JOURNAL OF CHEMICAL RESEARCH 2007 625
+
J = 2.4 Hz, ArH); m/z: 434 (M ) (Found C, 82.98; H, 9.71. C H O
2
0.055 mmol) at room temperature. After the reaction mixture was
3
0
42
(
434.67) requires C, 82.90; H, 9.74%).
syn-5,17-Di-tert-butyl-8,20-dimethoxy[2.6]metacyclophan-1-ene
stirred at room temperature for 1 h, it was poured into a large amount
3
3
of ice/water (50 cm ) and extracted with CH Cl (50 cm ¥ 2).
2
2
-1
(
2
syn-3b): Colourless prisms (MeOH), m.p. 62–64°C; n (KBr)/cm :
The combined extracts were washed with water, dried with Na SO
max
2 4
962, 1479, 1327, 1215, 1019, 883, 810; d (CDCl ): 0.51–0.58 (2H,
and concentrated to give 21 mg (71%) of a mixture of anti-13-
endo-bromo-14-exo-bromo- (rac-anti-6b) and anti-13-exo-bromo-
14-exo-bromo-9,17-di-tert-butyl-12,20-dimethoxy[6.2]metacyclo-
H
3
m, CH ), 0.77–0.93 (2H, m, CH ), 1.01–1.35 (4H, m, CH ), 1.11
2
2
2
(
18H, s, tBu), 2.25–2.28 (2H, m, CH ), 2.75–2.89 (2H, m, CH ), 3.67
2
2
(6H, s, OMe), 6.51 (2H, d, J = 2.4 Hz, ArH), 6.81 (2H, d, J = 2.4 Hz,
1
phane (meso-anti-6b) in the ratio of 80:20 (determined by H NMR
+
ArH) 6.88 (2H, s, CH); m/z: 434 (M ) (Found C, 82.89; H, 9.79.
C H O (434.67) requires C, 82.90; H, 9.74%).
anti-13-endo-Acetoxy-14-endo-acetoxy-9,17-di-tert-butyl-12,20-
dimethoxy[6.2]metacyclophane (meso-anti-5b): Colourless prisms
spectrum) as colourless solid; d (CDCl ): rac-anti-6b; 0.70–1.02
H
3
30
42
2
(4H, m, CH ), 1.29 (9H, s, tBu), 1.20–1.45 (4H, m, CH ), 1.36 (9H, s,
2
2
tBu), 2.03–2.20 (2H, m, CH ), 2.75–2.90 (2H, m, CH ), 3.20 (3H, s,
2
2
OMe), 3.36 (3H, s, OMe), 5.51 (1H, d, J = 3.9 Hz, CH), 5.78 (1H, d,
J = 3.9 Hz, CH), 6.92 (1H, d, J = 2.9 Hz, ArH), 7.10 (1H, d,
J = 2.9 Hz,ArH), 7.13 (1H, d, J = 2.2 Hz,ArH), 8.04 (1H, d, J = 2.2 Hz,
-
1
(
0
1
hexane), m.p. 214–216°C; n (KBr)/cm : 1744 (C=O); d (CDCl ):
max H 3
.51–0.93 (2H, m, CH ), 1.32 (18H, s, tBu), 1.25–1.36 (2H, m, CH ),
2 2
.42–1.58 (4H, m, CH ), 2.14 (6H, s, COMe), 2.20–2.30 (2H, m,
2
ArH); meso-anti-6b; 0.70–1.02 (4H, m, CH ), 1.07–1.43 (4H, m,
2
CH ), 2.41–2.53 (2H, m, CH ), 3.46 (6H, s, OMe), 6.25 (2H, s, CH),
2
2
CH ), 1.27 (18H, s, tBu), 2.16–2.38 (2H, m, CH ), 2.58–2.72 (2H,
2
2
7
5
7
.04 (2H, d, J = 2.4 Hz, ArH), 7.36 (2H, d, J = 2.4 Hz, ArH); m/z:
m, CH ), 3.65 (6H, s, OMe), 5.98 (2H, s, CH), 6.95 (2H, d, J = 2.4
+
2
52 (M ) (Found C, 73.96; H, 9.05. C H O (552.76) requires C,
3
4
48
6
+
Hz, ArH), 7.43 (2H, d, J = 2.4 Hz, ArH); m/z: 592, 594, 596 (M
)
3.88; H, 8.75%).
(
Found C, 60.45; H, 7.26. C H Br O (594.47) requires C, 60.61;
30 42 2 2
H, 7.12%).
Compounds syn-3a and meso-anti-4a were similarly prepared in
7 and 32% yields, respectively.
syn-5,16-Di-tert-butyl-8,19-dimethoxy[2.5]metacyclophan-1-ene
2
Received 10 October 2007; accepted 7 November 2007
Paper 07/4878
(
syn-3a): Colourless prisms (MeOH), m.p. 125–127°C; d (CDCl ):
doi: 10.3184/030823407X262445
H
3
–
0.90–0.10 (1H, m, CH ), 0.79–0.96 (1H, m, CH ), 1.12 (18H, s,
2 2
tBu), 1.10–1.22 (2H, m, CH ), 1.53–1.69 (2H, m, CH ), 2.07–2.18
2
2
References
(
2H, m, CH ), 2.91–3.02 (2H, m, CH ), 3.70 (6H, s, OMe), 6.58 (2H,
2
2
1
Medium-sized cyclophanes. part 76: J. Hu, R. Ueno, M. Miyazaki and
T. Yamato, J. Chem. Res., 2007, 408.
d, J = 2.7 Hz, ArH), 6.68 (2H, d, J = 2.7 Hz, ArH), 6.96 (2H, s, CH);
m/z: 420 (M ) (Found C, 82.55; H, 9.61. C H O (420.64) requires
+
2
9
40
2
2
3
M. Pelligrin, Recl. Trav. Chim. Pays-Bas Belg., 1899, 18, 458.
R.H. Mitchell, T.K. ꢀinod and G.W. Bushnell, J. Am. Chem. Soc., 1985,
C, 82.81; H, 9.59%).
anti-12-endo-Hydroxy-13-endo-hydroxy-8,16-di-tert-butyl-11,19-
1
07, 3340.
dimethoxy[5.2]metacyclophane (meso-anti-4a): Colourless prisms
4
5
Y. Fujise, Y. Nakasato and S. Itô, Tetrahedron Lett., 1986, 27, 2907.
(a) R.H. Mitchell and V. Boekelheide, J. Am. Chem. Soc., 1974, 96, 1547;
(b)Y.-H. Lai and H.-L. Eu, J. Chem. Soc., Perkin Trans. 1, 1993, 233.
H.A. Staab, W.R.K. Riebel and C. Krieger, Chem. Ber., 1985, 118, 1230.
(a) R.E. Singler and D.J. Cram, J. Am. Chem. Soc., 1972, 94, 3512;
(b) D.J. Cram, R.B. Hornby, E.A. Truesdale, H.J. Reich, M.H. Delton and
J.M. Cram, Tetrahedron, 1974, 30, 1757.
-
1
[
(
1
hexane/benzene (5:1)], m.p. 224–226°C; n (KBr)/cm : 3386
max
OH); d (CDCl ): 1.32 (18H, s, tBu), 1.15–1.35 (6H, m, CH ),
.98–2.11 (2H, m, CH ), 2.48–2.59 (2H, m, CH ), 2.81 (2H, s, OH,
H
3
2
2
2
6
7
replaced by D O), 3.32 (6H, s, OMe), 4.85 (2H, s, CH), 6.93 (2H, d,
2
+
J = 2.4 Hz, ArH), 7.47 (2H, d, J = 2.4 Hz, ArH); m/z: 454 (M ) (Found
C, 76.44; H, 9.33. C H O (454.66) requires C, 76.61; H, 9.31%).
29
42
4
8
9
T. Yamato, A. Miyazawa, K. Kobayashi, and M. Tashiro, J. Chem. Res.
(S), 1991, 182.
Reaction of syn-[2.n]metacyclophan-1-enes (3) with BTMA Br3–
(a) T. Yamato, J. Matsumoto, S. Ide, K. Suehiro, and M. Tashiro, Chem.
Ber., 1993, 126, 447; (b) T. Yamato, M. Sato, K. Noda, J. Matsumoto and
M. Tashiro, J. Chem. Res. (S) 1993, 394. (M) 2601.
typical procedure
To a solution of syn-3a (42 mg, 0.10 mmol) in CH Cl2 (4 cm3)
2
was added BTMA Br3 (43 mg, 0.11 mmol) at room temperature.
After the reaction mixture was stirred at room temperature for 1
10
(a) T. Yamato, K. Fujita, K. Futatsuki and H. Tsuzuki, Can. J. Chem.,
2
000, 78, 1089; (b) T. Yamato, K. Fujita and H. Tsuzuki, J. Chem. Soc.,
3
h, it was poured into a large amount of ice/water (50 cm ) and
Perkin Trans. 1, 2001, 2089; (c) T. Yamato, S. Miyamoto, T. Hironaka
and Y. Miura, Org. Lett., 2005, 7, 3.
11 (a) J.E. McMurry, M.P. Fleming, K.L. Kees and L.R. Krepski, J. Org.
Chem., 1978, 43, 3255; (b) J.E. McMurry, Acc. Chem. Res., 1983, 16,
405; (c) J.E. McMurry, G.J. Haley, J.R. Matz, J.C. Clardy and G.V. Duyne,
J. Am. Chem. Soc., 1984, 106, 5018; (d) J.E. McMurry, Chem. Rev., 1989,
89, 1513.
3
extracted with CH Cl (50 cm ¥ 2). The combined extracts were
2
2
washed with water, dried with Na SO and concentrated. The
2
4
residue recrystallised from hexane gave 56 mg (96%) of syn-12-
endo-bromo-13-endo-bromo-8,16-di-tert-butyl-11,19-dimethoxy[5.2]
metacyclophane (meso-syn-6a): Colourless prisms (hexane),
-
1
m.p. 195–198°C; n (KBr)/cm : 2962, 1480, 1461, 1295, 1205,
max
1
2
(a) T. Yamato, K. Fujita, K. Okuyama and H. Tsuzuki, New. J. Chem.,
1
005, 885, 581; d (CDCl ): –0.18–0.02 (2H, m, CH ), 0.58–0.79
H 3 2
2H, m, CH ), 1.16 (18H, s, tBu), 1.52–1.78 (2H, m, CH ), 2.05–2.27
2 2
2
000, 221; (b) T. Yamato, K. Fujita, T. Abe and H. Tsuzuki, New J. Chem.,
001, 25, 728.
(
2
(
2H, m, CH ), 2.72–2.93 (2H, m, CH ), 3.66 (6H, s, OMe), 6.55 (2H,
2
2
1
3
T. Yamato, J. Matsumoto, M. Sato, K. Noda and M. Tashiro, J. Chem.
Soc. Perkin Trans. 1, 1995, 1299.
s), 6.76 (2H, d, J = 2.4 Hz, ArH), 7.56 (2H, d, J = 2.4 Hz, ArH); m/z:
5
+
78, 580, 582 (M ) (Found C, 59.81; H, 6.76. C H Br O (580.45)
29 40 2 2
14 H. -F. Grützmacher and E. Neumann, Chem. Ber., 1993, 126, 1495.
15 (a) Cyclophanes (P.M. Keehn and S.M. Rosenfield (eds)), Academic
Press: New York, 1983, vols 1&2; (b) F. Vögtle, Cyclophane-Chemistry,
Wiley: Chichester, 1993.
16 (a) M. Tashiro and T.Yamato, J. Org. Chem., 1981, 46, 4556; (b) M. Tashiro
and T. Yamato, J. Org. Chem., 1983, 48, 1461.
requires C, 60.01; H, 6.95%).
Compound meso-syn-6b was similarly prepared in 93% yield.
syn-13-endo-Bromo-14-endo-bromo-9,17-di-tert-butyl-12,20-
dimethoxy[6.2]metacyclophane (meso-syn-6b): Colourless prisms
-
1
17 (a) M. Tashiro, T. Yamato and K. Kobayashi, J. Org. Chem., 1984, 49,
(
1
(
hexane), m.p. 181–182°C; n (KBr)/cm : 2962, 1480, 1461, 1295,
max
3
380; (b) T. Yamato, J. Matsumoto, T. Ando, K. Tokuhisa and M. Tashiro,
205, 1005, 885, 581; d (CDCl ): 0.44–0.58 (2H, m, CH ), 0.84–0.97
H 3 2
2H, m, CH ), 1.09–1.48 (4H, m, CH ), 1.16 (18H, s, tBu), 2.25–2.39
2 2
J. Chem. Res. (S), 1991, 276.
1
8
9
S. Kajigaeshi, T. Kakinami, H. Tokiyama, T. Hirakawa and T. Okamoto,
Chem. Lett., 1987, 627.
T.G. Traylor, Acc. Chem. Res., 1969, 2, 152.
(
2H, m, CH ), 2.70–2.84 (2H, m, CH ), 3.65 (6H, s, OMe), 6.33 (2H,
2
2
s, CH), 6.89 (2H, d, J = 2.4 Hz, ArH), 7.55 (2H, d, J = 2.4 Hz, ArH);
1
m/z: 592, 594, 596 (M + ) (Found C, 60.91; H, 7.12. C H Br O
3
0
42
2
2
20 (a) M.J.S. Dewar and R.C. Fahey, J. Am. Chem. Soc., 1963, 85, 2245;
(b) M.J.S. Dewar and R.C. Fahey, J. Am. Chem. Soc., 1963, 85, 2248;
(c) J. Meinwald, Y.C. Meinwald and T.N. Baker, J. Am. Chem. Soc., 1963,
85, 2613.
(
594.47) requires C, 60.61; H, 7.12%).
Bromination of anti-3b with BTMA Br : To a solution of anti-3b
3
3
(22 mg, 0.05 mmol) in CH Cl (2 cm ) was added BTMABr (21.4 mg,
2
2
3
PAPER: 07/4878