814
K. Azzouzi-Zriba et al. / Journal of Fluorine Chemistry 132 (2011) 811–814
4.1. Cyclopropanation reaction: general procedure
isolated after purification by silica gel chromatography (Ethyl
acetate/Hexane: 1/9) as yellow oil (251 mg, 98%).
To a solution of olefin (1.0 mmol) and Cu(OTf)2 (0.01 mmol) in
HFIP (1.5 ml) was added ethyldiazoacetate (EDA, 1.5 mmol) at 0 8C.
After stirring at room temperature until completion of reaction
(monitored by GC analysis), the reaction mixture was quenched
with a saturated aqueous solution of NH4Cl (2 ml), and extracted
with CH2Cl2 (2Â 5 ml). The organic layers were washed with brine
(10 ml), dried over anhydrous MgSO4, filtered and concentrated
under reduced pressure. The crude product was purified by
chromatography on silica gel.
1H NMR
d
(mixture cis/trans) 4.06 (q, J = 8.2 Hz, 4H), 1.01–1.39
(m, 50H); 0.81 (t, J = 7.7 Hz, 6H). 13C NMR
174.4, 172.9, 60.1, 60.0,
33.0, 31.8, 29.5, 29.0, 26.9, 22.8, 22.6, 21.8, 20.1, 18.1, 15.3, 14.3,
14.2, 14.0, 13.2. I.R. (neat):
= 1727 cmÀ1
d
n
.
4.1.5. Ethyl bicyclo[6.1.0]nonane-9-carboxylate 16 [8]
Product 16 was prepared from cyclooctene (109 mg, 1 mmol),
Cu(OTf)2 (2 mg, 0.01 mmol) and EDA (0.21 ml, 2 mmol). 16 was
isolated after purification by silica gel chromatography (Ethyl
acetate/Hexane: 1/9) as yellow oil (148 mg, 75%).
4.1.1. Ethyl 2-phenylcyclopropane-1-carboxylate 3 [8]
Using the general procedure, to a solution of styrene (105 mg,
1 mmol), Cu(OTf)2 (2 mg, 0.01 mmol) in 1 ml of HFIP was added
EDA (0.21 ml, 1.5 mmol). After purification by silica gel chroma-
tography (Et2O/Hexane: 1/9), 3 was isolated as colorless oil
product (174 mg, 86%).
1H NMR
2.08 (m, 2H), 1.47–1.73 (m, 12H), 1.26–1.46 (m, 12H), 1.12–1.24
(m, 6H), 0.48–1.08 (m, 4H). 13C NMR
174.3, 172.2, 60.0, 59.5, 29.3,
29.0, 27.2, 27.0, 26.3, 25.7, 24.5, 20.7, 14.2. I.R. (neat):
= 1730 cmÀ1
d (mixture of cis/trans): 4.05 (q, J = 7.2 Hz, 4H), 1.92–
d
n
.
1H NMR:
d
(trans-isomer) 7.09–7.31 (m, 5H), 4.17 (q, J = 7.2 Hz;
4.1.6. Ethyl bicyclo[5.1.0]octane-8-carboxylate 18 [13]
2H), 2.52 (ddd, J = 9.3; 6.6; 5.2 Hz, 1H), 1.90 (ddd, J = 8.7; 5.4; 4.5 Hz,
1H), 1.60 (ddd, J = 8.5; 6.5; 4.2 Hz, 1H), 1.28 (t, J = 7.2 Hz, 3H), 1.29–
Product 18 was prepared from cycloheptene (97 mg, 1 mmol),
Cu(OTf)2 (2 mg, 0.01 mmol) and EDA (0.21 ml, 2 mmol). 18 was
isolated after purification by silica gel chromatography (Ethyl
acetate/Hexane: 1/9) as yellow oil (167 mg, 82%).
1.32 (m, 1H). 13C NMR
d
(trans-isomer) 173.4, 140.1, 128.4, 126.4,
126.1, 60.7, 26.2, 24.2, 17.1, 14.3. I.R. (neat):
= 1720 cmÀ1
1H NMR:
(cis-isomer) 7.19–7.28 (m, 5H), 3.90 (q, J = 7.1 Hz,
n
.
d
1H NMR
16H); 13C NMR
22.7, 14.12. I.R. (neat):
d
trans-isomer: 4,08 (q, J = 7.0 Hz, 2H), 0.90–2.46 (m,
175.3, 60.5, 59.5, 32.3, 29.8, 29.3, 29.1, 28.5, 25.7,
= 1729 cmÀ1
2H), 2.59 (ddd, J = 7.4; 8.7; 9.3 Hz, 1H), 2.05 (ddd, J = 5.6; 7.8;
9.3 Hz, 1H), 1.70 (ddd, J = 5.1; 5.6; 7.4 Hz, 1H), 1.33 (ddd, J = 5.1;
d
n
.
7.8; 8.7 Hz, 1H), 0.89 (t, J = 7.1 Hz, 3H). 13C NMR
d
(cis-isomer)
170.9, 136.5, 129.2, 127.8, 126.6, 60.1, 25.4, 21.7, 14.0, 11.1. I.R.
(neat):
= 1728 cmÀ1
4.1.7. Ethyl 2-oxa-bicyclo[4. 1. 0]heptane-7-carboxylate 20 [14]
Product 20 was prepared from dihydropyrane (84 mg, 1 mmol),
Cu(OTf)2 (2 mg, 0.01 mmol) and EDA (0.21 ml, 2 mmol). 20 was
isolated after purification by silica gel chromatography (Ethyl
acetate/n-Pentane: 1/9) as colorless oil (93 mg, 55%).
n
.
Anal. calcd. for C15H14O2 C, 75.76; H, 7.42 found C, 75.63; H, 7.58.
4.1.2. Ethyl 2-(3-nitro-phenyl)-cyclopropanecarboxylate 6
Product 6 was prepared from 3-nitrostyrene (150 mg, 1 mmol),
Cu(OTf)2 (2 mg, 0.01 mmol) and EDA (0.21 ml, 2 mmol). 6 was
isolated after purification by silica gel chromatography (Ethyl
acetate/Hexane: 1/9), as yellow oil (24 mg, 10%).
1H NMR
3H), 2.1–1.2 (m, 6H), 1.18 (t, J = 7.1 Hz, 3H). 1H NMR
d
(trans-isomer): 4.06 (q, J = 7.1 Hz, 2H), 3.2–3.9 (m,
(cis-isomer):
d
4.13 (q, J = 7.1 Hz, 2H), 3.3–3.95 (m, 3H), 2.46 (d of d, J = 6.6; 7.8 Hz,
1H), 1–1.8 (m, 5H), 1.26 (t, J = 7.1 Hz, 3H).
Yellow oil 1H NMR
d 8.02–8.11 (m, 1H), 7.93 (s, 1H), 7.45 (d,
J = 7.8 Hz, 2H), 4.18 (q, J = 7.2 Hz, 2H), 2.54–2.69 (m, 1H), 1.98 (ddd,
J = 9.0; 8.0; 5.0 Hz, 1H), 1.92–2.21 (m, 1H), 1.35–1.51 (m, 1H),
Acknowledgements
1.28 (t, J = 7.2 Hz, 3H). 13C NMR
d
14.2; 172.5, 148.5, 142.4,
132.6, 129.3, 121.5, 120.9, 61.0, 25.3, 24.4, 17.1. I.R. (neat):
= 1725 cmÀ1
Central Glass Co. Ltd. is gratefully acknowledged for kindly
providing HFIP.
n
.
References
4.1.3. Ethyl 2-Benzylcyclopropanecarboxylate 12 [8]
Product 12 was prepared from allyl-benzene (118 mg, 1 mmol),
Cu(OTf)2 (2 mg, 0.01 mmol) and EDA (0.21 ml, 2 mmol). 12 was
isolated after purification by silica gel chromatography (Et2O/
Hexane: 1/9), as colorless oil (116 mg, 56%).
[1] (a) R.M. Moriarty, S. Tyagi, M. Kinch, Tetrahedron 66 (2010) 5801–5810;
(b) J. Salaun, The Chemistry of the Cyclopropyl Group, vol. 2, Wiley, New York,
NY, 1987, p. 809.
[2] (a) M.P. Doyle, D.C. Forbes, Chem. Rev. 98 (1998) 911–935;
(b) M.P. Doyle, M.A. McKervey, T. Ye, Modern Catalytic Methods for Organic
Synthesis with Diazo Compounds, John Wiley & Sons, New York, NY, 1998;
(c) H. Lebel, J.F. Marcoux, C.Molinaro, A.B. Charette, Chem. Rev. 103 (2003) 977–1050.
[3] I. Nicolas, P. Le Maux, G. Simonneaux, Coord, Chem. Rev. 252 (2008) 727–735, and
references cited herein.
[4] (a) For reviews see: J.P. Be´gue´, B. Crousse, D. Bonnet-Delpon, Synlett, (2004)
18–29;
(b) I.A. Shuklov, N.V. Dubrovina, A. Bo¨rner, Synthesis (2007) 2925–2943.
[5] Y. Chin, X.P. Zhang, J. Org. Chem. 69 (2004) 2431–2435.
[6] L. Dumitrescu, K. Azzouzi-Zriba, D. Bonnet-Delpon, B. Crousse, Org. Lett. 13 (2011)
692–695.
Trans-isomer: 1H NMR
d 7.27 (m, 5H), 4.13 (q, J = 7.0 Hz, 2H),
2.79 (dd, J = 6.0 Hz, 15.0 Hz, 1H), 2.59 (dd, J = 7.0 Hz, 15 Hz, 1H),
1.67–1.74 (m, 1H), 1.51–1.56 (m, 1H), 1.22 (t, J = 7.0 Hz, 3H), 1.20–
1.32 (m, 1H); 0.82–0.89 (m, 1H). 13C NMR
d 173.5, 141.0, 128.0,
127.9, 125.8, 60.4, 38.4, 22.9, 20.2, 15.1, 14.2. HRMS (Cl, NH3)
calculated for C13H20NO2: (M+NH4)+ 222.1494; found (M+NH4)+
222.1491. I.R. (neat):
Cis-isomer: 1H NMR
n .
= 1723 cmÀ1
d
7.28 (m, 5H), 4.14 (q, J = 7.0 Hz, 2H), 2.93
[7] In a mixture of CH2Cl2/HFIP; the reaction afforded dimerisation products of EDA
(>30%) and low conversion of cyclopropanes 3 (50%)
[8] A.G.M. Barrett, D.C. Braddock, I. Lenoir, H. Tone, J. Org. Chem. 66 (2001)
8260–8263.
(dd, J = 7.0 Hz, 15.0 Hz, 1H), 2.83 (dd, J = 7.0 Hz, 15 Hz, 1H), 1.78 (m,
1H), 1.54 (m, 1H), 1.23 (t, J = 7.0 Hz, 3H), 1.22–1.29 (m, 1H); 1.12
(m, 1H). 13C NMR
d 172.3, 139.6, 128.0, 127.8, 125.6, 61.2, 32.3,
[9] M.P. Doyle, Comprehensive OrganometallicChemistry, Pergamon, Oxford, 1995, p. 12.
[10] R.G. Salomon, J.K. Kochi, J. Am. Chem. Soc. 95 (1973) 3300–3310.
[11] M.R. Fructos, T.R. Belderrain, M.C. Nicasio, S.P. Nolan, H. Kaur, M.M. Diaz-Requejo,
22.1, 18.0, 13.7, 13.0. HRMS (Cl, NH3) calculated for C13H20NO2:
(M+NH4)+ 222.1494; found (M+NH4)+ 222.1454. I.R. (neat):
n
= 1733 cmÀ1
.
´
P.J. Perez, J. Am. Chem. Soc. 126 (2004) 10846–10850.
[12] A. Di Salvo, M. David, B. Crousse, D. Bonnet-Delpon, Adv. Synth. Catal. 348 (2006)
118–124.
4.1.4. Ethyl 2-decylcyclopropanecarboxylate 14
[13] A.J. Anciaux, A.J. Hubert, A.F. Noels, N. Petiniot, P. Teyssie´, J. Org. Chem. 45 (1980)
695–702.
[14] M.P. Doyle, D. Van Leusen, J. Org. Chem. 47 (1982) 5326–5339.
Product 14 was prepared from n-dodecene (168 mg, 1 mmol),
Cu(OTf)2 (2 mg, 0.01 mmol) and EDA (0.21 ml, 2 mmol). 14 was