6729; (h) B. Clapham, C. Spanka and K. D. Janda, Org. Lett., 2001,
Chiralpak AS column using hexane–i-PrOH (98:2) as eluant.
Rt/min: 5.0 (enantiomer-1) and 5.5 (enantiomer-2).
3, 2173; (i) K. Yamazaki and Y. Kondo, Chem. Commun., 2002, 210;
(j) F. A. Davis, B. Yang and J. Deng, J. Org. Chem., 2003, 68, 5147;
(k) Y. Wang, Y. Zhu, Z. Chen, A. Mi, W. Hu and M. P. Doyle, Org.
Lett.,2003,5,3923;(l) J. R. Davis,P. D. KaneandC. J. Moody, Tetra-
hedron, 2004, 60, 3967; (m) A. C. B. Burtoloso and C. R. D. Correia,
Tetrahedron Lett., 2004, 45, 3355.
3 P. Yates, J. Am. Chem. Soc., 1952, 74, 5376.
4 T. Saegusa, Y. Ito, S. Kobayashi, K. Hirota and T. Shimizu, Tetra-
hedron Lett., 1966, 7, 6131.
5 J.-F. Nicoud and H. B. Kagan, Tetrahedron Lett., 1971, 12, 2065.
6 R. Paulissen, E. Hayez, A. J. Hubert and P. Teyssie, Tetrahedron
Lett., 1974, 15, 607.
7 Selected papers: (a) E. Aller, R. T. Buck, M. J. Drysdale, L. Ferris,
D. Haigh, C. J. Moody, N. D. Pearson and J. B. Sanghera, J. Chem.
Soc., Perkin Trans. 1, 1996, 2879; (b) L. Ferris, D. Haigh and
C. J. Moody, J. Chem. Soc., Perkin Trans. 1, 1996, 2885; (c) K. E.
Bashford, A. L. Cooper, P. D. Kane, C. J. Moody, S. Muthusamy and
E. Swann, J. Chem.. Soc., Perkin Trans. 1, 2002, 1672.
8 R. T. Buck, C. J. Moody and A. G. Pepper, Arkivoc, 2002, 16.
9 C. F. Garcia, M. A. McKervey and T. Ye, Chem. Commun., 1996,
1465.
10 C.-D. Lu, Z.-Y. Chen, H. Liu, W.-H. Hu, A.-Q. Mi and M. P. Doyle,
J. Org. Chem., 2004, 69, 4856.
N-(4-Fluorophenyl)alanine ethyl ester 4e
1H NMR d 6.87 (t, 2H, J = 8.8 Hz, arom.), 6.54 (m, 2H, arom.),
4.18 (q, 2H, J = 6.8, OCH2), 4.05 (m, 2H, NH and CH), 1.45
(d, 3H, J = 6.4 Hz, CH3), 1.23 (t, 3H, J = 7.2 Hz, CH3); 13C
NMR d 174.5, 115.8, 115.6, 114.6, 114.4, 61.1, 52.7, 18.8,
12.7; HRMS (TOF ES+) calcd for C11H14FNO2 [M + Na]+
234.0906, found 234.0818. The ee was determined by GC on a
Chrompak CP-Chirasil Dex CB-column. Temperature program:
isotherm at 140 °C for 12 min. Rt/min: 10.5 (enantiomer-1); 10.8
(enantiomer-2).
N-(4-Trifluoromethylphenyl)alanine ethyl ester 4f
1H NMR d 7.40 (d, 2H, J = 8.4 Hz, arom.), 6.60 (d, 2H,
J = 8.4 Hz, arom.), 4.54 (br d, 1H, J = 8.0 Hz, NH), 4.20 (q, 2H,
J = 6.8, CH2O), 4.16 (dd, 1H, J = 8.0 and 14.8 Hz, CH), 1.49
(d, 3H, J = 6.8 Hz, CH3), 1.24 (t, 3H, J = 7.12 Hz); 13C NMR
d 173.9, 149.0, 126.6, 119.4, 115.2 112.5, 61.4, 51.4, 18.6, 14.1;
HRMS (TOF ES+) calcd for C12H14F3NO2 [M + Na]+ 284.0874,
found 284.0906. The ee was determined by GC on a Chrompak
CP-Chirasil Dex CB-column. Temperature program: from 70 °C
to 200 °C at a rate of 10 °C min−1. Rt/min: 11.4 (enantiomer-1);
11.5 (enantiomer-2).
11 M. E. Morilla, M. M. Diaz-Requejo, T. R. Belderrain, M. C.
Nicasio, S. Trofimenko and J. P. Pérez, Chem. Commun., 2002, 2998.
12 In the absence of a metal compound, no reaction between 1a and 2a
(1H NMR) was obtained by stirring the two compounds as a solution
in CH2Cl2 for 20 h in the dark.
13 S. Bachmann, K. R. Knudsen and K. A. Jørgensen, Org. Biomol.
Chem., 2004, 2, 2044.
14 J. B. Hendrickson and W. A. Wolf, J. Org. Chem., 1968, 33, 3610.
15 For an overview see: Comprehensive Asymmetric Catalysis, ed. E. N.
Jacobsen, A. Pfaltz and H. Yamamoto, Springer, Heidelberg, 2000,
chapter 16.
16 Besides the desired product, a unidentified byproduct was obtained
as well.
17 (a) S. B. Park, K. Murata, H. Matsumoto and H. Nishiyama, Tetra-
hedron: Asymmetry, 1995, 6, 2487; (b) H. Nishiyama, Enantiomer,
1999, 4, 569; (c) H. Nishiyama, Y. Ito, H. Matsumoto, S. B. Park
and K. Itoh, J. Am. Chem. Soc., 1994, 116, 2223; (d) J. R. Wolf,
C. G. Hamaker, J.-P. Djukic, T. Kodadek and L. K. Woo, J. Am.
Chem. Soc., 1995, 117, 9194; (e) M. M. Díaz-Requejo, P. J. Perez,
M. Brookhart and J. L. Templeton, Organometallics, 1997, 16, 4399;
(f) M. M. C. Lo and G. C. Fu, J. Am. Chem. Soc., 1998, 120, 10270;
(g) H. L. Wong, Y. Tian and K. S. Chan, Tetrahedron Lett., 2000, 41,
7723; (h) S. Bachmann and A. Mezzetti, Helv. Chim. Acta, 2001, 84,
3074.
N-(2-Methoxyphenyl)alanine ethyl ester 4g
1H NMR d 6.76 (t, 1H, J = 7.5 Hz, arom.), 6.71 (d, 2H,
J = 7.8 Hz, arom.), 6.63 (t, 1H, J = 7.7 Hz, arom.), 6.45 (d, 1H,
J = 7.8 Hz, arom.), 4.70 (br s, 1H, NH), 4.12 (q, 2H, J = 7.1
Hz, CH2O), 4.24–4.06 (m, 1H, CH), 3.85 (s, 3H, OCH3), 1.43
(d, 3H, J = 6.9 Hz, CH3), 1.18 (t, 3H, J = 7.1 Hz, CH3); 13C
NMR d 174.6, 147.0, 136.5, 121.1, 117.4, 110.3, 109.6, 61.0,
55.4, 51.7, 18.9, 14.2; HRMS (TOF ES+) calcd. for C12H17NO2
[M + Na]+ 246.1106, found 246.1112. The ee was determined on
a Chiralpak AD column using hexane–i-PrOH (98:2) as eluant.
Rt/min: 6.4 (enantiomer-1) and 6.7 (enantiomer-2).
N-Methyl-N-phenylalanine ethyl ester 4h23
HRMS (TOF ES+) calcd for C12H17NO2 [M + Na]+ 230.1157,
found 230.1159. The ee was determined by GC on a Astec G-TA
column. Temperature program: isotherm at 120 °C for 25 min.
Rt/min: 23.6 (enantiomer-1); 24.3 (enantiomer-2).
18 Due to bad separation on several HPLC colomns no value for the
enantiomeric excess can be given.
19 F. D’Angeli, P. Marchetti, G. Cavicchioni, G. Catelani and
F. M. K. Nejad, Tetrahedron: Asymmetry, 1990, 1, 155.
20 (a) Y. Cui and C. He, J. Am. Chem. Soc., 2003, 125, 16202;
(b) J. Cirakovic, T. G. Driver and K. A. Woerpel, J. Am. Chem.
Soc., 2002, 124, 9370; (c) N. Moniyama and H. Yamamoto, J. Am.
Chem. Soc., 2003, 125, 6038; (d) N. S. Josephson, M. L. Snapper
and A. H. Hoveyda, J. Am. Chem. Soc., 2003, 125, 4018; (e) C. Wei,
Z. Li and C.-J. Li, Org. Lett., 2003, 5, 4473; (f) K. Burgess, H.-J. Lim,
A. M. Porte and G. A. Sulikowski, Angew. Chem. Int. Ed., 1996,
35, 220; (g) H. V. R. Dias, R. G. Browning, S. A. Polach, H. V. K.
Diyabalanage and C. J. Loveley, J. Am. Chem. Soc., 2003, 125, 9270;
(h) H. V. R. Dias, R. G. Browning, S. A. Richey and C. J. Loveley,
Organometallics, 2004, 23, 1200.
N-Benzylalanine ethyl ester 4i24
The ee was determined on a Chiralpak AD column using
hexane–i-PrOH (98:2) as eluant. Rt/min: 5.8 (enantiomer-1) and
6.4 (enantiomer-2). The absolute configuration was determined
by optical rotation and compared to described literature
values.19
Acknowledgements
21 M. P. Sibi and M. Liu, Curr. Org. Chem., 2001, 5, 719.
22 For a selected series of recent examples of Lewis acid-catalyzed
decomposition of diazo compounds see e.g.: (a) B. Vanderhoydouck
and C. V. Stevens, Synthesis, 2004, 722; (b) W. G. Yao, M. Y. Liao,
X. M. Zhang, H. Xu and J. B. Wang, Eur. J. Org. Chem., 2003, 1784;
(c) J. S. Yadav, B. V. S. Reddy and G. Satheesh, Tetrahedron Lett.,
2003, 44, 8331; (d) D. Suhr, D. Lotscher, H. Stöckli-Evans and
A. von Zelewsky, Inorg. Chim. Acta, 2002, 341, 17; (e) S. Muthusamy,
S. A. Babu and C. Gunanathan, Tetrahedron Lett., 2002, 43,
3133; (f) M. Curini, F. Epifano, M. C. Marcotullio and O. Rosati,
Eur. J. Org. Chem., 2002, 1562; (g) S. V. Panasare, R. P. Jain and
A. Bhattacharyya, Tetrahedron Lett., 1999, 40, 5255; (h) K. Juhl,
R. G. Hazell and K. A. Jørgensen, J. Chem. Soc., Perkin Trans. 1,
1999, 2293; (i) K. G. Rasmussen and K. A. Jørgensen, J. Chem. Soc.,
Perkin Trans. 1, 1997, 1287.
This work has been made possible by a grant of the Danish
National Research Foundation.
References
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O r g . B i o m o l . C h e m . , 2 0 0 4 , 2 , 3 0 4 4 – 3 0 4 9
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