8458
R. Katoono et al. / Tetrahedron Letters 45 (2004) 8455–8459
Chemistry; Wiley: Chichester, 1993; (e) Gleiter, R.; Hopf,
&
9. Wright, V. A.; Gates, D. P. Angew. Chem., Int. Ed. 2002,
41, 2389.
10. Crystal data of (R,R)-2b: C30H26N2O2 M 446.55, ortho-
H. Modern Cyclophane Chemistry; John Wiley
Sons, 2004.
2. (a) Misumi, S.; Otsubo, T. Acc. Chem. Res. 1978, 11, 251;
(b) Yasutake, M.; Koga, T.; Sakamoto, Y.; Komatsu, S.;
Zhou, M.; Sako, K.; Tatemitsu, H.; Onaka, S.; Aso, Y.;
Inoue, S.; Shinmyozu, T. J. Am. Chem. Soc. 2002, 124,
10136; (c) Bartholomew, G. P.; Bazan, G. C. Acc. Chem.
Res. 2001, 34, 30.
3. (a) Bickelhaupt, F.; de Wolf, W. H. Trav. Chim. Pays-Bas
1988, 107, 459; (b) Bickelhaupt, F.; de Wolf, W. H. Adv.
Strain Org. Chem. 1993, 3, 185; (c) Tobe, Y. Top. Curr.
Chem. 1994, 172, 1; (d) de Meijere, A.; Ko¨nig, B. Synlett
1997, 1221; (e) Tsuji, T. Adv. Strained Interesting Org.
Mol. 1999, 7, 103.
4. Macrocyclic cyclophanes containing multiple aromatic
units and a huge cavity are the important members as
endotopic receptors in the fields of supramolecular chem-
istry and molecular devices: (a) Vo¨gtle, F. Supramolecular
Chemistry: An Introduction; VCH: Weinheim, 1991; (b)
Comprehensive Supramolecular Chemistry; Atwood, J. L.,
Davies, J. E. D., MacNicol, D. D., Vo¨gtle, F., Lehn,
J.-M., Eds.; Elsevier: Oxford, 1996; Vol. 2; (c) Balzani, V.;
Venturi, M.; Credi, A. Molecular Devices and Machines;
Wiley-VCH: Weinheim, 2003, and references cited therein.
5. Kawai, H.; Katoono, R.; Nishimura, K.; Matsuda, S.;
Fujiwara, K.; Tsuji, T.; Suzuki, T. J. Am. Chem. Soc.
2004, 126, 5034.
rhombic P212121 (No. 19), a = 6.337 (2), b = 15.805 (5),
3
˚
˚
c = 23.515 (7) A, V = 2355 (1) A , Dc (Z = 4)
= 1.259gcmꢁ3, T = 153K, l = 0.79cmꢁ1. The final R
value is 0.061 for 2422 independent reflections with
I > 3rI and 308 parameters. Esds for bond lengths and
˚
angles are 0.006–0.01A and 0.5–0.7ꢁ for non-hydrogen
atoms. Data of 4a: C28H24N2O2, M 420.51, orthorhombic
Pbca (No. 61), a = 12.157 (2), b = 7.752 (1), c = 22.952 (3)
3
A, V = 2163.0 (10) A , Dc (Z = 4) = 1.252gcmꢁ3
,
˚
˚
T = 153K, l = 0.81cmꢁ1. The final R value is 0.039
for 1105 independent reflections with I > 3rI and
145 parameters. Esds for bond lengths and angles
are 0.003–0.004A and 0.2–0.3ꢁ for non-hydrogen
atoms.
˚
11. (a) Karlsen, H.; Kolsaker, P.; Rømming, C.; Uggerud, E.
J. Chem. Soc., Perkin 2 2002, 404; (b) Jones, P. G.;
Ossowski, J.; Kus, P. Z. Naturforsh 2002, B57, 914.
12. According to the PM3 calculations, the values of heat of
formation are ꢁ56.8 and ꢁ57.3kcalmolꢁ1, respectively,
for the syn- and anti-isomers of N,N,N0,N0-tetramethyl-
benzene-1,4-dicarboxamide.
13. The rotational barrier for CAr–CCO seems much lower
than that for CCO–N, the latter of which was determined
to be 15.3kcalmolꢁ1 on the basis of VT-NMR (Tc = 323K
and dD = 135Hz for the CH2 unit of propargyl groups).
The comparable values (14–17kcalmolꢁ1) for the struc-
turally related systems were reported in Ref. 14.
14. Buhleier, E.; Wehner, W.; Vo¨gtle, F. Chem. Ber. 1979, 112,
559.
6. 1H NMR data (d) of new compounds measured in CDCl3
at room temperature are as follows: 1a: 7.53 (4H, s), 7.38–
7.28 (10H, m), 4.72 (4H, s), 2.90 (4H, t, J = 8.4Hz), 0.79
(4H, m), 0.69 (4H, m); (R,R)-1b: 7.49 (4H, s), 7.36–7.27
(10H, m), 6.22 (2H, q, J = 6.9Hz), 2.83–2.61 (4H, m),
1.543 (6H, d, J = 6.9Hz), 0.73–0.48 (6H, br), 0.42–0.15
(2H, m); 1c: 7.36–7.28 (10H, m), 4.72 (4H, s), 2.58 (4H, br
t), 2.20 (12H, s), 0.80 (8H, br m); 2a: 7.66 (4H, s), 7.37–
7.30 (10H, m), 4.82 (4H, s), 4.04 (4H, s); (R,R)-2b: 7.67
(4H, s), 7.41–7.28 (10H, m), 6.33 (2H, q, J = 6.9Hz), 3.88
(2H, d, J = 18.9Hz), 3.67 (2H, d, J = 18.9Hz), 1.59 (6H, d,
J = 6.9Hz); 2c: 7.38–7.37 (10H, m), 4.83 (4H, s), 3.88 (4H,
s), 2.23 (12H, s); 3a: 7.85 (4H, s), 7.38–7.31 (10H, m), 6.39
(2H, br), 4.66 (4H, d, J = 5.4Hz); 3c: 7.36–7.29 (10H, m),
5.83 (2H, br), 4.66 (4H, d, J = 5.7Hz), 2.17 (12H, s); 4a:
7.60 (4H, br s), 7.36–7.33 (10H, m), 4.87 (4H, br s), 3.84
(4H, br), 2.33 (2H, br); (R,R)-4b (60ꢁC): 7.57 (4H, s),
7.37–7.25 (10H, m), 5.58 (2H, br), 4.10 (2H, br d,
J = 17.1Hz), 3.60 (2H, dd, J = 17.1, 2.4Hz), 2.15 (2H, t,
J = 2.4Hz), 1.74 (6H, d, J = 6.9Hz); syn-4c: 7.46–7.27
(10H, m), 4.97 (4H, s), 3.69 (4H, d, J = 2.4Hz), 2.27 (2H,
t, J = 2.4Hz), 2.13 (12H, s); anti-4c: 7.47–7.27 (10H, m),
4.97 (4H, s), 3.70 (4H, d, J = 2.4Hz), 2.27 (2H, t,
J = 2.4Hz), 2.14 (12H, s); (1c and 4 adopt the conforma-
tions more than one, and the data are shown for their
major conformers). IR data (mC@O/cmꢁ1) measured in KBr
disks are as follows: 1a: 1638; (R,R)-1b: 1636; 1c: 1639;
(R,R)-2b: 1630; 3a: 1631; 3c: 1638; 4a: 1634; (R,R)-4b:
1638; syn-4c: 1627; anti-4c: 1632. Only 2a (kem 409,
431nm) and 2c (410, 436nm) emit weak fluorescence in
15. Berscheid, R.; Vo¨gtle, F. Synthesis 1992, 58.
16. To a 100mL solution of Cu(OAc)2 in pyridine–MeCN
(1:100, 7.14 · 10ꢁ3 moldmꢁ3) was added a solution of 4a
(100mL, 1.20 · 10ꢁ3 moldmꢁ3) over 6.5h at 75ꢁC. When
the addition of 4a was conducted much faster, a consid-
erable amount of oligomers were obtained.
17. Matsuoka, T.; Negi, T.; Otsubo, T.; Sakata, Y.; Misumi,
S. Bull. Chem. Soc. Jpn. 1972, 45, 1825.
18. Similar method was also revisited by Kanomata et al.,
independently who succeeded in obtaining [10]–[14]para-
cyclophanes via the diynes: (a) Kanomata, N.; Takizawa,
H. The 84th National Meeting of the Chemical Society of
Japan, Abstract Paper, 2004, 1F2-34; (b) Kanomata, N.;
Maruyama, S. 2004, 1F2-35.
19. The strained diyne in 2 seems responsible for their
instability. One of the possible decomposition paths may
be solid-state polymerization at the diyne unit: Zuihof, H.;
Barentsen, H. M.; van Dijk, M.; Sudholter, E. J. R.;
Hoofman, R. J. O. M.; Laurens, D. A.; de Haas, M. P.;
Warman, J. M. In Supramolecular Photosensitive and
Electroactive Materials: Polydiacetylenes; Nalwa, H. S.,
Ed.; Academic Press: San Diego, 2001; pp 339–347, The
crystal structure of stable (R,R)-2b has no short inter-
molecular contacts between diyne units.
20. The most bent triple bond in cyclophanes exhibits the
deviation of 16.5ꢁ from the linearity: Collins, S. K.; Yap,
G. P. A.; Fallis, A. G. Angew. Chem., Int. Ed. 2000, 39,
385.
22
CHCl3 (excitation at 350nm). ½aꢂD data measured in
CHCl3 (c 0.10) are as follows: (R,R)1b: ꢁ10.8; (R,R)-2b:
+267.9; (R,R)-4b: +180.9.
21. Deviations are much larger than the parent [10]paracyclo-
phane-4,6-diyne 6 (6.4–10.8ꢁ : Ref. 17) due to the shorter
bond distances for N–Csp2 [1.365 (7) and 1.349 (7) A] and
7. Khan, M. A.; Al-Saleh, B. J. Chem. Res. Miniprint 1989,
320.
˚
˚
8. Amine 5b was easily obtained in 86% yield by the reaction
(R)-1-phenylethylamine and propargyl bromide in MeCN
containing K2CO3: 1H NMR (d in CDCl3) 7.36–7.21 (5H,
m), 3.99 (1H, q, J = 6.6Hz), 3.34 (1H, dd, J = 17.1, 2.4Hz),
3.14 (1H, dd, J = 17.1, 2.4Hz), 2.44 (1H, t, J = 2.4Hz),
N–Csp3 [1.469 (7) and 1.489 (7) A] than Csp3–Csp3
˚
(standard: 1.54A). The transannular Cꢀ ꢀ ꢀC contacts in 6
˚
are in the range of 3.07–0.08A, showing the much closer
arrangement in (R,R)-2b.
22. Comparisons of the NMR chemical shifts in 2a (d 7.66), 1a
(7.53), and 4a (7.60) also support this explanation.
22
1.33 (3H, d, J = 6.6Hz); ½aꢂD +169.6 (c 0.10, CHCl3).