119, 6207–6208.
14 T.-Z. Zhang, L.-X. Dai and X.-L. Hou, Tetrahedron: Asymmetry, 2007,
1
8, 251–259.
5 F. Lauterwasser, J. Gall, S. Hofener and S. Br a¨ se, Adv. Synth. Catal.,
006, 348, 2068–2074; M. Kreis, M. Nieger and S. Br a¨ se, J. Organomet.
1
2
Chem., 2006, 691, 2171–2181; F. Lauterwasser, S. Vanderheiden and
S. Br a¨ se, Adv. Synth. Catal., 2006, 348, 443–448; F. Lauterwasser, M.
Nieger, H. Mansikkamaki, K. Nattinen and S. Br a¨ se, Chem.–Eur. J.,
2
005, 11, 4509–4525; S. Br a¨ se, S. Dahmen, S. Hofener, F. Lauterwasser,
M. Kreis and R. E. Ziegert, Synlett, 2004, 2647–2669; S. Dahmen and
S. Br a¨ se, Org. Lett., 2001, 3, 4119–4122.
1
1
1
1
6 M. Kreis, C. J. Friedmann and S. Br a¨ se, Chem.–Eur. J., 2005, 11, 7387–
7
394.
[2.2]paracyclophane chemistry.
7 C. Bolm and D. K. Whelligan, Adv. Synth. Catal., 2006, 348, 2093–2100;
D. K. Whelligan and C. Bolm, J. Org. Chem., 2006, 71, 4609–4618.
8 X.-W. Wu, T.-Z. Zhang, K. Yuan and X.-L. Hou, Tetrahedron:
Asymmetry, 2004, 15, 2357–2365.
9 X.-L. Hou, X.-W. Wu, L.-X. Dai, B.-X. Cao and J. Sun, Chem.
Commun., 2000, 1195–1196.
20 V. Rozenberg, N. Dubrovina, E. Sergeeva, D. Antonov and Y. Belokon’,
Tetrahedron: Asymmetry, 1998, 9, 653–656.
1 S. Banfi, A. Manfredi, F. Montanari, G. Pozzi and S. Quici, J. Mol.
Catal. A: Chem., 1996, 113, 77–86.
22 D. Pamperin, H. Hopf, C. Syldatk and M. Pietzsch, Tetrahedron:
Asymmetry, 1997, 8, 319–325.
3 V. Rozenberg, T. Danilova, E. Sergeeva, E. Vorontsov, Z. Starikova, A.
Korlyukov and H. Hopf, Eur. J. Org. Chem., 2002, 468–477.
4 A. Cipiciani, F. Bellezza, F. Fringuelli and M. G. Silvestrini, Tetrahe-
dron: Asymmetry, 2001, 12, 2277–2281; D. Pamperin, B. Ohse, H. Hopf
and M. Pietzsch, J. Mol. Catal. B: Enzym., 1998, 5, 317–319.
5 A. Cipiciani, F. Fringuelli, V. Mancini, O. Piermatti, F. Pizzo and R.
Ruzziconi, J. Org. Chem., 1997, 62, 3744–3747.
6 B. Ferber and H. B. Kagan, Adv. Synth. Catal., 2007, 349, 493–507;
O. Riant, G. Argouarch, D. Guillaneux, O. Samuel and H. B. Kagan,
J. Org. Chem., 1998, 63, 3511–3514.
Acknowledgements
I am grateful for support from the EPSRC, Chirotech (Dow-
pharma) Technologies Ltd, the University of Sussex and Massey
University. I must thank all my co-workers in both the UK and
NZ but in particular Rakesh Parmar and Richard Seacome, who
performed the majority of our work described in this article.
Finally, I’d like to thank my colleagues, Dr Martyn P. Coles, Dr
Peter B. Hitchcock, (the late) Dr Anthony Avent, Prof. James
Hanson, Prof. Steve Caddick, Prof. Geoff Cloke and A/Prof.
Trevor Kitson for their valuable input.
2
2
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2
Notes and references
1
2
F. V o¨ gtle, Cyclophane Chemistry, Wiley, Chichester, 1993.
P. J. Dyson, D. G. Humphrey, J. E. McGrady, D. M. P. Mingos and
D. J. Wilson, J. Chem. Soc., Dalton Trans., 1995, 4039–4043.
S. Br a¨ se, S. Dahmen, S. H o¨ fener, F. Lauterwasser, M. Kreis and R. E.
Ziegert, Synlett, 2004, 2647–2669.
27 H. J. Reich and K. E. Yelm, J. Org. Chem., 1991, 56, 5672–5679.
28 P. B. Hitchcock, R. Parmar and G. J. Rowlands, Chem. Commun., 2005,
4219–4221.
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