mixture was heated to reflux overnight. After cooling to room
temperature the solvent was removed by rotary evaporation. The
solid was dissolved in chloroform and filtered through a short
plug of silica gel. Crystallization from CH2Cl2–h◦exane yielded
Acknowledgements
This work was supported a grant no. KBN 118/T09/10. All
calculations were performed at Poznan Supercomputing Center.
1
an orange solid 2c (275 mg, 63%), mp. 115–117 C; H NMR
(300 MHz, CDCl3): dH11.07 (s, 1H, OH), 9.89 (s, 1H, CHO),
7.53 (d, J = 7.7 Hz, 1H), 7.17 (d, J = 1.3 Hz, 1H), 7.14 (s, 1H),
7.02 (s, 1H), 4.04 (t, J = 6.6 Hz, 2H), 1.9–1.8 (m, 2H), 1.6–1.3
(m, 10H), 0.85 (t, J = 6.8 Hz, 3H, CH3); 13C NMR (75 MHz,
CDCl3): dC 195.92, 161.61, 154.22, 133.75, 132.29, 123.32, 120.58,
120.42, 117.20, 114.23, 94.52, 90.85, 70.03, 32.30, 29.85, 29.80,
29.78, 26.58, 23.16, 14.60; IR (KBr): 3157, 2921, 2851, 2210, 1652,
1620, 1487, 1236, 1214, 973, 800, 744 cm-1; EIMS: m/z = 621.7
(M+, 100%); HREIMS: calcd. for C40H46O6: 622.33264, found:
622.32947.
Notes and references
1 N. E. Borisova, M. D. Reshetova and Y. A. Ustynyuk, Chem. Rev.,
2007, 107, 46.
2 (a) J. Gawronski, H. Kołbon, M. Kwit and A. Katrusiak, J. Org. Chem.,
2000, 65, 5768; (b) M. Chadim, M. Budeˇsˇinsky, J. Hodacˇova, J. Zavada
and P. C. Junk, Tetrahedron: Asymmetry, 2001, 12, 127.
3 N. Kuhnert and A. M. Lopez-Periago, Tetrahedron Lett., 2002, 43,
3329.
4 (a) N. Kuhnert, G. M. Rossignolo and A. M. Lopez-Periago, Org.
Biomol. Chem., 2003, 1, 1157; (b) N. Kuhnert, A. M. Lopez-Periago
and G. M. Rossignolo, Org. Biomol. Chem., 2005, 3, 524; (c) N. Kuhnert,
C. Strabnig and A. M. Lopez-Periago, Tetrahedron: Asymmetry, 2002,
13, 123; (d) N. Kuhnert, N. Burzlaff, C. Patel and A. Lopez-Periago,
Org. Biomol. Chem., 2005, 3, 1911.
Macrocycles 3a–3c—general procedure
5 M. Kwit, P. Skowronek, H. Kołbon and J. Gawronski, Chirality, 2005,
17, S93.
6 J. Gregolinski, J. Lisowski and T. Lis, Org. Biomol. Chem., 2005, 3,
3161.
To a solution of (1R,2R)-1,2-diaminocyclohexane (1) (57 mg,
0.5 mmol) in chloroform–acetonitrile (3:1) or dichloromethane
(10 mL) was added at 0 ◦C a solution of dialdehyde 2a, 2b or 2c
(0.5 mmol) in chloroform–acetonitrile (3:1) or in dichloromethane
(10 mL). The mixture was stirred at room temperature for
2–3 h, then the solvent was evaporated and the solid product
was triturated with diethyl ether. The trianglimines 3a–3c were
obtained sufficiently pure (>95%) according to 1H NMR analysis;
since they could not be crystallized, no elemental analyses were
obtained.
7 J. Gawronski, K. Gawronska, J. Grajewski, M. Kwit, A. Plutecka and
U. Rychlewska, Chem.–Eur. J., 2006, 12, 1807.
8 M. Kwit, A. Plutecka, U. Rychlewska, J. Gawron´ski, A. F. Khlebnikov,
S. I. Kozhushkov, K. Rauch and A. de Meijere, Chem.–Eur. J., 2007,
13, 8688.
9 (a) M. Kwit and J. Gawronski, Tetrahedron: Asymmetry, 2003, 14, 1303;
(b) S. Srimurugan, B. Viswanathan, T. K. Varadarajan and B. Varghese,
Org. Biomol. Chem., 2006, 4, 3044; (c) H. Shimakoshi, H. Takemoto, I.
Aritome and Y. Hisaeda, Tetrahedron Lett., 2002, 43, 4809.
10 J. Gawron´ski, M. Brzostowska, M. Kwit, A. Plutecka and U.
Rychlewska, J. Org. Chem., 2005, 70, 10147.
11 M. Kaik and J. Gawron´ski, Org. Lett., 2006, 8, 2921.
12 P. Skowronek and J. Gawron´ski, Org. Lett., 2008, 10, 4755.
13 C. Ma, A. Lo, A. Abdolmaleki and M. J. MacLachlan, Org. Lett., 2004,
6, 3841.
14 (a) A. J. Gallant and M. J. MacLachlan, Angew. Chem., Int. Ed., 2003,
42, 5307; (b) A. J. Gallant, B. O. Patrick and M. J. MacLachlan, J. Org.
Chem., 2004, 69, 8739; (c) A. J. Gallant, J. K.-H. Hui, F. E. Zachariev,
Y. A. Wang and M. J. MacLachlan, J. Org. Chem., 2005, 70, 7936.
15 (a) S. Akine, T. Taniguchi and T. Nabeshima, Tetrahedron Lett., 2001,
42, 8861; (b) S. Akine, D. Hashimoto, T. Saiki and T. Nabeshima,
Tetrahedron Lett., 2004, 45, 4225.
◦
Macrocycle 3a. Yield 95%, does not melt up to 360 C; [a]D20
1
-1438 (c 0.25, CHCl3): H NMR (300 MHz, CDCl3): dH 13.26
(s,1H, OH), 8.23 (s, 1H, CHN), 7.15 (d, J = 7.8 Hz, 1H), 6.99 (s,
1H), 6.92 (dd, J = 1.3, J = 7.8 Hz, 1H),3.31–3.28 (m, 1H), 1.95
-1.70 (m, 3H), 1.55–1.47 (m, 1H); 13C NMR (75 MHz, CDCl3):
dC 164.0, 160.5, 131.3, 126.4, 122.2, 119.6, 118.5, 90.7, 73.1, 32.9,
24.2, FAB-MS: m/z = 1033.1 ((M + H)+, 100%), IR (KBr): 3014,
2926, 2853, 2210, 1623, 1552, 1384, 1192, 808, 755 cm-1.
16 H. Brunner and H. Schiessling, Angew. Chem., Int. Ed. Engl., 1994, 33,
125.
◦
Macrocycle 3b. Yield 90%, does not melt up to 360 C; [a]D20
17 (a) E. N. Jacobsen, and M. H. Wu, Catalytic Asymmetric Synthesis,
ed. I. Ojima, Wiley-VCH, New York, 1993, pp. 159-202; (b) E. N.
Jacobsen, and M. H. Wu, Comprehensive Asymmetric Catalysis, ed.
E. N. Jacobsen, A. Pfaltz. H. Yamamoto, Springer, New York, 1999,
pp. 649–675; (c) T. Katsuki Catalytic Asymmetric Synthesis, ed.
I. Ojima, Wiley-VCH, New York, 2000, pp. 287–325; (d) Y. N. Belokon,
S. Caveda-Cepas, B. Green, N. S. Ikonnikov, V. N. Khrustalev, V. S.
Larichev, M. A. Moscalenko, M. North, C. Orizu, V. I. Tararov, M.
Tasinazzo, G. I. Timofeeva and L. V. Yashkina, J. Am. Chem. Soc.,
1999, 121, 3968; (e) T. R. J. Clutterbuck, L. A. Achard and M. North,
Synlett, 2005, 1828.
-716 (c 0.25, CHCl3): 1H NMR (300 MHz, CDCl3): dH 13.38 (s,1H,
OH), 8.32 (s, 1H, CHN), 7.20–7.05 (m, 3H), 6.95–6.89 (m, 1H),
3.89–3.82 (m, 2H), 3.35 (br s, 2H), 1.66–1.49 (m, 10H), 1.31–1.20
(m, 4H), 0.82 (t, J = 6.0 Hz 3H); 13C NMR (75 MHz, CDCl3): dC
164.1, 160.47, 150.0, 142.3, 130.6, 130.1, 121.5, 120.1, 117.5, 117.3,
115.8, 72.6, 69.4, 33.3, 31.7, 29.2, 26.0, 24.2, 22.7, 14.2; FAB-MS:
m/z = 1958.0 ((M + H)+; IR (KBr): 3055, 2925, 2853, 1623, 1373,
1203, 936, 811 cm-1.
18 (a) J. M. Ready and E. N. Jacobsen, Angew. Chem., Int. Ed., 2002, 41,
1374; (b) A. Martinez, C. Hemmert, C. Loup, G. Barre and B. Meunier,
J. Org. Chem., 2006, 71, 1449.
19 G. H. Clever, K. Polborn and T. Carell, Angew. Chem., Int. Ed., 2005,
44, 7204.
20 We find that desilylation of 4-trimethylsilylacetyle-2-hydroxy-
benzaldehyde (ref. 12), a precursor of 5, can be best carried out with
TBAF in THF at room temperature (yield 87%), cf . H. Miyaji, W.
Sato, D. An and J. L. Sessler, Collect. Czech. Chem. Commun., 2004,
69, 1027.
21 F. Babudri, D. Colangiuli, G. M. Farinola and F. Naso, Eur. J. Org.
Chem., 2002, 2785.
◦
Macrocycle 3c. Yield 93%, does not melt up to 360 C; [a]D20
-1387 (c 0.2, CHCl3): 1H NMR (300 MHz, CDCl3): dH 13.40 (s,1H,
OH), 8.23 (s, 1H, CHN), 7.11–7.01 (m, 3H), 6.96–6.93 (m, 1H),
4.00–3.96 (m, 2H), 3.30 (br s, 1H), 1.92–1.76 (m, 2H), 1.57–1.44
(m, 10H), 1.31–1.24 (m, 4H), 0.82 (t, J = 6.8 Hz, 3H); 13C NMR
(75 MHz, CDCl3): dC 164.1, 160.4, 153.5, 131.0, 126.9, 122.0,
121,8, 119.4, 119.2, 118.2, 116.8, 113.8, 94.5, 87.7, 72.9, 69.5, 33.0,
31.8, 29.3, 26.0, 24.3, 22.7, 14.1; FAB-MS: m/z = 2103.0 ((M +
H)+, 100%); IR (KBr): 3420, 2924, 2853, 2209, 1623, 1374, 1215,
972, 807, 636 cm-1.
22 H. Katayama, M. Nagao, T. Nishimura, Y. Matsui, Y. Fukuse, M.
Wakioka and F. Ozawa, Macromolecules, 2006, 39, 2039.
6788 | Dalton Trans., 2009, 6783–6789
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