58
H. T. Bonge, T. Hansen
LETTER
another portion of PhI(OAc)2 (203 mg, 0.616 mmol, 1.0
Acknowledgment
equiv), K2CO3 (187 mg, 1.36 mmol, 2.2 equiv), Rh2(esp)2
(23 mg, 0.031 mmol, 5 mol%) and nitromethane (1.0 mL)
was added and stirring was continued for another 3 h. The
crude reaction mixture was diluted with CH2Cl2, washed
with brine (3 × 5 mL), dried with MgSO4, filtered and the
solution concentrated in vacuo. Flash chromatography (0–
10% EtOAc–hexane) yielded cyclopropanes 2a and 2b. All
cyclopropanes 2–10a,b were characterized by 1H NMR and
13C NMR, MS, HRMS and, when solid, mp.
Financial support by the Chemistry Department, University of
Oslo is gratefully acknowledged. We would like to thank Mr. Dirk
Petersen for assistance with NMR data.
References and Notes
(1) Doyle, M. P.; Ye, T.; McKervey, M. A. Modern Catalytic
Methods for Organic Synthesis with Diazo Compounds:
From Cyclopropanes to Ylides; Wiley: New York, 1998.
(2) O’Bannon, P. E.; Dailey, W. P. Tetrahedron 1990, 46, 734.
(3) Charette, A. B.; Wurz, R. P.; Ollevier, T. J. Org. Chem.
2000, 65, 9252.
Spectroscopic Data for 2a.
1H NMR (300 MHz, CDCl3): d = 1.74–1.81 (ddd, 1 H,
J = 7.9, 7.2, 6.3 Hz, H3b), 2.26–2.33 (ddd, J = 10.6, 6.3, 3.9
Hz, H3a), 3.24–3.32 (ddd, 1 H, J = 10.6, 7.9, 3.0 Hz, H1),
4.46–4.51 (ddd, 1 H, J = 7.2, 3.9, 3.0 Hz, H2), 7.18–7.21
(dd, 1 H, J = 8.5, 1.8 Hz, Ar-H), 7.44–7.52 (m, 2 H, Ar-H),
7.56 (br s, 1 H, H1¢), 7.76–7.83 (m, 3 H, Ar-H).13C NMR (75
MHz, CDCl3): d = 18.7 (C3), 29.6 (C1), 61.6 (C2), 124.5
(Ar-CH), 125.5 (Ar-CH), 126.2 (Ar-CH), 126.6 (Ar-CH),
127.5 (Ar-CH), 127.7 (Ar-CH), 128.7 (Ar-CH), 132.7 (Ar-
C), 133.1 (Ar-C), 133.6 (Ar-C). MS (EI): m/z (relative
intensity) = 213 (24) [M+], 167 (100), 165 (53), 152 (33),
127 (15), 83 (13). Rf = 0.39 (10% EtOAc–hexane); mp 88–
89 °C.
(4) Charette, A. B.; Wurz, R. P.; Ollevier, T. Helv. Chim. Acta
2002, 85, 4468.
(5) Wurz, R. P.; Charette, A. B. Org. Lett. 2003, 5, 2327.
(6) Müller, P.; Ghanem, A. Synlett 2003, 1830.
(7) Müller, P.; Ghanem, A. Org. Lett. 2004, 6, 4347.
(8) Ghanem, A.; Aboul-Enein, H. Y.; Müller, P. Chirality 2005,
17, 44.
(9) Georgakopoulou, G.; Kalogiros, C.; Hadjiarapoglou, L. P.
Synlett 2001, 1843.
(10) Feuer, H.; Nielsen, A. Nitro Compounds: Recent Advances
in Synthesis and Chemistry; VCH: New York, 1990.
(11) Ono, N. The Nitro Group in Organic Synthesis; Wiley-VCH:
New York, 2001.
(12) Doyle, M. P.; Winchester, W. R.; Hoorn, J. A. A.; Lynch, V.;
Simonsen, S. H.; Ghosh, R. J. Am. Chem. Soc. 1993, 115,
9968.
(13) Espino, C. G.; Fiori, K. W.; Kim, M.; Du Bois, J. J. Am.
Chem. Soc. 2004, 126, 15378.
Spectroscopic Data for 2b.
1H NMR (300 MHz, CDCl3): d = 1.67–1.74 (m, 1 H, H3a),
2.43–2.50 (ddd, 1 H, J = 9.0, 6.7 Hz, 4.2 Hz, H3b), 2.94–
3.03 (m, 1 H, H1), 4.65–4.71 (ddd, 1 H, J = 8.3, 6.7, 4.2 Hz,
H2), 7.35–7.38 (dd, 1 H, J = 8.3, 1.8 Hz, Ar-H), 7.41–7.50
(m, 2 H, Ar-H), 7.75–7.81 (m, 4 H, Ar-H). 13C NMR (75
MHz, CDCl3): d = 13.7 (C3), 28.7 (C1), 60.5 (C2), 126.2
(Ar-CH), 126.3 (Ar-CH), 126.7 (Ar-CH), 127.6 (Ar-CH),
127.8 (Ar-CH), 128.2 (Ar-CH), 128.4 (Ar-CH), 129.8 (Ar-
C), 132.9 (Ar-C), 133.1 (Ar-C). MS (EI): m/z (relative
intensity) = 213 (27) [M+], 167 (100), 165 (47), 152 (30),
127 (13), 83 (11). HRMS (EI): m/z calcd for C13H11NO2:
213.0790 (–2.4 ppm); found: 213.0795. Rf = 0.27 (20%
EtOAc–hexane).
(14) General Experimental Procedure.
PhI(OAc)2 (203 mg, 0.616 mmol, 1.0 equiv) was added to a
mixture of Rh2(esp)2 (23 mg, 0.031 mmol, 5 mol%), alkene
(1.0 equiv), nitromethane (1.0 mL, 18.6 mmol, 30 equiv) and
K2CO3 (187 mg, 1.36 mmol, 2.2 equiv). The reaction
mixture was stirred at r.t. for 3 h. After 3 h reaction time,
Synlett 2007, No. 1, 55–58 © Thieme Stuttgart · New York