MHz, CDCl3): δ 7.24-7.02 (m, 5 H), 3.52-3.07 (m, 4 H), 2.54
(dd, J ) 8.2, 4.5 Hz, 1 H), 1.94 (dd, J ) 10.2, 4.5 Hz, 1 H), 1.09
(t, J ) 7.1 Hz, 3 H), 1.01 (t, J ) 7.1 Hz, 3 H), 0.78 (s, 9 H), 0.51
(dd, J ) 10.2, 8.2 Hz, 1 H), 0.04 (s, 3 H), -0.12 (s, 3 H); 13C
NMR (100 MHz, CDCl3): δ 171.8 (C), 139.3 (C), 128.8 (2 × CH),
127.9 (2 × CH), 126.2 (CH), 41.8 (CH2), 41.1 (CH2), 29.9 (CH),
26.5 (3 × CH3), 20.4 (CH), 16.9 (C), 14.4 (CH), 14.0 (CH3), 13.9
(CH3), -5.9 (CH3), -6.1 (CH3); MS (70 eV, EI) m/z (%): 331
[M]+ (3), 316 (27), 274 (100), 171 (33), 115 (44), 59 (34); IR (KBr):
3061, 2954, 1638, 1462 cm-1; HRMS (70 eV) calcd for
C20H33NOSi 331.2331. Found 331.2331; Rf ) 0.29 (hexane/EtOAc,
5:1).
(1S*,2R*,3S*)-2-(tert-Butyldimethylsilyl)-3-phenyl-N,N-diiso-
propylcyclopropanecarboxamide (6b): white solid.1H NMR (300
MHz, CDCl3): δ 7.23-7.04 (m, 5 H), 4.21-4.15 (m, 1 H),
3.70-3.57 (m, 1 H), 2.57 (dd, J ) 8.1, 4.5 Hz, 1 H), 1.93 (dd, J
) 10.3, 4.5 Hz, 1 H), 1.27-1.11 (m, 12 H), 0.79 (s, 9 H), 0.51
(dd, J ) 10.3, 8.1 Hz, 1 H), 0.00 (s, 3 H), -0.06 (s, 3 H); 13C
NMR (75 MHz, CDCl3): δ 170.0 (C), 142.5 (C), 128.3 (2 × CH),
125.8 (CH), 125.7 (2 × CH), 47.4 (CH), 45.5 (CH), 30.5 (CH),
27.4 (CH), 26.5 (3 × CH3), 21.5 (CH3), 21.4 (CH3), 20.6 (CH3),
20.4 (CH3), 17.2 (C), 15.9 (CH), -5.7 (CH3), -6.3 (CH3); MS (70
eV, EI) m/z (%): 359 [M]+ (17), 316 (25), 268 (69), 244 (50), 73
(100); IR (neat): 2927, 2366, 2243, 1633, 1470 cm-1; HRMS (70
eV) calcd for [C22H37NOSi-H] 358.2566. Found 358.2584; Rf )
0.50 (hexane/EtOAc, 5:1).
4-{(1S*,2R*,3S*)-[2-(tert-Butyldimethylsilyl)-3-phenylcyclo-
propyl]carbon-1-yl}morpholine (6c). White solid.1H NMR (300
MHz, CDCl3): δ 7.31-7.13 (m, 5 H), 3.82-3.27 (m, 8 H), 2.93
(dd, J ) 10.1, 4.4 Hz, 1 H), 2.25 (dd, J ) 6.4, 4.4 Hz, 1 H), 0.97
(apparent t, J ) 10.1, 6.4 Hz, 1 H), 0.89 (s, 9 H), -0.26 (s, 3 H),
-0.52 (s, 3 H); 13C NMR (75 MHz, CDCl3): δ 171.6 (C), 138.8
(C), 128.8 (2 × CH), 127.9 (2 × CH), 126.3 (CH), 66.7 (2 × CH2),
45.9 (CH2), 42.6 (CH2), 29.8 (CH), 26.3 (3 × CH3), 19.9 (CH),
16.9 (C), 14.5 (CH), -6.2 (2 × CH3); MS (70 eV, EI) m/z (%):
345 [M]+ (39), 330 (9), 288 (100), 254 (25), 73 (66); IR (neat):
2954, 2360, 1632, 1462 cm-1; HRMS (70 eV) calcd for
C20H31NO2Si 345.2124. Found 345.2147; Rf ) 0.23 (hexane/EtOAc,
3:1).
(1S*,2R*,3S*)-2-(tert-Butyldimethylsilyl)-N,N-diethyl-3-(4-
fluorophenyl)cyclopropanecarboxamide (6f): yellow oil.1H NMR
(300 MHz, CDCl3): δ 7.16 (dd, J ) 8.6, 5.5 Hz, 2 H), 6.94 (t, J )
8.6 Hz, 2 H), 3.62-3.52 (m, 2 H), 3.50-3.35 (m, 2 H), 2.81 (dd,
J ) 10.9, 4.4 Hz, 1 H), 2.19 (dd, J ) 6.8, 4.4 Hz, 1 H), 1.33 (t, J
) 7.1 Hz, 3 H), 1.13 (t, J ) 7.1 Hz, 3 H), 0.93 (dd, J ) 10.9, 6.8
Hz, 1 H), 0.84 (s, 9 H), -0.30 (s, 3 H), -0.48 (s, 3H); 13C NMR
1
(75 MHz, CDCl3): δ 171.6 (C), 161.4 (d, JCF ) 243.3 Hz, C),
135.0 (C), 130.3 (CH), 130.2 (CH), 114.7 (d, 3JCF ) 21.3 Hz, 2 ×
CH), 42.0 (CH2), 41.0 (CH2), 29.1 (CH), 26.3 (3 × CH3), 20.6
(CH), 16.9 (C), 15.1 (CH3), 14.5 (CH), 13.1 (CH3), -5.9 (CH3),
-6.0 (CH3); MS (70 eV, EI) m/z (%): 349 [M+] (43), 292 (100),
234 (26), 180 (23), 118 (34); IR (neat): 2955, 2856, 1636, 1513,
1463, 825 cm-1; HRMS (70 eV) calcd for C20H32FNOSi 349.2237.
Found 349.2236; Rf ) 0.30 (hexane/EtOAc, 5:1).
Synthesis of Silylcyclopropyl ketones 7. Butyl[(1R*,2R*,3S*)-
2-(tert-butyldimethylsilyl)-3-pentylcycloprop-1-yl]ketone (7a). A
2.0 M solution of n-BuLi in di-n-butyl ether (1.2 mmol, 3.0 equiv)
was added dropwise to a solution of the amide 4e (0.4 mmol, 1.0
equiv) in anhydrous THF (2 mL) at -78 °C under nitrogen
atmosphere. The mixture was stirred at -78 °C for 1 h. Then, the
reaction was quenched with an aqueous saturated solution of
ammonium chloride (5 mL) and extracted with dichloromethane
(3 × 10 mL). The organic layers were washed with water, dried
over Na2SO4, and concentrated under vacuum. Purification by
column chromatography on silica gel (hexane/EtOAc, 5:1) yielded
the butyl ketone 7a as colorless oil.1H NMR (300 MHz, CDCl3):
δ 2.54 (t, J ) 7.4 Hz, 1 H), 2.52 (t, J ) 7.4 Hz, 1 H), 1.79 (dd, J
) 9.2, 3.7 Hz, 1 H), 1.62-1.52 (m, 3 H), 1.39-1.25 (m, 13 H),
0.91 (t, J ) 7.3 Hz, 3 H), 0.88 (s, 9 H), 0.15 (apparent t, J ) 9.2
Hz, 1 H), 0.08 (s, 3 H), -0.15 (s, 3 H); 13C NMR (75 MHz, CDCl3):
δ 211.6 (C), 44.1 (CH2), 35.5 (CH2), 33.3 (CH), 31.5 (CH2), 29.6
(CH), 28.9 (CH2), 26.5 (3 × CH3), 26.1 (CH2), 22.5 (CH2), 22.3
(CH2), 18.4 (CH), 17.2 (C), 14.0 (CH3), 13.8 (CH3), -5.9 (2 ×
CH3); MS (70 eV, EI) m/z (%): 310 [M+] (<1), 253 (100), 169
(44), 141 (20), 75 (64); IR (neat): 2956, 2856, 1700, 1465, 1246,
1132 cm-1; HRMS (70 eV) calcd for C19H38OSi 310.2692. Found
310.2688; Rf ) 0.64 (hexane/EtOAc, 10:1).
Methyl[(1R*,2S*,3R*)-2-(tert-butyldimethylsilyl)-3-phenylcy-
cloprop-1-yl]ketone (7b): yellow oil.1H NMR (300 MHz, CDCl3):
δ 7.16-7.10 (m, 5 H), 2.84 (dd, J ) 11.1, 4.4 Hz, 1 H), 2.34 (dd,
J ) 6.8, 4.4 Hz, 1 H), 2.25 (s, 3 H), 0.85 (dd, J ) 11.1, 6.8 Hz, 1
H), 0.74 (s, 9 H), -0.35 (s, 3 H), -0.68 (s, 3 H); 13C NMR (75
MHz, CDCl3): δ 207.9 (C), 138.4 (C), 129.0 (2 × CH), 128.0 (2
× CH), 126.6 (CH), 32.7 (CH), 30.7 (CH), 30.3 (CH3), 26.4 (3 ×
CH3), 18.0 (CH), 17.0 (C), -6.1 (CH3), -6.5 (CH3); MS (70 eV,
EI) m/z (%): 274 [M+] (23), 218 (11), 217 (61), 143 (17), 128 (11),
75 (100), 73 (41); IR (neat): 3057, 2955, 1697, 1408, 1254, 1182
cm-1; HRMS (70 eV) calcd for C17H26OSi 274.1753. Found
274.1764; Rf ) 0.65 (hexane/EtOAc, 5:1).
Butyl[(1R*,2S*,3R*)-2-(tert-butyldimethylsilyl)-3-phenylcyclo-
prop-1-yl]ketone (7c): colorless oil.1H NMR (300 MHz, CDCl3):
δ 7.29-7.21 (m, 5 H), 2.93 (dd, J ) 11.1, 4.4 Hz, 1 H), 2.73 (dd,
J ) 16.2, 7.3 Hz, 1 H), 2.63 (dd, J ) 16.2, 7.3 Hz, 1 H), 2.47 (dd,
J ) 6.8, 4.4 Hz, 1 H), 1.75-1.65 (m, 2 H), 1.46-1.33 (m, 2 H),
1.00 (dd, J ) 11.1, 6.8 Hz, 1 H), 0.96 (t, J ) 7.3 Hz, 3 H), 0.87
(s, 9 H), -0.24 (s, 3 H), -0.53 (s, 3 H); 13C NMR (75 MHz,
CDCl3): δ 210.2 (C), 138.6 (C), 129.0 (2 × CH), 128.0 (2 × CH),
126.5 (CH), 43.4 (CH2), 32.8 (CH), 29.8 (CH), 26.4 (3 × CH3),
26.2 (CH2), 22.3 (CH2), 17.6 (CH), 17.0 (C), 13.8 (CH3), -6.1
(CH3), -6.4 (CH3); MS (70 eV, EI) m/z (%): 316 [M+] (24), 259
(75), 159 (14), 129 (16), 75 (100), 73 (69); IR (neat): 3054, 2956,
2360, 1691, 1420, 1254, 1265 cm-1; HRMS (70 eV) calcd for
C20H32OSi 316.2222. Found 316.2227; Rf ) 0.80 (hexane/EtOAc,
3:1).
(1S*,2R*,3S*)-2-(tert-Butyldimethylsilyl)-N,N-diethyl-3-(4-
methoxyphenyl)cyclopropanecarboxamide (6d): yellow oil.1H
NMR (300 MHz, CDCl3): δ 7.12 (d, J ) 8.6 Hz, 2 H), 6.79 (d, J
) 8.6 Hz, 2 H), 3.78 (s, 3 H), 3.58 (q, J ) 7.1 Hz, 2 H), 3.43 (m,
2 H), 2.79 (dd, J ) 10.8, 4.5 Hz, 1 H), 2.18 (dd, J ) 6.5, 4.5 Hz,
1 H), 1.34 (t, J ) 7.0 Hz, 3 H), 1.13 (t, J ) 7.0 Hz, 3 H), 0.92 (dd,
J ) 10.8, 6.5 Hz, 1 H), 0.85 (s, 9 H), -0.28 (s, 3 H) -0.46 (s, 3
H); 13C NMR (75 MHz, CDCl3): δ 171.9 (C), 158.0 (C), 131.3
(C), 129.8 (2 × CH), 113.3 (2 × CH), 55.1 (CH3), 41.9 (CH2),
41.0 (CH2), 29.2 CH), 26.4 (3 × CH3), 20.5 (CH), 16.9 (C), 15.1
(CH3), 14.2 (CH), 13.1 (CH3), -5.9 (CH3), -6.0 (CH3); MS (70
eV, EI) m/z (%): 361 [M+] (44), 346 (17), 304 (48), 246 (21), 240
(46), 73 (100); IR (neat): 2955, 2856, 1626, 1515, 1463, 1265 cm-1
;
HRMS (70 eV) calcd for C21H35NO2Si 361.2437. Found 361.2448;
Rf ) 0.28 (hexane/EtOAc, 5:1).
4-{(1S*,2R*,3S*)-[2-(tert-Butyldimethylsilyl)-3-(4-methoxy-
phenyl)cyclopropyl]carbon-1-yl}morpholine (6e): yellow oil.1H
NMR (300 MHz, CDCl3): δ 7.06 (d, J ) 8.7 Hz, 2 H), 6.67 (d, J
) 8.7 Hz, 2 H), 3.78 (s, 3 H), 3.67-3.60 (m, 8 H), 2.61 (dd, J )
8.2, 4.5 Hz, 1 H), 1.95 (dd, J ) 10.2, 4.5 Hz, 1 H), 0.90 (s, 9 H),
0.61 (dd, J ) 10.2, 8.2 Hz, 1 H), 0.07 (s, 3 H), 0.01 (s, 3 H); 13C
NMR (75 MHz, CDCl3): δ 170.3 (C), 158.0 (C), 133.7 (C), 127.0
(2 × CH), 113.8 (2 × CH), 66.8 (CH2), 66.6 (CH2), 55.2 (CH3),
45.9 (CH2), 42.2 (CH2), 27.7 (CH), 27.1 (CH), 26.5 (3 × CH3),
17.1 (C), 14.9 (CH), -5.8 (CH3), -6.2 (CH3); MS (70 eV, EI) m/z
(%): 375 [M+] (16), 360 (8), 319 (24), 318 (100), 254 (7), 69 (12);
IR (neat): 3053, 2856, 1638, 1515, 1266, 1116 cm-1; HRMS (70
eV) calcd for C21H33NO3Si 375.223. Found 375.2270; Rf ) 0.23
(hexane/EtOAc, 3:1).
Phenyl[(1R*,2S*,3R*)-2-(tert-butyldimethylsilyl)-3-phenylcy-
cloprop-1-yl]ketone (7d): white solid.1H NMR (300 MHz, CDCl3):
δ 8.02-7.99 (m, 2 H), 7.52-7.39 (m, 3 H), 7.23-7.09 (m, 5 H),
3.11 (dd, J ) 6.9, 4.4 Hz, 1 H), 3.03 (dd, J ) 11.0, 4.4 Hz, 1 H),
J. Org. Chem. Vol. 73, No. 10, 2008 3835