Angewandte
Chemie
[12] T. Danilova, V. Rozenberg, Z. A. Starikova, S. Bräse, Tetrahe-
[13] H. Hopf, H. Zitt, Eur. J. Org. Chem. 2002, 2298.
the corresponding a-amino nitriles also in reactions of
aliphatic aldimines.
[14] a) H. Kunz, W. Pfrengle, Angew. Chem. 1989, 101, 1041; Angew.
[15] The 1H NMR signals of the aldimine groups are found at d =
7.82–7.45 ppm for the aliphatic aldimines 7c–e, and at d = 8.32–
8.22 ppm for the aromatic aldimines 7a,b,f.
[16] Like 3, a compound analogous to 5 but having a bromo
substituent instead of the ester group in the second cyclophane
phenyl ring also leads to lower enantioselectivity.
Received: July 16, 2007
Revised: August 23, 2007
Published online: October 29, 2007
Keywords: glycosyl imines · organocatalysis · paracyclophanes ·
.
planar chirality · Strecker reaction
[17] M.p. 125–1278C, [a] = ꢀ139.2 (c = 1, CH3CN); FD-MS (posi-
tive): m/z 794 [M+H+]. Elemental analysis (C45H61O11N,
[2] Reviews on diastereoselective Strecker reactions: a) R. M.
see: J.-C. Rossi, M. Marull, L. Boiteau, J. Taillades, Eur. J. Org.
[3] Reviews on enantioselective Strecker reactions a) L. Yet,
875; b) H. Gröger, Chem. Rev. 2003, 103, 2795; c) P. R.
c) N. S. Josephsohn, K. W. Kuntz, M. L. Snapper, A. H. Hov-
12, 1147; B. Therrieu, M. Kawano, K. Yamaguchi, H. Danjo, Y.
Sei, A. Sato, S. Furusho, M. Shibasaki, J. Am. Chem. Soc. 2006,
128, 6768, and references therein.
c) A. G. Wenzel, M. P. Lalonde, E. N. Jacobsen, Synlett 2003,
1919; d) Z. Jiao, X. Feng, B. Liu, F. Chen, G. Zhang, Y. Jiang,
Lex, Synlett 2006, 41; f) T. Ooi, Y. Uematsu, J. Fujimoto, K.
[7] B. Liu, X. Feng, F. Chen, G. Zhan, X. Cui, Y. Jiang, Synlett 2001,
Schanzenbach, M. Decker, Liebigs Ann. Chem. 1991, 649; c) H.
[9] T. I. Danilova, V. I. Rozenberg, E. V. Vorontsov, Z. A. Starikova,
[10] a) S. El-Tamany, F. W. Raulfs, H. Hopf, Angew. Chem. 1983, 95,
Dissertation, Univ. Braunschweig, 1983.
[11] Y. Belokon, M. Moskalenko, N. Ikonikov, L. Yashikina, D.
791.97): found (calcd): C 66.53(66.58), H 7.68 (7.69), N 1.67
1
=
(1.76). H NMR (400 MHz, CDCl3, COSY): d = 8.38 (s, 1H, -N
4
CH-), 7.14 (d, J5-H,7-H,or 16-H,12-H = 1.86 Hz, 1H, Phan-5 or Phan-
16), 6.71 (dd, 4J7-H,5-H = 1.83Hz, J7-H,8-H=5.88 Hz, 1H, Phan-7),
3
6.60 (d, 3J12-H,13-H = 7.71 Hz, 1H, Phan-12), 6.54 (dd,
3J8-H,7-H = 6.24 Hz, 4J12-H,16-H = 1.83Hz, 2H, Phan-8, Phan-16),
6.47 (d, J13-H,12-H=7.71 Hz, 1H, Phan-13), 5.51 (d, 3J = 1.47 Hz,
3
4
1H, Gal-4), 5.21 (m, 2H, Gal-2, Gal-3), 4.75 (dd, J = 1.83Hz,
3J1/2 = 7.35 Hz, 1H, Gal-1), 4.26–4.13 (m, 3H, Gal-5, Gal-6a,b),
3.76 (s, 3H, OCH3), 3.72–3.69 (m, 1H, Phan-2s), 3.11–2.91 (m,
7H, Phan-2a, Phan-1a,s, Phan-9a,s, Phan-10a,s), 1.25, 1.18, 1.07,
0.89 ppm (4 s, 36H, PivCH3) 13C NMR (100.6 MHz CDCl3,
=
HMQC): d = 177.9, 177.7, 177.3, 175.9 (PivC O), 166.7 (Phan-
17), 160.5 (-C N-), 142.4 (qCAr), 141.7(qCAr), 139.9 (qCAr), 136.3
=
(qCAr), 138.1, 136.0 (Phan-7, Phan-12), 134.9, 134.7, 134.4, 133.7
(Phan-8, Phan-13, Phan-5, Phan-16), 130.4 (qCAr), 129.5 (qCAr),
85.4 (Gal-1), 72.6, 71.2, 69.8, 67.1 (Gal-2, Gal-3, Gal-4, Gal-5),
61.2 (Gal-6), 51.5 (Phan-18), 39.0, 38.7, 38.6, 38.5 (PivCMe3),
35.0, 34.9 (Phan-2, Phan-10), 34.4, 30.8 (Phan-9, Phan-1), 27.14,
27.11, 27.02 ppm (PivCH3). Crystal structure analysis: Mr =
791.95 gmolꢀ1; absorption: m = 0.64 mmꢀ1; Crystal size: 0.128
0.192 0.8 mm3, colorless needles; space group: P21 (mono-
clinic); lattice constants: a = 15.472(2), b = 10.061(1), c =
30.791(4) , b = 95.649(6)8, V= 4770(1) 3, Z = 4; temperature:
ꢀ808C; density: d = 1.103gcm ꢀ3; irradiation: CuKa graphite
monochromator, l = 1.54178 ; 2qmax = 1408; number of reflec-
tions: measured 19513, independent 9894 (Rint = 0.0902); dis-
crepancy factor: wR2 = 0.1262 (R1 = 0.0480 for observed reflec-
tions, 0.0606 for all reflections); diff. Fourier synthesis: 0.21,
ꢀ0.23e ꢀ3; CCDC 619295 contains the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
[18] 8a: HPLC (Chiralpak AS, n-hexane/2-propanol 95:5): tr (major
comp.) 7.8 min, (minor) 5.5 min; [a] = 53.1 (c = 1, CH2Cl2)
[Ref. [4b]: [a] = 57.7 (c = 1, CH2Cl2)]; 8b: HPLC (Chiralpak
AS, n-hexane/2-propanol 95:5): tr (major) 7.7 min, (minor)
5.65 min; [a] = 45.1 (c = 1, CH2Cl2) [Ref. [4b]: [a] = 42.4 (c = 1,
CH2Cl2)]; 8c: HPLC (Chiralpak AS, n-hexane/2-propanol 98:2):
tr (major) 9.5 min, (minor) 12.5 min; [a] = 5.5 (c = 1, CH2Cl2);
8d: HPLC (Chiralpak AS, n-hexane/2-propanol 70:30): tr
(major) 3.6 min, (minor) 5.3 min; [a] = ꢀ10.5 (c = 1, CH2Cl2)
[Ref. [4b]: [a] = ꢀ10.4 (c = 1, CH2Cl2)]; 8e: HPLC (Chiralpak
AS, n-hexane/2-propanol 70:30): tr (major) 6.5 min, (minor)
7.7 min (from racemic mixture); [a] = ꢀ19.7 (c = 1, CHCl3); 8 f:
HPLC (Chiralpak AS, n-hexane/2-propanol 60:40): tr (major)
3.2 min, (minor) 5.4 min; [a] = ꢀ2.12 (c = 0.67, CHCl3).
Angew. Chem. Int. Ed. 2007, 46, 9339 –9341
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
9341
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