4JHH = 1.5 Hz, 1H, CH); 6.86 (dt, 3JHH = 15.5 Hz, 3JHH = 7.0 Hz,
1H, CH); dC (CDCl3) 14.03 (s, CH3CH2O); 14.15 (s, CH3CH2O);
16.28 (d, 3JPC = 5.7 Hz, 2 × CH3CH2OP); 29.34 (d, 2JPC = 3.8 Hz,
CH2); 44.38 (d, 1JPC = 131.3 Hz, CHP); 60.31 (s, CH2O); 61.65 (s,
CH2O); 62.84 (d, 2JPC = 7.15 Hz, CH2OP); 62.97 (d, 2JPC = 7.2 Hz,
2 (a) D. B. Denney and M. J. Boskin, J. Am. Chem. Soc., 1959, 81, 6330;
(b) W. S. Wadsworth and W. D. Emmons, J. Am. Chem. Soc., 1961, 83,
1733; (c) D. B. Denney, J. J. Vill and M. J. Boskin, J. Am. Chem. Soc.,
1962, 84, 3944; (d) I. To¨mo¨sko¨zi, Tetrahedron, 1963, 19, 1969; (e) R. A.
Izydore and R. G. J. Ghirardelli, J. Org. Chem., 1973, 38, 1790.
3 (a) B. J. Fitzsimmons and B. Fraser-Reid, Tetrahedron, 1984, 40, 1279;
(b) R. C. Petter, Tetrahedron Lett., 1989, 30, 399; (c) R. C. Petter,
S. Banerjee and S. Englard, J. Org. Chem., 1990, 55, 3088; (d) J. A.
Robl, E. Sieber-McMaster and R. Sulsky, Tetrahedron Lett., 1996, 37,
8985; (e) V. Padmavathi, K. Sharmila, A. S. Reddy and D. B. Reddy,
Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem., 2001, 40, 11;
(f) A. K. Singh, M. N. Rao, J. H. Simpson, W. S. Li, J. E. Thornton,
D E. Kuehner and D. J. Kacsur, Org. Process Res. Dev., 2002, 6, 618;
(g) A. K. Singh, J. S. Prasad and E. J. Delaney, Asymmetric Catalysis
on Industrial Scale: Challenges, Approaches and Solutions, Wiley-VCH,
Weinheim, 2004, p. 335; (h) A. Armstrong and J. N. Scutt, Org. Lett.,
2003, 5, 2331; (i) A. Armstrong and J. N. Scutt, Chem. Commun., 2004,
510; (j) G. Sturtz, Bull. Soc. Chim. Fr., 1964, 2349; (k) M. Baboulene
and G. Sturtz, Phosphorus Relat. Group V Elem., 1973, 2, 195; (l) T. E.
Jacks, H. Nibbe and D. F. Wiemer, J. Org. Chem., 1993, 58, 4584.
CH2OP); 123.45 (s, CH); 144.21 (d, 3JPC = 15.7 Hz, CH); 165.96
2
=
=
(s, C O); 167.99 (d, JPC = 4.7 Hz, C O). C14H25O7P: requires C
50.00, H 7.49; found C 49.77, H 7.44.
Compound 36. Yield (0.13 g, 13%); colourless oil; (Rf = 0.63);
mmax 1764, 1724, 1220, 1024; dP (CDCl3) 23.16; dH (CDCl3) 1.18 (td,
4
3JHH = 7.0 Hz, JPH = 1.2 Hz, 3H, CH3CH2OP); 1.20–1.38 (m,
12H, 2 × CH3CH2O, CH3CH2OP, CH2, CH); 2.24 (ddddd, 3JHH
=
=
3
3
3
3
11.0 Hz, JHH = 10.5 Hz, JPH = 7.0 Hz, JHH = 6.0 Hz, JHH
5.0 Hz, 1H, CH); 3.12 (dd, 2JPH = 23.2 Hz, 3JHH = 10.5 Hz, 1H,
CH); 4.11–4.24 (m, 8H, 2 × CH2O, 2 × CH2OP); dC (CDCl3) 14.03
(s, CH3CH2O); 15.13 (s, CH3CH2O); 16.28 (d, 3JPC = 5.7 Hz, 2 ×
CH3CH2OP); 21.10 (d, 3JPC = 2.6 Hz, CH2); 28.95 (s, CH); 30.88
(d, 2JPC = 3.0 Hz, PCH); 41.41 (d, 1JPC = 131.3 Hz, CHP); 61.28
4 H. Krawczyk, K. Wasek and J. Kędzia, Synlett, 2005, 2648.
ꢀ
5 (a) T. Minami, Y. Kitajima and T. Chikugo, Chem. Lett., 1986, 1229;
(b) T. Minami, K. Watanabe, T. Chikugo and Y. Kitajima, Chem. Lett.,
1987, 2369; (c) T. Janecki, A. Kus´, H. Krawczyk and E. Błaszczyk,
Synlett, 2000, 611; (d) T. Janecki and E. Błaszczyk, Synthesis, 2001,
403.
2
(s, CH2O); 62.14 (s, CH2O); 62.63 (d, JPC = 6.2 Hz, CH2OP);
62.95 (d, 2JPC = 6.1 Hz, CH2OP); 168.92 (d, 2JPC = 3.1 Hz, C O);
=
6 C. K. McClure and K.-Y. Jung, J. Org. Chem., 1991, 56, 867.
7 T. C. Myers, R. G. Harvey and E. V. Jensen, J. Am. Chem. Soc., 1955,
77, 3101.
=
175.14 (s, C O). C14H25O7P: requires C 50.00, H 7.49; found C
50.19, H 7.45.
8 J. M. Varlet, G. Fabre, F. Sauveur, N. Collignon and P. Savignac,
Tetrahedron, 1981, 37, 1377.
9 M. K. Tay, E. About-Jandet, N. Collignon, M. P. Teulade and P.
Savignac, Synth. Commun., 1988, 18, 1349.
10 I. Truel, A. Mohamed-Hachi, E. About-Jaudet and N. Collignon,
Synth. Commun., 1997, 27, 1165.
11 S. Touil and H. Zantour, Phosphorus, Sulfur Silicon Relat. Elem., 1997,
131, 183.
12 G. A. Kraus and P. K. Choudhury, Eur. J. Org. Chem., 2004, 2193.
13 D.-J. Cho, S.-J. Jean, H.-S. Kim, C.-S. Cho, S.-C. Shim and T.-J. Kim,
Tetrahedron: Asymmetry, 1999, 10, 3833.
14 S. Ahmad, L. M. Doweyko, S. Dugar, N. Grazier, K. Ngu, S. C. Wu,
K. J. Yost, B.-C. Chen, J. Z. Gougoutas, J. D. DiMarco, S.-J. Lan, B. J.
Gavin, A. Y. Chen, C. R. Dorso, R. Serafino, M. Kirby and K. S. Atwal,
J. Med. Chem., 2001, 44, 3302.
Crystal structure determination of 1-benzyl-2-methylcyclopro-
panecarboxylate anion derived from the ester 7h. C12H13NO2·
C12H24N, Mw = 371.55, colourless crystal 0.40 × 0.20 × 0.10 mm,
˚
triclinic, a = 10.2817(1), b = 10.6027(1), c = 11.7395(2) A, a =
◦
3
˚
64.164(1), b = 86.195(1), c = 73.578(1) , V = 1102.46(2) A ,
space group P1, Z = 2, qcalc = 1.20 g cm−3, l = 0.537 mm−1,
¯
F(000) = 408, semi-empirical absorption correction based on
multiple scanned equivalent reflections (0.827 < T < 0.943), k(Cu-
˚
Ka) = 1.54178 A, T = 293 K, x scans, 12 592 reflections collected
( h, k, l), 2hmax = 142◦, 4052 unique reflections (Rint = 0.014),
392 refined parameters, refinement on F2, final R = 0.048 for
3765 observed reflections [Fo > 4r(Fo)], Rall = 0.050, wRall(F2) =
15 A. G. M. Barret, D. C. Braddock, I. Lenoir and H. Tone, J. Org. Chem.,
2001, 66, 8260.
−3
˚
0.140, residual electron density Dqmax = 0.19 Dqmin = −0.22 e A ,
16 Spectral data of trans-1-benzyl-2-phenylcyclopropanecarboxylic acid.
all hydrogen atoms refined with individual isotropic temperature
factors. X-Ray data were collected with a Bruker SMART APEX
CCD area detector diffractometer. Computer programs used:
data collection: SMART APEX,24 data reduction: SAINT-Plus,25
absorption correction: SADABS,26 structure solution, refinement
and molecular graphics: SHELXTL.27 CCDC reference number
653900. For crystallographic data in CIF or other electronic
format see DOI: 10.1039/b712145h
White crystals (m.p. 90–92 ◦C); mmax 1744; dH (CDCl3) = 1.40 (dd,
2
3
3JHH = 7.0 Hz, JHH = 5.0 Hz, 1H, CHH); 1.86 (dd, JHH = 9.2 Hz,
2JHH = 5.0 Hz, 1H, CHH); 2.01 (d, 2JHH = 15.0 Hz, 1H, CHH); 2.80
(dd, 3JHH = 9.2 Hz, 3JHH = 7.0 Hz, 1H, CH); 3.22 (d, 2JHH = 15.0 Hz,
1H, CHH); 7.23–7.30 (m, 5H, CHAr); dC (CDCl3): 17.80 (CH2); 30.95
(CH2); 31.14 (C); 32.27 (CH); 125.64 (2 × CHAr); 128.01 (2 × CHAr);
=
128.42 (CHAr); 140.60 (CAr); 179.98 (C O). C19H20O2: requires C 81.40,
H 7.19; found C 81.64, H 7.15.
17 H. Krawczyk, K. Wasek, J. Kędzia, J. Wojciechowski and W. M. Wolf,
ꢀ
Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 2007, in press.
18 Spectral data of the dicyclohexylammonium salt of trans-1-benzyl-2-
methylcyclopropanecarboxylic acid. Light yellow crystals (m.p. 91–
94 ◦C); mmax 1760, 1150; dH (CDCl3) = 0.62 (dd, 3JHH = 6.7 Hz, 2JHH
=
Acknowledgements
4.0 Hz, 1H, CHH); 1.11–1.36 (m, 9H, 3 × CH2, CH3), 1.42–1.68 (m,
7H, 3 × CH2, CHH); 1.60 (dd, 3JHH = 9.2 Hz, 3JHH = 6.7 Hz, 3JHH
=
The authors thank Professor Ryszard Bodalski (Technical Uni-
versity of Lodz) for stimulating discussions.
6.2 Hz, 1H, CH); 1.69 1.80 (m, 4H, 2 × CH2); 1.98–2.06 (m, 4H, 2 ×
2
CH2); 2.76 (d, JHH = 16.0 Hz, 1H, CHH); 2.80–3.05 (m, 2H, 2 ×
CHN); 3.22 (d, 2JHH = 16.0 Hz, 1H, CHH); 7.23–7.30 (m, 5H, CHAr);
dC (CDCl3): 14.00 (CH3); 21.75 (CH2); 22.27 (CH); 24.32 (2 × CH2);
24.75 (4 × CH2); 27.69 (C); 33.04 (4 × CH2); 33.26 (CH2); 24.32 (2 ×
CH); 125.64 (2 × CHAr); 128.01 (2 × CHAr); 128.37 (CHAr); 140.60
References and notes
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=
(CAr); 179.66 (C O). C24H37NO2: requires C 77.58, H 10.04, N 3.77;
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