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4.2.2. Methyl 2-chloro-2-phenylcyclopropane-1-
carboxylate (2).14a CAS RN: 39822-09-8 (R*,S*), 39822-
10-1 (R*,R*).
139 (18), 131 (26), 119 (18), 115 (15), 111 (15), 83 (13), 55
(10). IR n (cmK1) (film) 3100, 2990, 2970, 1750, 1730, 1440.
4.2.6. Methyl 2-chloro-1-methyl-2-phenylcyclopropane-
1-carboxylate (6). (C12H13ClO2); MW: 224.687; CAS RN:
91433-96-4 (R*,S*), 91434-02-5 (R*,R*). Pentane (100) to
pentane–ether (95/5); obtained: 1.64 g (yield: 73%, (R*,S*)/
4.2.3. Dimethyl 2-chloro-1-methoxycarbonylmethylcyclo-
propane-1,2-dicarboxylate (3).14a CAS RN: 424790-89-6
(R*,S*), 424790-88-5 (R*,R*).
1
(R*,R*): 25:75, process B; (R*,S*) and (R*,R*): oil. H
NMR (200 MHz, CDCl3) d (R*,S*): 7.4–7.6 (Ph, 5H, m);
4.0 (OCH3, 3H, s); 2.4 (H-3 or H-30, 1H, d, JZ6.8 Hz); 1.7
(H-3 or H-30, 1H, d, JZ6.8 Hz); 1.2 (CH3, 3H, s); for the
couple H-3/H-30 (Dn/JZ20.0 AX system). (R*,R*):
7.5–7.45 (Ph, 5H, m); 3.5 (OCH3, 3H, s); 2.6 (H-3 ou H-
30, 1H, d, JZ6.5 Hz); 1.95 (CH3, 3H, s); 1.6 (H-3 or H-30,
1H, d, JZ6.5 Hz); for the couple H-3/H-30 (Dn/JZ32.3 AX
system). 13C NMR (50 MHz, CDCl3) d (R*,S*): CO: 171.0;
C(Ph): 137.9, 128.8, C-2: 52.1; OCH3: 49.9; C-1: 33.1; C-3:
24.5; CH3: 17.6. (R*,R*): C-4: 171.4; C-7: 139.6; other
aromatic C: 128.4; C-2: 53.9; C-5: 51.8; C-1: 32.4; C-3:
26.0; C-6: 18.0. EI-MS m/z (R*,S*): 225 (M, 6), 189 (35),
167 (12), 165 (34), 161 (8), 157 (8), 131 (15), 130 (12), 129
(base peak), 128 (28), 105 (10). (R*,R*): 225 (M, 9), 189
(35), 167 (10), 165 (35), 161 (10), 157 (10), 131 (16), 130
(15), 129 (base peak), 128 (27), 105 (10). IR n (cmK1) (film)
3030, 2920, 1720, 1580, 1500, 1450.
4.2.4. Methyl 2-chloro-1-methoxycarbonylmethyl-2-
phenylcyclopropane-1-carboxylate (4) (new compound).
(C14H15ClO4); MW: 282.723. Anal. Calcd for C14H15ClO4:
C, 59.48; H, 5.35; O, 22.63; Cl, 12.54. Found: C, 59.28; H,
5.33; O, 22.63; Cl, 12.66. Pentane–ether (95/5) to (90/10);
obtained: 1.16 g (yield: 41%, (R*,S*)/(R*,R*): 35:65,
process A), 1.61 g (yield: 57%, (R*,S*)/(R*,R*): 36:64,
process B); (R*,S*): oil, (R*,R*): mpZ76–78 8C. 1H NMR
(200 MHz, CDCl3) d (R*,S*): 7.3–7.2 (Ph, 5H, m); 3.75
(OCH3, 3H, s); 3.5 (OCH3, 3H, s); 3.1 (CH2, 1H, d,
JZ17.6 Hz); 2.35 (H-3 or H-30, 1H, d, JZ7.4 Hz); 1.65 (H-
3 or H-30, 1H, d, JZ7.4 Hz); 1.3 (CH2, 1H, d, JZ17.6 Hz);
for the couple H-3/H-30 (Dn/JZ19.0 AX system); for the
methylene group (Dn/JZ21.0 AX system). (R*,R*): 7.4–7.2
(Ph, 5H, m); 3.7 (OCH3, 3H, s); 3.4 (CH2, 1H, d,
JZ17.6 Hz); 3.2 (OCH3, 3H, s); 2.9 (CH2, 1H, d,
JZ17.6 Hz); 2.5 (H-3 or H-30, 1H, d, JZ6.9 Hz); 1.5
(H-3 or H-30, 1H, d, JZ6.9 Hz); for the couple H-3/H-30
(Dn/JZ29.0 AX system); for the methylene group (Dn/JZ
5.5 AB system). 13C NMR (50 MHz, CDCl3) d (R*,S*): CO:
170.9, 169.9; C(Ph): 138.5, 128.5; C-2: 53.3; OCH3: 52.0,
51.9; CH2: 37.3; C-1: 33.3; C-3: 25.6. (R*,R*): CO: 171.7,
169.7; C(Ph): 137.8, 128.7; C-2: 53.4; OCH3: 51.7, 49.7;
CH2: 37.5; C-1: 34.3; C-3: 23.7. EI-MS m/z (R*,S*): 282
(M, 1), 220 (32), 219 (13), 218 (base peak), 192 (14), 191
(20), 190 (46), 187 (13), 165 (26), 164 (16), 163 (78), 162
(17), 159 (20), 155 (11), 149 (24), 145 (20), 129 (17), 128
(56), 127 (30), 115 (11). (R*,R*): 282 (M, 1), 220 (30), 219
(12), 218 (base peak), 192 (16), 191 (19), 190 (41), 187 (14),
165 (26), 164 (13), 163 (71), 162 (15), 159 (21), 155 (10),
149 (22), 145 (20), 129 (20), 128 (64), 127 (30), 115 (11). IR
n (cmK1) (CDCl3) 3080, 3030, 2990, 2970, 2900, 1735,
1600, 1570, 1470.
4.2.7. trans-Trimethyl 1-chlorocyclopropane-1,2,3-
tricarboxylate (7).14d CAS RN: 205320-46-3.
4.2.8. trans-Dimethyl 3-chloro-3-phenylcyclopropane-
1,2-dicarboxylate (8).14d CAS RN: 205320-44-1.
4.2.9. (1RS,6RS,7RS)-Methyl 7-chloro-2-oxobicyclo
[4.1.0]heptane-7-carboxylate (9). (C9H11ClO3); MW:
202.637; CAS RN: 406217-16-1. Pentane–ether (90/10) to
(80/20); obtained: 1.17 g (yield: 58%, process A), 1.07 g
1
(yield: 53%, process B); oil. H NMR (200 MHz, CDCl3)
3.5 (OCH3, 3H, s); 2.3–2.1 (2H, m); 2.1–1.8 (3H, m);
1.7–1.5 (3H, m). 13C NMR (50 MHz, CDCl3) d COR: 202.5;
COOR: 168.7; OCH3: 53.5; C-7: 48.7; C-3: 38.9; C-1: 34.1;
C-6: 30.1; C-4 and C-5: 23.9, 17.6. EI-MS m/z 202 (M, 10),
176 (23), 174 (73), 172 (28), 171 (13), 170 (88), 148 (10),
147 (31), 146 (14), 145 (34), 144 (36), 143 (51), 142 (base
peak), 139 (13), 135 (32), 117 (12), 116 (10), 115 (21), 111
(11), 107 (41), 106 (10), 87 (13), 81 (14), 80 (11), 79 (99),
78 (15), 77 (43), 53 (11), 51 (40). IR n (cmK1) (CDCl3)
1750, 1720.
4.2.5. Dimethyl 1-chloro-2-methylcyclopropane-1,2-
dicarboxylate (5). (C8H11ClO4); MW: 206.625; CAS RN:
42392-04-1 (R*,S*), 132785-43-4 (R*,R*). Pentane (100) to
pentane–ether (95/5); obtained: 1.45 g (yield: 70%, (R*,S*)/
1
(R*,R*): 45:55, process B; (R*,S*) and (R*,R*): oil. H
NMR (200 MHz, CDCl3) d (R*,S*): 3.5 (OCH3, 3H, s); 3.4
(OCH3, 3H, s); 2.0 (H-3 or H-30, 1H, d, JZ6.5 Hz); 1.3
(CH3, 3H, s); 1.0 (H-3 or H-30, 1H, d, JgemZ6.5 Hz); for the
couple H-3/H-30 (Dn/JZ31.4 AX system). (R*,R*): 3.65
(OCH3, 3H, s); 3.6 (OCH3, 3H, s); 1.85 (H-3 or H-30, 1H, d,
JZ6.6 Hz); 1.7 (H-3 or H-30, 1H, d, JZ6.6 Hz); 1.2 (CH3,
3H, s); for the couple H-3/H-30 (Dn/JZ5.6 AB system). 13C
NMR (50 MHz, CDCl3) d (R*,S*): CO: 170.8, 167.8;
OCH3: 53.1, 52.4; C-1: 48.5; C-2: 33.7; C-3: 27.9; CH3:
17.3. (R*,R*): CO: 169.0, 166.9; OCH3: 53.0, 52.1; C-1:
45.2; C-2: 35.1; C-3: 25.5; CH3: 14.8. EI-MS m/z (R*,S*):
206 (M, !1), 177 (13), 176 (15), 175 (37), 174 (32), 171
(22), 170 (51), 148 (35), 147 (17), 146 (base peak), 139 (16),
133 (12), 131 (31), 127 (11), 119 (18), 115 (20), 111 (12), 87
(15), 83 (15). (R*,R*): 206 (M, 1), 176 (11), 175 (22), 174
(26), 171 (13), 170 (36), 148 (34), 147 (17), 146 (base peak),
4.2.10. (1RS,6RS,7RS)-7-Chloro-7-phenylbicyclo[4.1.0]-
heptane-2-one (10). (C13H13ClO); MW: 220.699; CAS
RN: 126252-39-9. Pentane (100) to pentane–ether (95/5);
obtained: 0.662 g (yield: 30%, process A), 1.10 g (yield:
50%, process B); mpZ69–70 8C. 1H NMR (200 MHz,
CDCl3) 7.6–7.2 (Ph, 5H, m); 2.3–1.6 (H-1 to H-6, 8H, m).
13C NMR (50 MHz, CDCl3) d CO: 204.9; C(Ph): 141.9,
128.3, 127.5; C-7: 54.9; C-3: 39.1; C-1: 33.6; C-6: 29.0; C-4
and C-5: 24.9, 18.6. EI-MS m/z 220 (M, 8), 192 (15), 185
(10), 157 (28), 141 (8), 130 (12), 129 (base peak), 128 (27),
127 (9), 115 (15). IR n (cmK1) (CDCl3) 3080, 3020, 2980,
1700, 1600, 1580, 1500.
4.2.11. (1RS,5RS,6RS)-Methyl 6-chloro-2-oxobicyclo
[3.1.0]hexane-6-carboxylate (11). (C8H9ClO3); MW: