Synthesis of catenane structures via ring-closing metathesis

Article abstract of DOI:10.1021/jo990268c

This study presents a detailed description of a synthetic strategy to obtain catenane architectures through ring-closing metathesis. The approach is based on phenanthroline-based ligands containing terminal olefinic units that were designed to coordinate in a tetrahedral arrangement around a copper atom. Treatment of the assembled copper complexes with ruthenium catalyst 1 resulted in [2]catenates in high yields of 88-92%. Demetalation produced the corresponding [2]catenand in nearly quantitative yields. Hydrogenation of the catenates with Crabtree's catalyst and subsequent demetalation yielded fully saturated catenands. The presently described procedure makes [2]catenanes very accessible since the synthetic route consists of six steps (Schemes 2 and 4) from commercially available 1,10-phenanthroline, the overall yield being 51%.

Full text of DOI:10.1021/jo990268c

J . Org. Chem. 1999, 64, 5463-5471
5463
Syn th esis of Ca ten a n e Str u ctu r es via Rin g-Closin g Meta th esis
Marcus Weck,† Bernhard Mohr,‡ J ean-Pierre Sauvage,*,‡ and Robert H. Grubbs*,†
Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical
Engineering, California Institute of Technology, Pasadena, California 91125, and Laboratoire de Chimie
Organo-Mine´rale, UMR 7513 au CNRS, Faculte´ de Chimie, Universite´ Louis Pasteur, 4, rue Blaise
Pascal, 67070 Strasbourg
Received February 12, 1999
This study presents a detailed description of a synthetic strategy to obtain catenane architectures
through ring-closing metathesis. The approach is based on phenanthroline-based ligands containing
terminal olefinic units that were designed to coordinate in a tetrahedral arrangement around a
copper atom. Treatment of the assembled copper complexes with ruthenium catalyst 1 resulted in
[2]catenates in high yields of 88-92%. Demetalation produced the corresponding [2]catenand in
nearly quantitative yields. Hydrogenation of the catenates with Crabtree’s catalyst and subsequent
demetalation yielded fully saturated catenands. The presently described procedure makes
[2]catenanes very accessible since the synthetic route consists of six steps (Schemes 2 and 4) from
commercially available 1,10-phenanthroline, the overall yield being 51%.
In tr od u ction
strategies, thus making the preparation of threaded and
interlocked systems more accessible. Specifically, a sig-
nificant number of catenane systems have been reported.
Since 1983, a copper-metal template based strategy has
allowed catenanes,6 knots,7 and rotaxanes8 to be obtained.
In the last 10 years, Stoddart and his group have worked
on the synthesis of interlocked systems based on second-
ary dialkylammonium salts and crown ethers9 and on
systems based on π-electron-rich/π-electron-deficient aro-
matic systems.10 Catenane systems based on hydrogen
bonds, as reported by Hunter,11 Vo¨gtle,11 and Leigh,12
cyclodextrins as introduced by Ogino, Wenz, and Hara-
da,13 and rotaxanes based on crown ether frameworks
presented by Gibson14 have also been reported.1,15-28
Mechanically linked molecules, rotaxanes, pseudoro-
taxanes, and catenanes1 constitute a major research field
in supramolecular chemistry.2 Catenanes, from the Latin
catena meaning chain, are molecules that contain two
or more interlocked ring systems.3 These rings are
inseparable without breaking a covalent bond.
Catenanes and rotaxanes started to attract consider-
able attention in the late 1960s because they presented
a unique synthetic challenge.4 Also, they appeared to be
promising chemical objects with novel physical properties
and precursors to new materials. After the pioneering
work of Schill4 and Wasserman,5 only a few research
groups continued working on these kinds of systems.
However, over the last 15 years the field has experienced
a renaissance in response to the introduction of template
(6) (a) Livoreil, A.; Sauvage, J .-P.; Armaroli, N.; Balzani, V.;
Flamigni, L.; Ventura, B. J . Am. Chem. Soc. 1997, 119, 12114. (b)
Ca´rdenas, D. J .; Gavin˜a, P.; Sauvage, J .-P. J . Am. Chem. Soc. 1997,
119, 2656. (c) Dietrich-Buchecker, C.; Sauvage, J .-P. Tetrahedron 1990,
46, 503. (d) Nierengarten, J .-F.; Dietrich-Buchecker, C. O.; Sauvage,
J .-P. J . Am. Chem. Soc. 1994, 116, 375. (e) Collin, J .-P.; Gavin˜a, P.;
Sauvage, J .-P. J . Chem. Soc., Chem. Commun. 1996, 2005. (f) Bau-
mann, F.; Livoreil, A.; Kaim, W.; Sauvage, J .-P. J . Chem. Soc., Chem.
Commun. 1997, 35. (g) Chambron, J .-C.; Dietrich-Buchecker, C.;
Nierengarten, J .-F.; Sauvage, J .-P.; Solladie´, N.; Albrecht-Gary, A.-
M.; Meyer, M. New J . Chem. 1995, 19, 409. (h) Dietrich-Buchecker,
C.; Leize, E.; Nierengarten, J .-F.; Sauvage, J .-P.; Dorsselaer, A. V. J .
Chem. Soc., Chem. Commun. 1994, 2257. (i) Livoreil, A.; Dietrich-
Buchecker, C. O.; Sauvage, J .-P. J . Am. Chem. Soc. 1994, 116, 9399.
(j) Dietrich-Buchecker, C. O.; Guilhem, J .; Kern, J .-M.; Pascard, C.;
Sauvage, J .-P. Inorg. Chem. 1994, 33, 3498. (k) Chambron, J .-C.;
Mitchell, D. K.; Sauvage, J .-P. J . Am. Chem. Soc. 1992, 114, 4625. (l)
Dietrich-Buchecker, C.; Sauvage, J .-P.; Kern, J .-M. J . Am. Chem. Soc.
1989, 111, 7791. (m) Cesario, M.; Dietrich-Buchecker, C. O.; Guilhem,
J .; Pascard, C.; Sauvage, J .-P. J . Chem. Soc., Chem. Commun. 1985,
244. (n) Dietrich-Buchecker, C.; Sauvage, J .-P. Tetrahedron Lett. 1983,
24, 5091. (o) Dietrich-Buchecker, C.; Sauvage, J .-P.; Kern, J .-M. J . Am.
Chem. Soc. 1984, 106, 3043.
(7) (a) Dietrich-Buchecker, C. O.; Nierengarten, J .-F.; Sauvage, J .-
P.; Armaroli, N.; Balzani, V.; DeCola, L. J . Am. Chem. Soc. 1993, 115,
11237. (b) Carina, R. F.; Dietrich-Buchecker, C.; Sauvage, J .-P. J . Am.
Chem. Soc. 1996, 118, 9110. (c) Dietrich-Buchecker, C. O.; Sauvage,
J .-P.; DeCian, A.; Fischer, J . J . Chem. Soc., Chem. Commun. 1994,
2231. (d) Dietrich-Buchecker, C. O.; Nierengarten, J .-F.; Sauvage, J .-
P. Tetrahedron Lett. 1992, 33, 3625. (e) Dietrich-Buchecker, C. O.;
Sauvage, J .-P.; Kintzinger, J .-P.; Malte`se, P.; Pascard, C.; Guilhelm,
J . New. J . Chem. 1992, 16, 931. (f) Dietrich-Buchecker, C. O.; Sauvage,
J .-P. Angew. Chem., Int. Ed. Engl. 1989, 28, 8, 189.
† California Institute of Technology.
‡ Universite´ Louis Pasteur.
(1) For some recent reviews of interlocked and intertwined struc-
tures, see: (a) Amabilino, D. B.; Stoddart, J . F. Chem. Rev. 1995, 95,
2725. (b) Fyfe, M. C. T.; Stoddart, J . F. Acc. Chem. Res. 1997, 30, 393.
(c) Philp, D.; Stoddart, J . F. Angew. Chem., Int. Ed. Engl. 1996, 35,
1154. (d) Chambron, J .-C.; Dietrich-Buchecker, C.; Sauvage, J .-P. Top.
Curr. Chem. 1993, 165, 132. (e) Sauvage, J .-P.; Dietrich-Buchecker,
C. O.; Chambron, J . C. In Comprehensive Supramolecular Chemistry;
Pergamon Press: Oxford, 1996; Vol. 9, p 43. (f) Fujita, M.; Ogura, K.
Coord. Chem. Rev. 1996, 148, 249. (g) Vo¨gtle, F.; Du¨nnwald, T.;
Schmidt, T. Acc. Chem. Res. 1996, 29, 451. (h) Chapman, R. G.;
Sherman, J . C. Tetrahedron 1997, 53, 15911. (i) J a¨ger, R.; Vo¨gtle, F.
Angew. Chem., Int. Ed. Engl. 1997, 36, 931. (j) Sauvage, J .-P. Acc.
Chem. Res. 1998, 31, 611.
(2) (a) Lehn, J . M. Supramolecular Chemistry; VCH: Weinheim,
1995; and references therein. (b) Balzani, V.; De Cola, L. Supramo-
lecular Chemistry; Kluwer Academic Publishers: Dordrecht, 1992; and
references therein. (c) Lehn, J . M. Angew. Chem., Int. Ed. Engl. 1988,
27, 89. (d) Ringsdorf, H.; Schlarb, V.; Venzmer, J . Angew. Chem., Int.
Ed. Engl. 1988, 27, 113. (e) Whitesides, G. M.; Simanek, E. E.; Mathias,
J . P.; Seto, C. T.; Chin, D. N.; Mammen, M.; Gordon, D. M. Acc. Chem.
Res. 1995, 28, 37.
(3) The nomenclature employed in these systems involves placing
(in square brackets) the number of the components before the name
of the compounds. Therefore, a [2]catenane is comprised of two
interlocked macrocycles.
(4) Schill, G. Catenanes, Rotaxanes and Knots; Academic Press: New
York, 1971.
(5) (a) Frisch, H. L.; Wassermann, E. J . Am. Chem. Soc. 1961, 83,
3789. (b) Ben-Efraim, D. A.; Batich, C.; Wasserman, E. J . Am. Chem.
Soc. 1970, 92, 2132.
(8) (a) Kern, J .-M.; Sauvage, J .-P.; Bidan, G.; Bilon, M.; Divisa-
Blohorn, B. Adv. Mater. 1996, 8, 580. (b) Chambron, J .-C.; Sauvage,
J .-P. Chem. Eur. J . 1998, 4, 1362.
10.1021/jo990268c CCC: $18.00 © 1999 American Chemical Society
Published on Web 07/02/1999

5464 J . Org. Chem., Vol. 64, No. 15, 1999
Weck et al.
In modern approaches, a large number of functional
groups have been introduced into the catenanes and
rotaxanes, thus enabling these compounds to fulfill
increasingly complex chemical and physical functions.
Additionally, they display interesting physical properties,
such as photoinduced intramolecular electron transfer,29
electrochemically triggered molecular motions, and pho-
tochemical dethreading processes. A number of these
multicomponent systems have been named “molecular
machines”.10 In addition, a few groups have recently
described transition-metal-incorporating catenanes and
rotaxanes, these compounds being most of the time
obtained in good yields, under very mild conditions.1f,30
For all more recent supramolecular systems, the use
of a template, or auxiliary linkage, is essential for an
efficient synthesis. The components of the rings that are
to be incorporated into the architecture are brought
together in a specific orientation so that the most
favorable outcomes are interlocked rings.
Therefore, the synthesis relies on a quantitative as-
sembly step followed by ring closure. In most cases, the
cyclization reaction is restricted to the formation of ethers
and amide bonds or quarternary ammonium salts by an
intramolecular pathway.1 However, this cyclization reac-
tion also constitutes the biggest challenge in the synthe-
sis of catenanes and rotaxanes because the yield of the
product is oftentimes quite low.
(9) (a) Ashton, P. R.; Chrystal, E. J . T.; Glink, P. T.; Menzer, S.;
Schiavo, C.; Spencer, N.; Stoddart, J . F.; Tasker, P. A.; White, A. J . P.;
Williams, D. J . Chem. Eur. J . 1996, 2, 709. (b) Ashton, P. R.; Baxter,
I.; Cantrill, S. J .; Fyfe, M. C. T.; Glink, P. T.; Stoddart, J . F.; White, A.
J . P.; Williams, D. J . Angew. Chem., Int. Ed. Engl. 1998, 37, 1294. (c)
Ashton, P. R.; Baxter, I.; Fyfe, M. C. T.; Raymo, F. M.; Spencer, N.;
Stoddart, J . F.; White, A. J . P.; Williams, D. J . J . Am. Chem. Soc. 1998,
120, 2297. (d) Ashton, P. R.; Ballaedini, R.; Balzani, V.; Go´mez-Lo´pez,
M.; Lawrence, S. E.; Mart´ıne-D´ıaz, M. V.; Montalti, M.; Piersanti, A.;
Prodi, L.; Stoddart, J . F.; Williams, D. J . J . Am. Chem. Soc. 1997, 119,
10641. (e) Ashton, P. R.; Collins, A. N.; Fyfe, M. C. T.; Menzer, S.;
Stoddart, J . F.; Williams, D. J . Angew. Chem., Int. Ed. Engl. 1997, 36,
735. (f) Ashton, P. R.; Glink, P. T.; Stoddart, J . F.; Tasker, P. A.; White,
A. J . P.; Williams, D. J . Chem. Eur. J . 1996, 2, 729. (g) Ashton, P. R.;
Chrystal, E. J . T.; Glink, P. T.; Menzer, S.; Schiavo, C.; Stoddart, J .
F.; Tasker, P. A.; Williams, D. J . Angew. Chem., Int. Ed. Engl. 1995,
34, 1869. (h) Ashton, P. R.; Campbell, P. J .; Chrystal, E. J . T.; Glink,
P. T.; Menzer, S.; Philp, D.; Spencer, N.; Stoddart, J . F.; Tasker, P. A.;
Williams, D. J . Angew. Chem., Int. Ed. Engl. 1995, 34, 1865. (i) Ashton,
P. R.; Fyfe, M. C. T.; Glink, P. T.; Menzer, S.; Stoddart, J . F.; White,
A. J . P.; Williams, D. J . J . Am. Chem. Soc. 1997, 119, 12514.
(10) (a) Anelli, P. L.; Ashton, P. R.; Ballardini, R.; Balzani, V.;
Delgado, M.; Gandolfi, M. T.; Goodnow, T. T.; Kaifer, A. E.; Philp, D.;
Pietraszkiewicz, M.; Prodi, L.; Reddington, M. V.; Slawin, A. M. Z.;
Spencer, N.; Stoddart, J . F.; Vicent, C.; Williams, D. J . J . Am. Chem.
Soc. 1992, 114, 193. (b) Amabilino, D. B.; Ashton, P. R.; Brown, C. L.;
Co´rdova, E.; God´ınez, L. A.; Goodnow, T. T.; Kaifer, A. E.; Newton, S.
P.; Pietraszkiewicz, M.; Philp, D.; Raymo, F. M.; Reder, A. S.; Rutland,
M. T.; Slawin, A. M. Z.; Spencer, N.; Stoddart, J . F.; Williams, D. J . J .
Am. Chem. Soc. 1995, 117, 1271. (c) Ashton, P. R.; J oachimi, D.;
Spencer, N.; Stoddart, J . F.; Tschierske, C.; White, A. J . P.; Williams,
D. J .; Zab, K. Angew. Chem., Int. Ed. Engl. 1994, 33, 1503. (d)
Amabilino, D. B.; Ashton, P. R.; Pe´rez-Garcia, L.; Stoddart, J . F. Angew.
Chem., Int. Ed. Engl. 1995, 34, 2378. (e) Asakawa, M.; Ashton, P. R.;
Boyd, S. E.; Brown, C. L.; Menzer, S.; Pasini, D.; Stoddart, J . F.; Tolley,
M. S.; White, A. J . P.; Williams, D. J .; Wyatt, P. G. Chem. Eur. J . 1997,
3, 463. (f) Anelli, P.-L.; Asakawa, M.; Ashton, P. R.; Bissell, R. A.;
Clavier, G.; Go´rski, R.; Kaifer, A. E.; Langford, S. J .; Mattersteig, G.;
Menzer, S.; Philp, D.; Slawin, A. M. Z.; Spencer, N.; Stoddart, J . F.;
Tolley, M. S.; Williams, D. J . Chem. Eur. J . 1997, 3, 1113. (g) Ashton,
P. R.; Horn, T.; Menzer, S.; Preece, J . A.; Spencer, N.; Stoddart, J . F.;
Williams, D. J . Synthesis 1997, 481. (h) Asakawa, M.; Ashton, P. R.;
Balzani, V.; Credi, A.; Mattersteig, G.; Matthews, O. A.; Montalti, O.
A.; Spencer, N.; Stoddart, J . F.; Venturi, M. Chem. Eur. J . 1997, 3,
1992. (i) Gillard, R. E.; Raymo, F. M.; Stoddart, J . F. Chem. Eur. J .
1997, 3, 1933. (j) Ashton, P. R.; Boyd, S. E.; Menzer, S.; Pasini, D.;
Raymo, F. M.; Spencer, N.; Stoddart, J . F.; White, A. J . P.; Williams,
D. J .; Wyatt, P. G. Chem. Eur. J . 1998, 4, 299. (k) Amabilino, D. B.;
Stoddart, J . F.; Williams, D. J . Chem. Mater. 1994, 6, 1159. (l) Menzer,
S.; White, A. J . P.; Williams, D. J .; Belohradsky, M.; Hamers, C.;
Raymo, F. M.; Shipway, A. N.; Stoddart, J . F. Macromolecules 1998,
31, 295. (m) Amabilino, D. B.; Ashton, P. R.; Balzani, V.; Boyd, S. E.;
Credi, A.; Lee, J . Y.; Menzer, S.; Stoddart, J . F.; Venturi, M.; Williams,
D. J . J . Am. Chem. Soc. 1998, 120, 4295.
Ring-closing metathesis (RCM) has been established
as an efficient approach to macrocyclic systems via
intramolecular formation of carbon-carbon double
bonds.5,31,32 Ruthenium benzylidene catalyst 1 has been
shown to be highly effective in these reactions mostly
because of its high activity and tolerance to a wide array
of functional groups.33
While RCM was initially applied to the synthesis of
smallsfive to eight-membered rings32,34sthis methodol-
(16) (a) Fujita, M.; Ogura, K. Bull. Chem. Soc. J pn. 1996, 69, 1471.
(b) Fujita, M.; Aoyagi, M.; Ibukuro, F.; Ogura, K.; Yamaguchi, K. J .
Am. Chem. Soc. 1998, 120, 611.
(17) Whang, D.; Park, K.-M.; Heo, J .; Ashton, P.; Kim, K. J . Am.
Chem. Soc. 1998, 120, 0, 4899.
(18) Rowan, A. E.; Aarts, P. P. M.; Koutstaal, K. W. M. J . Chem.
Soc., Chem. Commun. 1998, 611.
(19) Kaes, C.; Hosseini, M. W.; Rickard, C. E. F.; Skelton, B. W.;
White, A. H. Angew. Chem., Int. Ed. Engl. 1998, 37, 920.
(20) Zhu, S. S.; Swager, T. M. J . Am. Chem. Soc. 1997, 119, 12568.
(21) Anderson, S.; Claridge, T. D. W.; Anderson, H. L. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 1310.
(22) Schmittel, M.; Ganz, A. J . Chem. Soc., Chem. Commun. 1997,
999.
(23) Kolchinsi, A. G.; Busch, D. H.; Alcock, N. W. J . Chem. Soc.,
Chem. Commun. 1995, 1289.
(24) Owen, G. J .; Hodge, P. J . Chem. Soc., Chem. Commun. 1997,
11.
(25) Gruter, G.-J . M.; Akkerman, O. S.; Bickelhaupt, F. Tetrahedron
1996, 52, 2565.
(11) (a) Fischer, C.; Nieger, M.; Mogck, O.; Bo¨hmer, V.; Ungaro, R.;
Vo¨gtle, F. Eur. J . Org. Chem. 1998, 155. (b) Du¨nnwald, T.; J a¨ger, R.;
Vo¨gtle, F. Chem. Eur. J . 1997, 3, 2043. (c) Hunter, C. A. J . Am. Chem.
Soc. 1992, 114, 5303. (d) Carver, F. J .; Hunter, C. A.; Shannon, R. J .
J . Chem Soc., Chem. Commun. 1994, 1277.
(12) (a) Lane, A. S.; Leigh, D. A.; Murphy, A. J . Am. Chem. Soc.
1997, 119, 11092. (b) Leigh, D. A.; Moody, K.; Smart, J . P.; Watson,
K. J .; Slawin, M. Z. Angew. Chem., Int. Ed. Engl. 1996, 35, 306. (c)
Leigh, D. A.; Murphy, A.; Smart, J . P.; Slawin, A. M. Z. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 728. (e) J ohnston, A. G.; Leigh, D. A.; Pritchard,
R. J .; Deegan, M. D. Angew. Chem., Int. Ed. Engl. 1995, 34, 1209.
(13) (a) Wenz, G.; Steinbrunn, M. B.; Landfester, K. Tetrahedron
1997, 53, 15575. (b) Herrmann, W.; Schneider, M.; Wenz, G. Angew.
Chem., Int. Ed. Engl. 1997, 36, 2511. (c) Ogino, H. J . Am. Chem. Soc.
1981, 103, 1303. (d) Harada, A.; Li, J .; Kamachi, M. Nature 1992, 356,
325.
(26) Mingos, D. M. P.; Yau, J .; Menzer, S.; Williams, D. J . Angew.
Chem., Int. Ed. Engl. 1995, 34, 1894.
(14) (a) Gibson, H. W.; Liu, S.; Gong, C.; J i, Q.; J oseph, E.
Macromolecules 1997, 30, 3711. (b) Gong, C.; Gibson, H. W. J . Am.
Chem. Soc. 1997, 119, 5862. (c) Gong, C.; Gibson, H. W. J . Am. Chem.
Soc. 1997, 119, 8585. (d) Gibson, H. W.; Nagvekar, D. S.; Powell, J .;
Gong, C.; Bryant, W. S. Tetrahedron 1997, 53, 15197. (e) Gong, C.;
Gibson, H. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2331. (f) Gong,
C.; Gibson, H. W. Angew. Chem., Int. Ed. Engl. 1998, 37, 310. (g) Gong,
C.; Glass, T. E.; Gibson, H. W. Macromolecules 1998, 31, 308.
(15) (a) Hamilton, D. G.; Feeder, N.; Prodi, L.; Teat, S. J .; Clegg,
W.; Sanders, J . K. M. J . Am. Chem. Soc. 1998, 120, 1096. (b) Hamilton,
D. G.; Davies, J . E.; Prodi, L.; Sanders, J . K. M. Chem. Eur. J . 1998,
4, 608.
(27) Benniston, A. C.; Mackie, P. R.; Harriman, A. Angew. Chem.,
Int. Ed. Engl. 1998, 37, 7, 354.
(28) Meschke, C.; Buschmann, H.-J .; Schollmeyer, E. Macromol.
Rapid Commun. 1998, 19, 59.
(29) (a) Chambron, J .-C.; Harriman, A.; Heitz, V.; Sauvage, J .-P. J .
Am. Chem. Soc. 1993, 115, 7419. (b) Harriman, A.; Sauvage, J .-P.
Chem. Soc. Rev. 1996, 41.
(30) (a) Fujita, M.; Ibukura, F.; Hajihara, H.; Ogura, K. Nature 1994,
367, 720. (b) Whang, D. M.; Park, K. M.; Heo, J .; Ashton, P.; Kim, K.
J . Am. Chem. Soc. 1998, 120, 4899.
(31) For early attempts to synthesize catenanes via RCM, see:
Wolovsky, R. J . Am. Chem. Soc. 1970, 92, 2132.

Synthesis of Catenane Structures
J . Org. Chem., Vol. 64, No. 15, 1999 5465
Sch em e 1. Sch em a tic Dr a w in g of th e Ap p r oa ch Utilizin g a Com bin a tion of a Tr a n sition -Meta l-Ba sed
Tem p la te Str a tegy a n d RCM To P r ovid e Access to [2]Ca ten a n esa
a
Key: (A) formation of a threaded complex followed by RCM and decomplexation; (B) formation of an intertwined complex followed by
2-fold RCM, decomplexation, and hydrogenation. The circle represents the transition ion.
ogy has recently been extended to larger ring systems
incorporating up to 38 atoms.35 Recently, we reported in
a preliminary communication a combination of a su-
pramolecular template strategy and RCM to provide
ready access to [2]catenanes with different ring sizes in
high yields.36-38 Herein, we report the full synthetic
strategy to obtain [2]catenanes using RCM.
Resu lts a n d Discu ssion
One of the most efficient syntheses of interlocked
molecules relies on the use of a transition-metal ion as a
template.6-8 This approach takes advantage of the pre-
ferred tetrahedral geometry of certain low-valent transi-
tion metals such as copper(I), in particular, once coordi-
nated to two 2,9-disubstituted 1,10-phenanthroline units.
In this general strategy, a complex formed between 2,9-
dianisyl-1,10-phenanthroline and copper(I) initiates the
construction of the catenane. Reaction of this complex
with a diiodide derived from pentaethylene glycol in the
presence of cesium carbonate as base resulted in the [2]-
catenate in 27% yield, after difficult and time-consuming
chromatographic separation.6c In this study, a general
strategy for the synthesis of catenanes utilizing a com-
bination of transition metal (copper)-based preorganiza-
tion and RCM will be described. Scheme 1 presents a
schematic presentation of the general approach.
(32) For recent reviews on RCM, see: (a) Grubbs, R. H.; Miller, S.
J .; Fu, G. C. Acc. Chem. Res. 1995, 28, 446. (b) Schmalz, H.-G. Angew.
Chem., Int. Ed. Engl. 1995, 34, 1833. (c) Schuster, M.; Blechert, S.
Angew. Chem., Int. Ed. Engl. 1997, 36, 2037. (d) Chang, S.; Grubbs,
R. H. Tetrahedron 1998, 54, 4413. (e) Armstrong, S. K. J . Chem. Soc.,
Perkin Trans. 1 1998, 371.
(33) (a) Nguyen, S. T.; J ohnson, L. K.; Grubbs, R. H. J . Am. Chem.
Soc. 1992, 114, 3974. (b) Schwab, P.; Grubbs, R. H.; Ziller, J . W. J .
Am. Chem. Soc. 1996, 118, 100.
(34) Fu, G. C.; Grubbs, R. H. J . Am. Chem. Soc. 1992, 114, 5426.
(35) (a) Miller, S. J .; Blackwell, H. E.; Grubbs, R. H. J . Am. Chem.
Soc. 1996, 118, 9606. (b) Fu¨rstner, A.; Langemann, K. J . Org. Chem.
1996, 61, 3942. (c) Clark, T. D.; Ghadiri, M. R. J . Am. Chem. Soc. 1995,
117, 12364. (d) Ko¨nig, B.; Horn, C. Synlett 1996, 1013. (e) Fu¨rstner,
A.; Kindler, N. Terahedron Lett. 1996, 37, 7005. (f) Bertinato, P.;
Sorensen, E. J .; Meng, D.; Danishefsky, S. J . J . Org. Chem. 1996, 61,
8000. (g) Xu, Z.; J ohannes, C. H.; Salman, S. S.; Hoveyda, A. H. J .
Am. Chem. Soc. 1996, 118, 10926. (h) Nicolaou, K. C.; He, Y.;
Vourloumis, D.; Vallberg, H.; Yang, Z. Angew. Chem., Int. Ed. Engl.
1996, 35, 2399. (i) Fu¨rstner, A.; Langemann, K. Synthesis 1997, 792.
(36) Mohr, B.; Weck, M.; Sauvage, J .-P.; Grubbs, R. H. Angew.
Chem., Int. Ed. Engl. 1997, 36, 1308.
(37) Since the first report of this research,36 Sauvage et al. synthe-
sized a molecular knot using RCM: Dietrich-Buchecker, C.; Rapenne,
G.; Sauvage, J .-P. J . Chem. Soc., Chem. Commun. 1997, 2053.
(38) For other catenane systems cyclized via RCM, see: (a) Hamil-
ton, D. G.; Feeder, N.; Teat, S. J .; Sanders, J . K. M. New. J . Chem.
1998, 1019. (b) Kidd, T. J .; Leigh, D. A.; Wilson, A. J . J . Am. Chem.
Soc. 1999, 121, 1599.

5466 J . Org. Chem., Vol. 64, No. 15, 1999
Sch em e 2. Syn th esis of th e Ca ten a n e Bu ild in g Block s 6 a n d 7
Weck et al.
The building blocks for this system are the 30-
membered macrocycle 8, bearing a 2,9-diphenyl-1,10-
phenanthroline (dpp) bidentate in its backbone, and the
acyclic ligands 6 and 7, in which the dpp moiety was
symmetrically substituted with ethylene oxide groups
terminated with olefins. Compound 8 was synthesized
in analogy to literature.6c Ligands 6 and 7 were synthe-
sized by coupling 4-lithioanisole with 1,10-phenanthro-
line, followed by hydrolysis and oxidation to produce
dianisol phenanthroline (dap, 2) in high yield. Deprotec-
tion yielded dpp 3, which was reacted with chlorodieth-
yleneglycol or chlorotriethyleneglycol to give compounds
4 and 5. Subsequent alkylation using allyl bromide
resulted in ligands 6 and 7 in high yields (Scheme 2).
To ensure the compatibility of these building blocks
with the ruthenium catalyst 1, several NMR experiments
were carried out in which building blocks 2 and 3, both
with and without copper, were added to a dichlo-
romethane solution of 1 at room temperature under
argon. No decomposition of the catalyst over a period of
several hours was detected, which indicated the compat-
ibility of these compounds with 1.
Threaded complexes 9 and 10 assembled instantly and
quantitatively by the reaction of 8 with a stoichiometric
amount of [Cu(MeCN)4]PF6 in dichloromethane/acetoni-
trile followed by the addition of diolefins 6 and 7 (Scheme
3).6 In a similar manner, the intertwined complex 15 was
obtained in quantitative yields by complexation of 2 equiv
of 6 with [Cu(MeCN)4] (Scheme 4). The full complexation
of these compounds could be easily monitored by NMR
spectroscopy since specific aromatic proton resonances
were characteristically shifted upon complexation.6
After complexation, complexes 9, 10, and 15 were
subjected to intramolecular RCM with catalyst 1 to yield
the corresponding [2]catenates 11, 12, and 16 through
the formation of 32- (11, 16) and 38-membered (12) rings
(Schemes 3 and 4). All reactions were carried out at room
temperature under argon for several hours. A total of 10
mol % catalyst was used, which was added to the reaction
in 5 mol % portions, once at the beginning of the reaction
and again after 6 h. To drive this RCM reaction closer to
completion, ethylene, a product of the RCM, was removed
from the reaction by opening the reaction vessel for a
short period of time every 2 h to a weak vacuum.
Two-fold RCM of 15 led exclusively to systems with
two interlocked rings. The twisted product, formed by the
intramolecular reaction between the olefins of different
ligands, was not detected. The formation of catenates 11,
12, and 16 could be unequivocally shown by 1H NMR
spectroscopy and fast atom bombardment (FAB-MS)
mass spectroscopy.39,6h Figure 1 presents the FAB-MS
spectra of catenates 11 and 16.
Yields of these cyclization reactions ranged from 88 to
92% as summarized in Table 1. The cyclization yields for
these systems exceeded those for most other medium- or
large-ring systems, where hydrogen bonding,32,35 confor-
mational constraints,35 or template effects40 are present
to facilitate the reaction. It is believed that the remark-
able efficiency of these RCM reactions stemmed, at least
in part, from a preorganization of the olefins due to
electrostatic interactions between the oxygen atoms and
the phenanthroline systems,41 in combination with a
locked conformation of the phenyl rings (π-donors) and
phenanthroline systems (π-acceptor).42 This assumption
is supported by the exclusive formation of the interlocked
species in the RCM of 15 and the observation that RCM
of the free ligands 6 and 7 proceeds in lower yields
between 70 and 75%.
(39) Vetter, W.; Logemann, E.; Schill, G. Org. Mass. Spectrom. 1977,
12, 351.
(40) Marsella, M. J .; Maynard, H. D.; Grubbs, R. H. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 1101.
(41) Desiraju, G. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 2311.
(42) These interactions have been observed in the solid state for
structurally related [2]catenates (see ref 6j,m).

Synthesis of Catenane Structures
J . Org. Chem., Vol. 64, No. 15, 1999 5467
Sch em e 3. Syn th esis of [2]Ca ten a tes 11 a n d 12 Usin g RCM
Sch em e 4. Syn th esis of [2]Ca ten a te 16 Usin g RCM
For all catenates, the energetically favored trans
FAB-MS. Figure 2 shows the FAB-MS spectra of cat-
enands 13 and 17. Both spectra display the characteristic
pattern for catenated species, the absence of peaks
between the molecular ion peaks and the peaks corre-
sponding to the individual macrocycles.6 When an in-
tramolecular RCM reaction between the olefins of dif-
ferent ligands had occurred, peaks in the region between
the molecular ion peak and the peaks corresponding to
the individual macrocycles would be expected. Therefore,
these FAB-MS provide further proof for the exclusive
formation of catenates 11, 12, and 16 in the RCM steps.
Upon standing at room temperature under argon for
4-5 months, catenands 13, 14, and 17 changed in color
from white to yellow, indicating decomposition. This
configuration at the double bond prevailed, which is
commonly reported for macrocycles made via RCM.32,35,40
The olefin E/Z ratio could be determined by the integra-
1
tion of the H NMR signals of the isomeric olefin protons
(cis multiplet around 5.80 ppm, trans multiplet around
5.95 ppm).
Demetalation of catenates 11, 12, and 16 with potas-
sium cyanide in aqueous acetonitrile in analogy to
literature procedures6-8 afforded [2]catenands 13, 14, and
17 in high yields. Scheme 5 shows the demetalation of
catenates 11 and 12.
In analogy to the catenates, the composition of cat-
1
enands 13, 14, and 17 was confirmed by H NMR and

5468 J . Org. Chem., Vol. 64, No. 15, 1999
Weck et al.
F igu r e 2. Positive FAB-MS spectra of catenands 13 (a) and
17 (b) in a p-nitrobenzyl alcohol matrix. The peaks at m/z )
1159 and m/z ) 1185 correspond to catenanes 13 and 17. The
absence of peaks between the molecular ion peak and the
peaks corresponding to the individual macrocycles is charac-
teristic for catenate species.6m
F igu r e 1. Positive FAB-MS spectra of (a) catenate 11 and
(b) catenate 16 in a p-nitrobenzyl alcohol matrix. The peaks
at m/z ) 1221 and 1247 correspond to catenates 11 and 16,
respectively. The absence of peaks between the molecular ion
peak and the peaks corresponding to the individual macro-
cycles is characteristic of catenate species.6m
Ta ble 1. Resu lts of th e Rin g-Closin g Meta th esis a n d
Dem eta la tion Rea ction s
catenate
yielda (%)
trans/ cisb
catenand
yielda (%)
11
12
16
92
88
92
97/3
95/5
98/2
13
14
17
19
92
93
90
96
a
b
Yield of isolated product. Determined by integration of the
1H NMR signals of the isomeric olefin protons.
decomposition seems to occur at least partially at the
carbon-carbon double bonds that were formed during the
RCM. Therefore, a selective hydrogenation of these
double bonds has been carried out using Crabtree’s
iridium-based catalyst as outlined in Scheme 6. In a
general procedure, the catenate was dissolved in dichlo-
romethane, a catalytic amount of the iridium catalyst was
added, and the reaction was stirred overnight under 200
psi hydrogen pressure. Using this procedure, the hydro-
genated catenate 18 was obtained in quantitative yield.
As described above, demetalation was carried out using
potassium cyanide to yield the free catenands in 96%
yield (Scheme 6).
F igu r e 3. Positive FAB-MS spectra of catenand 19 in a
p-nitrobenzyl alcohol matrix. The peak at m/z ) 1162 corre-
sponds to catenand 19. The absence of peaks between the
molecular ion peak and the peaks corresponding to the
individual macrocycles is characteristic for catenate species.6m
Con clu sion
1
Catenand 19 was characterized by H NMR and FAB-
Herein, we present a new approach to obtain inter-
locked architectures through RCM. Two new phenan-
throline-based ligands that contain terminal olefinic
groups were synthesized. These ligands were cyclized
MS. Figure 3 shows the positive FAB-MS of 19. As
expected, no decomposition occurred after hydrogenation
of the double bond over a period of several months.

Synthesis of Catenane Structures
J . Org. Chem., Vol. 64, No. 15, 1999 5469
Sch em e 5. Dem eta la tion of [2]Ca ten a tes 11 a n d 12 To Yield [2]Ca ten a n d s 13 a n d 14
Sch em e 6. Hyd r ogen a tion of [2]Ca ten a te 9 Usin g Cr a btr ee’s Ir id iu m -ba sed Ca ta lyst To Yield th e
Dou ble-Bon d -F r ee [2]Ca ten a te 18 F ollow ed by Dem eta la tion To Yield [2]Ca ten a n d 19
Ma ter ia ls. Dichloromethane used in the RCM reactions was
distilled from calcium hydride and degassed by repeated
freeze-pump-thaw cycles. All other solvents were used
without further purification unless otherwise noted. All chemi-
cals were purchased from the Aldrich Chemical Co. and used
without further purification. The ruthenium complex 1 was
graciously provided by Dr. Peter Schwab. Compounds 2, 3, and
8 were synthesized as reported in the literature.6c
after complexation around copper using a ruthenium
catalyst in nearly quantitative yield to obtain catenane
precursors with different ring sizes. Demetalation of the
complexes using potassium cyanide produced the corre-
sponding [2]catenands in high yields. To prevent decom-
position at the olefinic group, hydrogenation of the
carbon-carbon double bonds was carried out using
Crabtree’s catalyst. After demetalation, the fully satu-
rated catenand did not show any decomposition over a
period of several months. The strategy presented herein
establishes a highly efficient approach to interlocked
structures and can be used for a large variety of inter-
locked structures including rotaxanes and knot struc-
tures.37
Syn t h esis of Com p ou n d 4. A mixture of 3 (2.0 g, 5.50
mmol), chlorodiethyleneglycol (1.5 g, 12.0 mmol), and Cs2CO3
(4.9 g, 15.0 mmol) in 150 mL of DMF was heated for 12 h at
80 °C under argon. The solvent was removed in vacuo, and
the residue was extracted with 250 mL of dichloromethane.
The dichloromethane extract was washed three times with
water and subsequently dried over magnesium sulfate. Final
purification was achieved by silica gel column chromatography
using dichloromethane/methanol (99:1) as eluent to yield 2.46
g of an amorphous white solid: yield 83%; 1H NMR (CDCl3) δ
8.43 (d, 4H, J ) 8.8 Hz), 8.26 (d, 2H, J ) 8.5 Hz), 8.08 (d, 2H,
J ) 8.5 Hz), 7.74 (s, 2H), 7.13 (d, 4H, J ) 8.8 Hz), 4.27 (t, 4H,
J ) 4.7 Hz), 3.94 (t, 4H, J ) 4.7 Hz), 3.79-3.69 (m, 8H); 13C
NMR (CDCl3) δ 160.0, 156.3, 146.1, 136.8, 132.6, 129.1, 127.6,
Exp er im en ta l Section
Gen er a l Con sid er a tion s. Argon was purified by passage
through columns of BASF R3-11 catalyst (Chemalog) and 4 Å
molecular sieves (Linde). Elemental analyses were performed
by Fenton Harvey at the California Institute of Technology
Elemental Analysis Facility.

5470 J . Org. Chem., Vol. 64, No. 15, 1999
Weck et al.
125.7, 119.4, 114.9, 72.7, 69.7, 67.6, 61.8, 50.8; HRMS (FAB)
calcd for C32H32N2O6 (MH)+ 541.2353, found 541.2347.
117.0, 113.4, 72.5, 71.6, 71.2, 70.1, 69.8, 69.3, 67.9, 67.5; HRMS
(FAB) calcd for C76H82N4O14Cu (MH)+ 1337.5, found 1337.5.
P r eca ten a te 15: H NMR (CD2Cl2) δ 8,49 (d, 2H, J ) 8.4
1
Syn th esis of Com p ou n d 5. 5 was synthesized in a manner
analogous to that of 4 by reacting 3 with chlorotriethyleneg-
lycol: yield 86%; 1H NMR (CDCl3) δ 8.43 (d, 4H, J ) 8.8 Hz),
8.26 (d, 2H, J ) 8.5 Hz), 8.08 (d, 2H, J ) 8.5 Hz), 7.74 (s, 2H),
7.13 (d, 4H, J ) 8.8 Hz), 4.28 (t, 4H, J ) 4.8 Hz), 3.93 (t, 4H,
J ) 4.8 Hz), 3.81-3.61 (m, 12H); 13C NMR (CDCl3) δ 160.0,
156.4, 146.0, 136.8, 132.7, 129.0, 127.6, 125.6, 119.2, 114.8,
72.7, 69.7, 69.5, 67.6, 61.6; HRMS (FAB) calcd for C36H40N2O8
(MH)+ 629.2874, found 629.2875.
Syn th esis of Liga n d 6. To a mixture of 4 (2.0 g, 3.7 mmol)
and allyl bromide (1.0 g, 8.2 mmol) in 150 mL of DMF under
argon atmosphere was added NaH (0.2 g, 8.3 mmol). The
reaction mixture was heated to 80 °C, and after 2 h another
portion of NaH (0.1 g, 4.2 mmol) was added. After the mixture
was stirred for 8 h at 80 °C, the solvent was removed in vacuo
and the residue was extracted with 250 mL of dichlo-
romethane. The dichloromethane extract was washed three
times with water and subsequently dried over magnesium
sulfate. Final purification was achieved by silica gel column
chromatography using dichloromethane/methanol (99:1) as
eluent to yield 1.97 g of an amorphous white solid: yield 86%;
1H NMR (CDCl3) δ 8.43 (d, 4H, J ) 8.8 Hz), 8.26 (d, 2H, J )
8.5 Hz), 8.08 (d, 2H, J ) 8.5 Hz), 7.74 (s, 2H), 7.13 (d, 4H, J
) 8.8 Hz), 6.05-5.85 (m, 2H), 5.35-5.18 (m, 4H), 4.27 (t, 4H,
J ) 4.9 Hz), 4.04-4.08 (m, 4H), 3.94 (t, 4H, J ) 4.9 Hz), 3.78
(m, 4H), 3.67 (m, 4H); 13C NMR (CDCl3) δ 160.2, 156.4, 146.1,
136.8, 134.8, 132.4, 129.0, 127.6, 125.7, 119.3, 117.2, 114.9,
72.4, 71.0, 69.9, 69.6, 67.6; HRMS (FAB) calcd for C38H40N2O6
(MH)+ 621.2977, found 621.2982.
Hz), 8.03 (s, 2H), 7.84 (d, 2H, J ) 8.4 Hz), 7.43 (d, 4H, J ) 8.6
Hz), 6.08 (d, 4H, J ) 8.6 Hz), 6.05-5.87 (m, 2H), 5.36-5.16
(m, 4H), 4.07-4.04 (m, 4H), 3.72-3.63 (m, 32H); 13C NMR
(CD2Cl2) δ 159.8, 156.8, 143.9, 137.6, 135.5, 131.9, 129.7, 128.5,
126.7, 124.8, 117.0, 113.4, 72.5, 71.2, 70.1, 69.8, 67.9; HRMS
(FAB) calcd for C76H80N4O12Cu (MH)+ 1303.5, found 1303.2.
Gen er a l P r oced u r e for th e Rin g-Closin g Meta th esis
of th e Cop p er -Ba sed Ca ten a tes 11, 12, a n d 16. Under
exclusion of air and moisture, 1 (5 mol %) was added in
dichloromethane to a 0.01 M solution of the diolefin (typically
200-900 mg) in dichloromethane. After the mixture was
stirred for 6 h at room temperature, additional catalyst (5 mol
%) was added, and stirring was continued for an additional 6
h. The solvent was then removed in vacuo, and the crude
reaction mixture was purified by repeated silica gel column
chromatography using dichloromethane/methanol (96:4) to
yield the [2]catenates as burgundy solids.
1
Ca ten a te 11: yield 92%; H NMR (CDCl3) δ 8.62 (d, 2H, J
) 8.4 Hz), 8.52 (d, 2H, J ) 8.4 Hz), 8.23 (s, 2H), 8.14 (s, 2H),
7.80 (m, 4H), 7.32 (m, 8H), 6.09 (m, 2H), 6.00 (m, 8H), 4.16
(m, 4H), 3.80-3.48 (m, 36H); 13C NMR (acetone-d6) δ 159.0,
158.9, 155.9, 143.3, 143.2, 137.7, 137.3, 132.1, 131.7, 129.5,
129.4, 129.3, 128.1, 127.1, 126.8, 123.7, 123.6, 112.7, 112.6,
71.5, 71.1, 70.8, 70.7, 70.5, 69.1, 68.8, 67.4, 66.9; HRMS (FAB)
calcd for C70H70N4O12Cu (MH)+ 1221.4, found 1221.4. Anal.
Calcd for C70H70N4O12CuPF6: C, 61.41; H, 5.16; N, 4.09.
Found: C, 60.92; H, 5.05; N, 3.96.
1
Ca ten a te 12: yield 88%; H NMR (CDCl3) δ 8.62 (d, 2H, J
) 8.4 Hz), 8.55 (d, 2H, J ) 8.4 Hz), 8.22 (s, 2H), 8.12 (s, 2H),
7.84 (m, 4H), 7.47 (d, 4H, J ) 8.7 Hz), 7.30 (d, 4H, J ) 8.7
Hz), 6.09 (d, 8H, J ) 8.7 Hz), 5.98 (d, 2H, J ) 8.7 Hz), 5.83
(m, 2H), 4.16 (m, 4H), 3.80-3.48 (m, 44H); 13C NMR (acetone-
d6) δ 159.2, 158.9, 156.3, 155.9, 143.4, 143.3, 137.7, 137.3,
132.4, 132.1, 131.4, 129.5, 129.4, 129.3, 129.2, 128.2, 128.1,
127.3, 126.8, 126.4, 124.4, 123.7, 123.6, 113.0, 112.8, 112.6,
71.1, 71.0, 70.9, 70.8, 70.7, 70.5, 70.3, 69.7, 69.4, 68.8, 67.6,
66.9; HRMS (FAB) calcd for C74H78N4O14Cu (MH)+ 1309.1,
found 1309.3. Anal. Calcd for C74H78N4O14CuPF6: C, 61.05;
H, 5.40; N, 3.85. Found: C, 61.05; H, 5.28; N, 3.95.
Syn th esis of Liga n d 7. 7 was synthesized in analogy to 6
by reacting 5 with allyl bromide: yield 89%; 1H NMR (CDCl3)
δ 8.42 (d, 4H, J ) 8.9 Hz), 8.26 (d, 2H, J ) 8.5 Hz), 8.08 (d,
2H, J ) 8.5 Hz), 7.74 (s, 2H), 7.12 (d, 4H, J ) 8.9 Hz), 6.03-
5.83 (m, 2H), 5.33-5.14 (m, 4H), 4.26 (t, 4H, J ) 4.9 Hz), 4.03
(m, 4H), 3.93 (t, 4H, J ) 4.9 Hz), 3.81-3.60 (m, 12H); 13C NMR
(CDCl3) δ 160.2, 156.4, 146.1, 136.8, 134.8, 132.4, 129.0, 127.6,
125.7, 119.4, 117.1, 114.9, 72.3, 71.0, 70.8, 69.8, 69.5, 67.6;
HRMS (FAB) calcd for C42H48N2O8 (MH)+ 709.3489, found
709.3486.
Gen er a l P r oced u r e for th e Meta l Com p lexa tion To
F or m th e P r eca ten a tes 9, 10, a n d 15. In a Schlenk flask, 1
equiv of 2 (for the synthesis of 9 or 10) or 6 (for the synthesis
of 15) was dissolved under argon in a 1:1 mixture of dichlo-
romethane and acetonitrile. After addition of 1 equiv of Cu-
(MeCN)4, the reaction was stirred at room temperature under
argon for 15 min. In a second Schlenk flask, 1 equiv of 6 (for
the synthesis of 9 and 15) or 7 (for the synthesis of 10) was
dissolved in dichloromethane and cannula filtered into the first
solution. The solution was stirred under argon at room
temperature for an additional 30 min, followed by removal of
the solvent in vacuo. Final purification was achieved by
precipitation with dichloromethane/pentane and silica gel
column chromatography using dichloromethane/methanol (96:
4) to yield a dark red, crystalline solid in quantitative yield.
1
Ca ten a te 16: yield 92%; H NMR (CDCl3) δ 8.51 (d, 4H, J
) 8.4 Hz), 8.13 (s, 4H), 7.81 (d, 4H, J ) 8.4 Hz), 7.41 (d, 8H,
J ) 8.7 Hz), 6.11 (m, 4H), 6.02 (d, 8H, J ) 8.7 Hz), 4.18 (m,
8H), 3.80-3.67 (m, 32H); 13C NMR (acetone-d6) δ 159.0, 155.9,
143.3, 137.5, 131.7, 129.5, 129.3, 128.1, 126.8, 123.7, 112.7,
71.5, 70.8, 70.6, 69.1, 67.5; HRMS (FAB) calcd for C72H72N4O12
-
-
Cu (MH)+ 1247.2, found 1247.1. Anal. Calcd for C72H72N4O12
CuPF6: C, 61.83; H, 5.48; N, 3.88. Found: C, 62.04; H, 5.31;
N, 4.00.
Gen er a l P r oced u r e for th e Dem eta la tion of th e Cop -
p er -Ba sed Ca ten a tes 11, 12, a n d 16. The catenate was
dissolved in acetonitrile followed by addition of an excess of
potassium cyanide in water. The mixture was stirred for 30
min at room temperature, during which time the dark bur-
gundy color vanished and a brown solid precipitated. The
solution was decantated and the precipitate dissolved in
dichloromethane. The dichloromethane phase was washed
several times with water and dried over magnesium sulfate.
The solvent was removed in vacuo to yield a slightly milky
solid. Final purification was achieved by silica gel column
chromatography to yield a white solid.
P r eca ten a te 9: 1H NMR (CD2Cl2) δ 8.63 (d, 2H, J ) 8.4
Hz), 8.50 (d, 2H, J ) 8.4 Hz), 8.24 (s, 2H), 8.05 (s, 2H), 7.88
(d, 2H, J ) 8.4 Hz), 7.84 (d, 2H, J ) 8.8 Hz), 7.48 (d, 4H, J )
8.6 Hz), 7.31 (d, 4H, J ) 8.6 Hz),), 6.09 (d, 4H, J ) 8.6 Hz),
5.99 (d, 4H, J ) 8.6 Hz), 6.05-5.87 (m, 2H), 5.36-5.15 (m,
4H), 4.03-4.07 (m, 4H), 3.73-3.48 (m, 36H,); 13C NMR (CD2-
Cl2) δ 159.8, 159.4, 157.0, 156.3, 143.7, 138.3, 137.4, 135.5,
132.8, 131.9, 129.8, 129.6, 128.7, 128.4, 127.6, 126.6, 124.4,
117.0, 113.4, 72.5, 71.6, 71.2, 70.1, 69.8, 69.3, 67.9, 67.5; HRMS
(FAB) calcd for C72H74N4O12Cu (MH)+ 1249.5, found 1249.3.
Ca ten a n d 13: yield 92%; 1H NMR (CDCl3) δ 8.48 (m, 8H),
8.19 (d, 2H, J ) 2.7 Hz), 8.17 (d, 2H, J ) 2.7 Hz), 8.05 (s, 2H),
8.02 (s, 2H), 7.67 (m, 4H), 7.16 (t, 8H, J ) 8.7 Hz), 5.96 (m,
2H), 4.19-3.56 (m, 42H); 13C NMR (CDCl3) δ 161.5, 160.0,
156.3, 156.2, 146.1, 146.0, 136.7, 132.5, 132.4, 129.7, 129.3,
129.2, 127.4, 125.5, 119.2, 115.3, 115.2, 71.6, 71.1, 70.9, 70.7,
70.1, 68.8, 68.4, 66.8, 66.5; HRMS (FAB) calcd for C70H70N4O12
(MH)+ 1159.5, found 1159.5. Anal. Calcd for C70H70N4O12: C,
72.52; H, 6.09; N, 4.83. Found: C, 72.43; H, 5.95; N, 4.69.
Ca ten a n d 14: yield 93%; 1H NMR (CDCl3) δ 8.48 (m, 8H),
8.18 (m, 2H), 8.17 (m, 2H), 8.07 (s, 2H), 8.03 (s, 2H), 7.67 (m,
4H), 7.16 (t, 8H, J ) 8.7 Hz), 5.99 (m, 2H), 4.17-3.54 (m, 48H);
1
P r eca ten a te 10: H NMR (CD2Cl2) δ 8.63 (d, 2H, J ) 8.4
Hz), 8.50 (d, 2H, J ) 8.4 Hz), 8.23 (s, 2H), 8.05 (s, 2H), 7.88
(d, 2H, J ) 8.4 Hz), 7.84 (d, 2H, J ) 8.8 Hz), 7.48 (d, 4H, J )
8.6 Hz), 7.30 (d, 4H, J ) 8.6 Hz),), 6.09 (d, 4H, J ) 8.6 Hz),
5.99 (d, 4H, J ) 8.6 Hz), 6.05-5.81 (m, 2H), 5.31-5.10 (m,
4H), 4.01-3.97 (m, 4H), 3.73-3.48 (m, 44H,); 13C NMR (CD2-
Cl2) δ 159.8, 159.4, 157.0, 156.3, 143.8, 138.3, 137.4, 135.5,
132.8, 131.9, 129.8, 129.6, 128.7, 128.4, 127.6, 126.6, 124.4,

Synthesis of Catenane Structures
J . Org. Chem., Vol. 64, No. 15, 1999 5471
13C NMR (CDCl3) δ 160.0, 159.8, 156.4, 156.2, 146.2, 146.0,
136.8, 132.5, 132.4, 129.7, 129.2, 129.1, 127.4, 125.6, 119.2,
114.9, 114.8, 71.3, 70.9, 70.8, 70.7, 69.8, 69.6, 68.4, 67.4, 66.8,
66.4; HRMS (FAB) calcd for C74H78N4O14 (MH)+ 1242.5, found
1242.5. Anal. Calcd for C74H78N4O14: C, 71.47; H, 6.00; N, 4.51.
Found: C, 71.22; H, 5.96; N, 4.41.
2H), 8.21 (s, 2H), 7.85 (t, 4H, J ) 7.5 Hz), 7.35 (m, 8H), 6.04
(t, 8H, J ) 8.1 Hz), 3.86-3.48 (m, 44H); 13C NMR (CDCl3) δ
158.8, 158.7, 155.8, 155.7, 143.0, 142.9, 137.6, 137.1, 131.8,
131.0, 128.9, 128.8, 127.9, 127.8, 126.8, 126.5, 123.6, 123.5,
112.7, 71.3, 70.8, 70.7, 70.4, 70.3, 68.8, 68.7, 67.4; HRMS (FAB)
calcd for C70H72N4O12Cu (MH)+ 1223.4, found 1223.4. Anal.
Calcd for C70H72N4O12CuPF6: C, 61.39; H, 5.30; N, 4.09.
Found: C, 61.52; H, 5.11; N, 4.05.
Syn th esis of Ca ten a n d 19. 19 was synthesized in analogy
to 13 in 96% yield: 1H NMR (CD2Cl2) δ 8.53 (d of d, 8H, J )
9 Hz), 8.24 (d, 2H, J ) 12.6 Hz), 8.21 (d, 2H, J ) 12.6 Hz),
8.09 (s, 2H), 8.07 (s, 2H), 7.71 (d, 4H, J ) 10.5 Hz), 7.27 (d,
4H, J ) 8.7 Hz), 7.16 (d, 4H, J ) 9 Hz), 4.36-3.48 (m, 44H);
13C NMR (CD2Cl2) δ 158.8, 158.7, 155.8, 155.7, 143.0, 142.9,
137.6, 137.1, 131.8, 131.0, 128.9, 128.8, 127.9, 127.8, 126.8,
126.5, 123.6, 123.5, 112.7, 71.3, 70.8, 70.7, 70.4, 70.3, 68.8, 68.7,
67.4; HRMS (FAB) calcd for C70H72N4O12 (MH)+ 1161.5, found
1161.5. Anal. Calcd for C70H72N4O12: C, 72.38; H, 6.25; N, 4.83.
Found: C, 72.22; H, 6.17; N, 4.62.
Ca ten a n d 17: yield 90%; 1H NMR (CDCl3) δ 8.47 (d, 8H, J
) 2.7 Hz), 8.21 (d, 4H, J ) 8.4 Hz), 8.05 (d, 4H, J ) 8.4 Hz),
7.70 (s, 4H), 7.16 (d, 8H, J ) 9.6 Hz), 5.93 (m, 4H), 4.18-3.56
(m, 40H); 13C NMR (CDCl3) δ 160.0, 155.9, 146.0, 136.6, 132.4,
129.5, 129.1, 127.5, 125.6, 119.1, 115.1, 71.5, 70.9, 70.1, 68.8,
66.9; HRMS (FAB) calcd for C72H72N4O12 (MH)+ 1185.5, found
1185.5. Anal. Calcd for C72H72N4O12: C, 72.94; H, 6.13; N, 4.73.
Found: C, 72.51; H, 6.12; N, 4.69;
Syn th esis of Ca ten a te 18. In a Schlenk flask, 11 was
dissolved under argon in dichloromethane and cannula-filtered
into a Schlenk flask containing Crabtree’s iridium catalyst
dissolved in dichloromethane. The reaction was stirred at room
temperature under argon under 200 psi hydrogen pressure for
2 h. After filtration of the reaction over a plug containing
Celite, the solvent was removed in vacuo to yield a dark
burgundy solid. Final purification was achieved by silica gel
column chromatography (dichloromethane/methanol (95:5)) to
afford a burgundy solid in quantitative yield: 1H NMR (CDCl3)
δ 8.68 (d, 2H, J ) 8.4 Hz), 8.59 (d, 2H, J ) 8.4 Hz), 8.27 (s,
Ack n ow led gm en t. This work was supported by a
postdoctoral fellowship from the European Community
and by the United States Air Force.
J O990268C