and 0.6 mL (584 μmol, 1.2 equiv.) of a 1 M allylmagnesium
bromide solution in diethylether was added slowly. The mixture
was stirred for 30 min at -78 °C (reaction control by TLC). After
full conversion it was hydrolysed with 5 mL of water and 0.8 mL
of 1 M HCl. The mixture was warmed to room temperature and
the two layers have been separated. The aqueous layer was
extracted with diethylether three times. The combined organic
layers were dried with MgSO4, filtered and the solvent was
evaporated. The crude product was purified by column
chromatography (PE : EE 95 : 5). 70 mg (376 μmol, 77%, 97%
ee) of ketone (S,S)-12 could be isolated as a colourless oil.
dichloromethane. The organic layers were combined, dried with
MgSO4, filtered and the solvent was evaporated under reduced
pressure. The crude product was purified via column
chromatography (PE : EE = 90 : 10). The clean product (R,S,S)-
17 could be isolated as a colourless oil [1.06 g (4.37 mmol, 97%,
>98% ee)].
Dienes (S,S,S)-17 and (R,R,R)-17 have been synthesized
according to the same protocol.
(1R,1'S,2'S)-1-(2'-Phenylcyclopropyl)but-3-en-1-yl
acrylate
[(R,S,S)-17]
(R,R)-12 could be synthesized with the same protocol, using
119 mg (580 μmol, 1.0 equiv.) of (1R,2R)-N,N-methoxymethyl-
2-phenylcyclopropancarboxamide [(R,R)-11] at -78 °C with 1.16
mL (1.16 mmol, 2.0 equiv.) of a 1 M allylmagnesium bromide
solution in diethylether. The mixture was stirred for 30 min at -78
°C and hydrolysis with saturated ammonium carbonate solution
at -60 °C. The mixture of two layers was warmed to room
temperature and 2 mL of 1 M HCl was added. It was added water
and ether until both layers were clear. The layers have been
separated and the organic layer was extracted with diethylether a
couple of times, followed by two times with ethyl acetate. The
combined organic layers were dried with MgSO4, filtered and the
solvent was evaporated. The crude product was purified by
column chromatography (PE : EE 95 : 5). 70 mg (38 μmol, 66%,
98% ee) of ketone (R,R)-12 could be isolated as a colourless oil.
ͦͤ
Rf = 0.8 (PE : EE = 70 : 30); ꢀꢁꢂꢀ = +147 (c = 1.0, CHCl3);
MS (EI, 70 eV): m/z (%) = 241 (<5) [M+], 207 (<5)
[(C13H13O2)+], 187 (<5) [(C13H15O)+], 170 (19) [(C13H14)+], 161
(28) [(C11H13O)+], 142 (10) [(C11H10O)+], 129 (56) [(C10H9)+],
117 [(C9H9)+], 104 (40) [(C8H8)+], 91 (34) [(C7H7)+], 70 (15)
[(C6H7)+], 55 (100) [(C3H5O)+]. Elemental analysis: C16H18O2
(242.31 g/mol): calc.: C 79.31 H 7.49; found: C 79.22 H 7.58. IR
(ATR, film): 3077, 3028, 2944, 1721 (C=O), 1619, 1638, 1605,
1498, 1404, 1295, 1270, 1195, 1092, 1047, 983, 916, 809, 751,
1
698 cm-1. H-NMR (CDCl3, 600 MHz): δ [ppm] = 0.96 (ddd,
3J3’”a,2" = 8.9 Hz, J3”a,1” = 5.5 Hz, J3”a,3”b= 5.3 Hz, 1 Hz, 3”-Ha),
3
2
1.03 (ddd, 3J3”b,1” = 8.7 Hz, 3J3”b,2” = 5.3 Hz, 2J3”b,3”a = 5.3 Hz, 1 H,
3
3
3
3”-Hb), 1.35 (dddd, J1”,3”b = 8.7 Hz, J1”,1’ = 8.6 Hz, J1”,3”a = 5.5
Hz, 3J1”,2” = 4.5 Hz, 1 H, 1”-H), 2.07 (ddd, 3J2”,3”a = 8.9 Hz, 3J2”,3”b
= 5.3 Hz, 3J2”,1” = 4.5 Hz, 1 H, 2”-H), 2.49 (ddddd, 2J2’a,2’b = 14.3
Hz, 3J2’a,3’ = 7.5 Hz, 3J2’a,1’ = 6.8 Hz, 4J2’a,4’a = 1.2 Hz, 4J2’a,4’b = 1.2
ͦͤ
Rf = 0.2 (PE : EE = 70 : 30); (S,S)-12 ꢀꢁꢂꢀ = +475 (c = 1.2,
ͦͤ
CHCl3, 97% ee); (R,R)-12 ꢀꢁꢂꢀ = -479 (c = 0.6, CHCl3, >98%
2
3
Hz, 1 H, 2’-Ha), 2.54 (ddddd, J2’b,2’a = 14.3 Hz, J2’b,3’ = 6.6 Hz,
ee); HPLC: column: Chiracel OD-H (250 mm · 4.6 mm, Fa.
Daicel); solvent: heptane : 2-propanol = 99.8 : 0.2; flowrate: 0.5
mL/min, pressure: 33 bar; detection: UV 225 nm; tR[(S,S)-12]:
29.4 min; tR[(R,R)-12]: 32.3 min. MS (EI, 70 eV): 186 (8) [M+],
145 (91) [(M-C3H5)+], 127 (78), 117 (100) [(C9H9)+], 115 (85)
[(C9H7)+], 91 (45) [(C7H7)+], 69 (19) [(C4H5O)+]. Elemental
analyse: C13H14O2 (186.25 g/mol) calc.: C 83.83 H 7.58; found: C
83.40 H 7.63, IR (ATR, film): 3081, 3031, 1698 (C=O), 1636,
1604, 1497, 1457, 1432, 1398, 1342, 1212, 1180, 1120, 1058,
1044, 1016, 993, 918, 837, 749, 698 cm-1. 1H-NMR (CDCl3, 600
3J2’b,1’ = 5.5 Hz, J2’b,4’a = 1.3 Hz, J2’b,4’b = 1.3 Hz, 1 H, 2’-Hb),
4
4
3
3
3
4.62 (ddd, J1’,1” = 8.6 Hz, J1’,2’a = 6.8 Hz, J1’,2’b = 5.5 Hz, 1 H,
1’-H), 5.08 (dddd, 3J4’a,3’ = 10.2 Hz, 2J4’a.4’b = 2.1 Hz, 4J4’a,2’b = 1.3
4
3
Hz, J4’a,2’a = 1.2 Hz, 1 H, 4’-Ha), 5.21 (dddd, J4’b,3’ = 17.0 Hz,
2J4’b,4’a = 2.1 Hz, J4’b,2’b = 1.3 Hz, J4’b,2’a = 1.2 Hz, 1 H, 4’-Hb),
4
4
5.81 (dd, 3J3a,2 = 10.4 Hz, 2J3a,3b = 1.5 Hz, 1 H, 3-Ha), 5.83 (dddd,
3J3’,4’b = 17.0 Hz, J3’,4’a = 10.2 Hz, J3’,2’a = 7.5 Hz, J3’,2’b = 6.6
3
3
3
Hz, 1 H, 3'-H), 6.11 (dd, 3J2,3b = 17.3 Hz, 3J2,3a = 10.4 Hz, 1 H, 2-
3
2
H), 6.40 (dd, J3b,2 = 17.3 Hz, J3b,3a = 1.5 Hz, 1 H, 3-Hb), 7.04-
7.29 (m, 5 H, arom. CH). 13C-NMR (CDCl3, 151 MHz):δ [ppm]
= 13.3, 21.5, 26.3, 38.9, 76.8, 117.9,125.7, 126.1, 128.3, 128.7,
130.7, 133.4, 142.2, 165.9.
3
3
2
MHz): δ [ppm] = 1.39 (ddd, J3'a,1' = 8.1 Hz, J3'a,2' = 6.6 Hz, J
3'a,3'b = 4.2 Hz 1 H, 3'-Ha), 1.69 (ddd, 3J3'b,2' = 9.1 Hz, 3J3'b,1' = 5.3
Hz, 2J3'b,3'a = 4.2 Hz, 1 H, 3'-Hb) 2.23 (ddd, 3J1',3'a = 8.1 Hz, 3J1',3'b
=
3
3
5.3 Hz, J1',2' = 4.0 Hz, 1 H, 1'-H), 2.53 (ddd, J2',3'b = 9.1 Hz,
(1S,1'S,2'S)-1-(2'-Phenylcyclopropyl)but-3-en-1-yl
[(S,S,S)-17] and (1R,1'R,2'R)-1-(2'-Phenylcyclopropyl)but-3-en-
1-yl acrylate [(R,R,R)-17]
acrylate
3J2',3'a = 6.6 Hz, 3J2',1' = 4.0 Hz, 1 H, 2'-H), 3.36 (dt, 3J 2,3 = 6.8 Hz,
4J2,4 = 1.4 Hz, 2 H, 2-H), 5.17 (ddt, J4a,3 = 17.2 Hz, J4a,4b = 3.0
3
2
4
3
2
Hz, J4a,2 = 1.4 Hz, 1 H, 4-Ha) 5.20 (ddt, J4b,3 = 10.2 Hz, J4b,4a
=
3.0 Hz, 4J4b,2 = 1.4 Hz, 1 H, 4-Hb) 5.97 (ddt, 3J3,4a = 17.2 Hz, 3J3,4b
(S,S,S)-17: 514 mg (2.12 mmol, 89%), colourless oil.
[(R,R,R)-17: 1.3 g (5.4 mmol, 95%), colourless oil. Rf = 0.8 (PE :
EE = 70 : 30). [(R,R,R)-17 ꢀꢁꢂꢀ = -38 (c = 1.0, CHCl3). MS (EI,
3
= 10.2 Hz, J3,2 = 6.8 Hz, 1 H, 3-H), 7.08-7.29 (m, 5 H, arom.
ͦͤ
CH). 13C-NMR (CDCl3, 151 MHz): δ [ppm] = 19.2 (C-3'), 29.2
(C-2') 31.8 (C-1'), 48.7 (C-2), 119.0 (C-4), 126.1 (arom. CH),
126.6 (arom. CH), 128.5 (arom. CH), 130.5 (C-3), 140.3 (i-C),
206.6 (C-1).
70 eV): m/z (%) = 242 (<5) [M+], 201 (<5) [(M-C3H5)+], 187
(<5) [(C13H15O)+], 170 (26) [(C13H14)+], 161 (51) [(C11H13O)+],
142 (13) [(C11H10O)+], 129 (69) [(C10H9)+], 104 (44) [(C8H8)+], 91
(41) [(C7H7)+], 55 (100) [(C3H5O)+]. Elemental analysis:
C16H18O2 (242.31 g/mol): calc.: C 79.31 H 7.49; found: C 79.07
H 7.50. IR (ATR, film): 3078, 3028, 3008, 2942, 1720 (C=O),
1637, 1605, 1498, 1465, 1404, 1295, 1270, 1195, 1044, 983, 919,
808, 752, 697 cm-1. 1H-NMR (CDCl3, 600 MHz): δ [ppm] = 0.97
4.7. Synthesis of (1R,1'S,2'S)-1-(2'-Phenylcyclopropyl)but-3-en-
1-yl acrylate [(R,S,S)-17]
850 mg (4.51 mmol, 1.00 equiv.) of homoallyl alcohol
(R,S,S)-9 was dissolved in 15 mL absolute dichloromethane
under an argon atmosphere. The solution was cooled to -78 °C
when 2.32 mL ethyldiisopropylamine (13.5 mmol, 3.00 equiv.)
and 55 mg (0.45 mmol, 0.1 equiv.) DMAP was added. To this
mixture 550 μl (6.77 mmol, 1.50 equiv.) acryloyl chloride was
added slowly. The mixture was stirred 2 h at -78 °C until no
starting material could be detected (TLC control). After
hydrolysis with a saturated ammonium chloride-solution at -78
°C the mixture was warmed to RT and the two layers were
separated. The aqueous phase was extracted three times with
3
3
2
(ddd, J3''a,1'' = 8.5 Hz, J3''a,2'' = 5.3 Hz, J3''a,3''b = 5.3 Hz, 1 H, 3''-
Ha), 1.12 (ddd, 3J3''b,2'' = 8.9 Hz, 3J3''b,1'' = 5.5 Hz, 2J3''b,3''a = 5.3 Hz,
1 H, 3''-Hb), 1.37 (dddd, 3J1'',1' = 8.6 Hz, 3J1'',3''a = 8.5 Hz, 3J1'',3''b
=
3
3
5.5 Hz, J1'',2'' = 4.5 Hz, 1 H, 1''-H), 1.88 (ddd, J2'',3''b = 8.9 Hz,
3J2'',3''a = 5.3 Hz, 3J2'',1'' = 4.5 Hz, 1 H, 2''-H), 2.50-2.53 (m, 2 H, 2'-
3
3
3
H), 4.61 (ddd, J1',1'' = 8.6 Hz, J1',2' = 6.4 Hz, J1',2' = 5.9 Hz, 1 H,
3
2
4
1'-H), 5.05 (dddd, J4'a,3' = 10.2 Hz, J4'a,4'b = 2.0 Hz, J4'a,2' = 1.1
4
3
Hz, J4'a,2' = 1.1 Hz, 1 H, 4'-Ha), 5.07 (dddd, J4'b,3' = 17.1 Hz,
2J4'b,4'a = 2.0 Hz, 4J4'b,2' = 1.5 Hz, 4J4'b,2' = 1.5 Hz, 1 H, 4'-Hb), 5.80