(s, 3 H) and 1.62 (m, 4 H); dC (CDCl3) 140.0, 128.1, 128.0, 126.9, 83.5, 33.3
and 23.0; m/z 315, 286, 246 and 172; HRMS calc. for M+ 315.1987, found
315.1989. For 9: mp 167–168 °C; dH (300 MHz, CDCl3) 7.50 (m, 4 H), 7.15
(m, 7 H), 6.84 (m, 2 H), 6.57 (m, 2 H), 3.20 (s, 2 H), 2.74 (s, 4 H) and 1.64
(m, 4 H); dC (CDCl3) 141.8, 139.9, 128.6, 128.2, 127.7, 126.9, 126.8, 125.0,
83.9, 50.5, 47.3 and 23.1; m/z 391, 301 and 91; anal. calc. for C29H29N: C,
88.96; H, 7.47; N, 3.58. Found: C, 88.84; H, 7.44; N, 3.54%. For 11: mp
190 °C; dH (300 MHz, CDCl3) 7.4 (dd, 4 H, J 6.6 and 1 Hz), 7.1 (m, 6 H),
6.9 (m, 3 H), 6.7 (m, 2 H), 5.9 (s, 4 H), 3.2 (s, 2 H) and 3.1 (s, 4 H); dC
(CDCl3) 141.2 (2), 134.6. 129.1, 128.7, 127.7, 127.2, 126.9, 125.6, 97.3,
54.7 and 49.7; HRMS calc. for M+ 387.1987, found 387.1990. For 12: mp
201 °C; dH (300 MHz, CDCl3) 7.3 (dd, 4 H, J 7.0 and 1 Hz), 7.15 (m, 6 H),
6.95 (m, 3 H), 6.9 (m, 2 H), 3.55 (s, 4 H), 3.36 (s, 2 H) and 3.3 (s, 4 H); dC
(CDCl3) 141.7, 141.0, 128.9, 128.1, 128.0, 127.4, 126.6, 125.6, 90.8, 77.4,
53.3 and 41.7; m/z 388, 322, 309, 246, 233, 218 and 91; HRMS calc. for M+
387.1987, found 387.1992.
‡ Crystal data for 11: The compound crystallized from acetone as colourless
–
needles in the tetragonal system P4. Unit cell dimensions are as follows:
a = b = 18.44(4), c = 6.13(1) Å, V = 2086(7) Å3, Z = 4. The crystal was
examined on a Syntex (Crystal Logic) diffractometer, Cu-Ka radiation, at
298 K. Total data collected = 1715 and 1326 with I > 3s(I). Full-matrix
least-squares refinement based on F of 275 parameters has an agreement
value, R, of 0.046 and a weighted R of 0.054. The error of fit is 1.715 and
Fig. 1 ORTEP view of the molecular structure of 11. The hydrogens have
been omitted for clarity. Thermal ellipsoids are drawn at the 50%
probability level. Selected bond distances (Å) and angles (°) for 11:
C(1)–C(8) 1.607(7), C(4)–C(5) 1.595(7), C(1)–C(2) 1.505(7), C(3)–C(4)
1.520(7), C(1)–C(11) 1.564(6), C(4)–C(11) 1.578(7), C(2)–C(3) 1.323(8),
C(6)–C(7) 1.320(8), C(9)–N(10) 1.459(6), C(12)–N(10) 1.464(6),
C(9)–C(20) 1.507(6), C(9)–N(10)–C(11) 97.2(3).
the maximum residual density is 0.69 e Å23. For 12: The compound
–
crystallized from acetone as colourless needles in the tetragonal system P4.
Unit cell dimensions are as follows: a = b = 18.399(8), c = 6.038(3) Å,
V = 2044(2) Å3, Z = 4. The crystal was examined on a Syntex (Crystal
Logic) diffractometer, Cu-Ka radiation, at 298 K. Total data collected =
1678 and 1104 with I > 3s(I). Full-matrix least-squares refinement based
on F of 271 parameters has an agreement value, R, of 0.044 and a weighted
R of 0.048. The error of fit is 1.405 and the maximum residual density is
0.32 e Å23. Atomic coordinates, bond lengths and angles, and thermal
parameters have been deposited at the Cambridge Crystallographic Data
Centre (CCDC). See Information for Authors, Issue No. 1. Any request to
the CCDC for this material should quote the full literature citation and the
reference number 182/444.
References
1 A. P. Marchand, Chem. Rev., 1989, 89, 1011; T.-C. Chou, Y.-L. Yeh and
G.-H. Lin, Tetrahedron Lett., 1996, 37, 8779; T. D. Golobish and
W. P. Dailey, Tetrahedron Lett., 1996, 37, 3239.
2 S. L. Sacks, J. R. Scheffer, C.-Z. Teh and A. Tse, J. Med. Chem., 1985,
28, 819; D. P. Becker, R. Nosal, D. L. Zabrowski and D. L. Flynn,
Tetrahedron, 1997, 53, 1.
3 G. W. Gribble and B. H. Hirth, J. Heterocycl. Chem., 1996, 33, 719;
G. W. Gribble, F. L. Switzer, J. H. Bushweller, J. G. Jewett, J. H. Brown,
J. L. Dion, C. H. Bushweller, M. P. Byrn and C. E. Strouse, J. Org.
Chem., 1996, 61, 4319; C. H. Bushweller, J. H. Brown, C. M. DiMeglio,
G. W. Gribble, J. T. Eaton, C. S. LeHoullier and E. R. Olson, J. Org.
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Tetrahedron Lett., 1970, 1075.
4 For the synthesis of pentaprismane, see P. E. Eaton, Y. S. Or and
S. J. Branca, J. Am. Chem. Soc., 1981, 103, 2134; P. E. Eaton, Y. S. Or,
S. J. Branca and B. K. R. Shankar, Tetrahedron, 1986, 42, 1621;
W. G. Dauben and A. F. Cunningham, Jr., J. Org. Chem., 1983, 48,
2842.
Fig. 2 ORTEP view of the molecular structure of 12. The hydrogens have
been omitted for clarity. Thermal ellipsoids are drawn at the 50%
probability level. Selected bond distances (Å) and angles (°) for 12:
C(2)–C(6) 1.547(7), C(9)–C(10) 1.555(7), C(6)–C(7) 1.555(7), C(8)–C(9)
1.550(7), C(6)–C(7) 1.567(8), C(5)–C(9) 1.550(7), C(7)–C(8) 1.562(9),
C(1)–C(11) 1.560(9), C(1)–C(7) 1.560(8), C(8)–C(11) 1.568(7), C(3)–N(4)
1.485(6), C(12)–N(4) 1.470(7), C(3)–C(20) 1.512(7), C(3)–N(4)–C(5)
97.0(4).
5 P. M. Weintraub, J. Chem. Soc., Chem. Commun., 1970, 760.
6 For a recent study of this reaction, see G. W. Gribble and B. H. Hirth,
J. Heterocycl. Chem., 1996, 33, 719.
7 R. R. Fraser, G. Boussard, I. D. Postescu, J. J. Whiting and
Y. Y. Wigfield, Can. J. Chem., 1973, 51, 1109.
8 R. Huisgen, H. Gotthardt, H. O. Bayer and F. C. Schaefer, Chem. Ber.,
1970, 103, 2611.
9 W. K. Anderson and A. R. Heider, Synth. Commun., 1986, 16, 357.
10 G. W. Gribble, F. L. Switzer, J. H. Bushweller, J. G. Jewett, J. H. Brown,
J. L. Dion, C. H. Bushweller, M. P. Byrn and C. E. Strouse, J. Org.
Chem., 1996, 61, 4319.
11 K. Saito, Y. Omura, E. Maekawa and P. G. Gassman, Bull. Chem. Soc.
Jpn., 1990, 63, 395.
We thank the donors of the Petroleum Research Fund
administered by the American Chemical Society for support of
this project and for a summer faculty fellowship to F. L. S., and
the National Science Foundation Research Experiences for
Undergraduates Program for a fellowship to F. J. D. We also
thank Professors David Lemal and David Glueck of this
department for their assistance with the photolysis experiments
and useful discussions, and Professor Michael Walters for the
use of his laboratory.
12 A. P. Marchand, T.-C. Chou, J. D. Ekstrand and D. van der Helm,
J. Org. Chem., 1976, 41, 1438.
Footnotes
* E-mail: grib@dartmouth.edu
† Selected physical and spectroscopic data for 8: oil; dH (300 MHz, CDCl3)
7.56 (m, 4 H), 7.38 (m, 4 H), 7.28 (m, 2 H), 2.71 (s, 4 H), 1.80 (m, 4 H), 1.69
Received in Corvallis, OR, USA, 5th February 1997; Com.
7/00857K
994
Chem. Commun., 1997