Cyclopropanation Catalyzed by Co Porphyrins
CDC13) trans-isomer: δ 172.1, 145.8, 128.4, 127.2, 126.4, 60.4,
30.5, 27.8, 20.7, 19.8, 14.4.1H NMR (300 MHz, CDC13) cis-
isomer: δ 7.18-7.32 (m, 5H), 3.69 (m, J ) 4.2 Hz, 2H), 1.92
(dd, J ) 7.8, 5.5 Hz, 1H), 1.80 (m, 1H), 1.48 (s, 3H), 1.16 (dd,
J ) 7.8, 4.5 Hz, 1H), 0.96 (t, J ) 7.2 Hz, 3H). 13C NMR (75
MHz, CDC13) cis-isomer: δ 171.2, 141.8, 128.7, 128.1, 126.6,
60.0, 32.0, 28.5, 28.4, 19.4, 13.9. HRMS-EI ([M]+): calcd for
C13H16O2 204.1150, found 204.1152 with an isotope distribution
pattern that is the same as the calculated one.
Eth yl 2-(4-m eth ylp h en yl)cyclop r opa n e-1-ca r boxyla te22
was synthesized from 4-methylstyrene. 1H NMR (300 MHz,
CDC13) trans-isomer: δ 7.11 (d, J ) 7.8 Hz, 2H), 7.01 (d, J )
8.1 Hz, 2H), 4.19 (q, J ) 7.2 Hz, 2H), 2.51 (ddd, J ) 9.3, 6.3,
4.2 Hz, 1H), 2.33 (s, 3H), 1.88 (ddd, J ) 8.4, 5.1, 4.2 Hz, 1H),
1.59 (ddd, J ) 9.0, 5.4, 4.5 Hz, 1H), 1.26-1.36 (m, 1H), 1.30
(t, J ) 7.2 Hz, 3H). 13C NMR (75 MHz, CDC13) trans-isomer:
δ 173.5, 137.0, 136.0, 129.1, 126.0, 60.6, 25.9, 24.0, 20.9, 16.9,
14.2. 1H NMR (300 MHz, CDC13) cis-isomer: δ 7.18 (d, J )
7.8 Hz, 2H), 7.09 (d, J ) 8.1 Hz, 2H), 3.92 (q, J ) 7.2 Hz, 2H),
2.56 (m, 1H), 2.32 (s, 3H), 2.07 (ddd, J ) 9.3, 7.8, 5.6 Hz, 1H),
1.59 (ddd, J ) 9.0, 5.4, 4.5 Hz, 1H), 1.26-1.36 (m, 1H), 1.03
(t, J ) 7.2 Hz, 3H). 13C NMR (75 MHz, CDC13) cis-isomer: δ
171.0, 136.0, 133.4, 129.1, 128.5, 60.6, 25.1, 21.6, 21.0, 14.0,
11.1. HRMS-EI ([M]+): calcd for C13H16O2 204.1150, found
204.1153 with an isotope distribution pattern that is the same
as the calculated one.
calcd for C16H22O2 246.1620, found 246.1610 with an isotope
distribution pattern that is the same as the calculated one.
Eth yl 2,2-d ip h en ylcyclop r op a n e-1-ca r boxyla te21b,22 was
1
synthesized from 1,1-diphenylethylene. H NMR (CDC13): δ
7.10-7.36 (m, 10H), 3.90 (m, 2H); 2.53 (dd, J ) 8.4, 6.0 Hz,
1H), 2.16 (dd, J ) 5.9, 4.8 Hz, 1H), 1.56 (dd, J ) 8.1, 4.8 Hz,
1H), 0.99 (t, J ) 7.2 Hz). 13C NMR (75 MHz, CDC13): δ 170.5,
144.7, 140.1, 129.6, 128.3, 128.2, 127.5, 126.8, 126.4, 60.3, 39.7,
28.9, 20.0, 13.9. HRMS-EI ([M]+): calcd for C18H18O2 266.1307,
found 266.1298 with an isotope distribution pattern that is
the same as the calculated one.
Syn th esis of 5,10,15,20-tetr a k is(2,6-d im eth oxyp h en yl)-
21H,23H-p or p h yr in (1).16 An oven-dried, three-necked, 2-L,
round-bottomed flask equipped with a magnetic stirring bar
and a gas-dispersion tube was charged with 2,6-dimethoxy-
benzaldehyde (2.5 g, 0.015 mol), pyrrole (1.04 mL, 0.015 mol),
and chloroform (1.5 L). The solution was purged with nitrogen
for 15 min. Boron trifluoride diethyl etherate (0.570 mL, 2.16
mmol) was added via syringe and the flask was wrapped with
aluminum foil to shield it from light. The solution was stirred
under nitrogen atmosphere at room temperature 1.5 h, and
2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (2.55 g, 0.0112
mol) was added as powder at one time. The flask was then
immersed in a 65 °C bath for another 1.5 h and cooled to room
temperature, and 10 mL of triethylamine was added to
neutralize the excessive acid. The reaction solution was then
directly poured on the top of a silica gel column that was
packed with dichloromethane. The column was eluted with a
mixture of dichloromethane and ethyl acetate (9:1). The
fractions containing pure product were pooled and concen-
trated on a rotary evaporator. The residue was suspended in
a small volume of acetone, and the precipitate of product was
collected on a funnel and washed with hexanes to afford the
title compound as a purple crystal-like solid (1.31 g, 40.8%).
1HNMR (CDCl3, 300 MHz): δ 8.65 (s, 8H), 7.66 (t, J ) 8.7 Hz,
4H), 6.94 (d, J ) 8.1 Hz, 8H), 3.47 (s, 24H), -2.52 (s, 2H).
HRMS-EI ([M+]): calcd for C52H46N4O8 854.3316, found
854.3324 with an isotope distribution pattern that is the same
as the calculated one.
Syn th esis of 5,10,15,20-tetr a k is(2,6-d ih yd r oxyp h en yl)-
21H,23H-p or p h yr in (2).16 A 50-mL, round-bottomed flask
equipped with a magnetic stirring bar and a gas-dispersion
tube was charged with compound 1 (1.31 g, 1.53 mmol) and
anhydrous dichloromethane (25 mL). The solution was purged
with nitrogen for 5 min and boron tribromide (5 mL, 0.053
mol) was added via syringe. The solution was stirred gently
under nitrogen atmosphere at room temperature for 5 h, and
20 mL of water was added carefully. The mixture was stirred
thoroughly for 20 min and transferred to a separatory funnel.
The product was extracted with ethyl acetate and concentrated
on a rotary evaporator. The residue was suspended in a small
volume of acetone and the product was collected on a funnel
and washed with hexanes to afford the title compound as
purple solid (1.0 g, 88%). 1HNMR ((CD3)2CO, 300 MHz): δ 8.88
(s, 8H), 8.13 (s, 4H,), 7.48 (t, J ) 8.1 Hz, 4H), 6.87 (d, J ) 8.1
Hz, 8H), 5.83 (s, 4H), -2.68 (s, 2H). HRMS-EI ([M+]): calcd
for C44H30N4O8 742.2064, found 742.2043 with an isotope
distribution pattern that is the same as the calculated one.
Eth yl 2-(2-m eth ylp h en yl)cyclopr op a n e-1-ca r boxyla te22
was synthesized from 2-methylstyrene. 1H NMR (300 MHz,
CDC13) trans-isomer: δ 7.00-7.22 (m, 4H), 4.22 (q, J ) 7.2
Hz, 2H), 2.54 (ddd, J ) 9.0, 6.6, 4.2 Hz), 2.41 (s, 3H), 1.81 (m,
1H), 1.60 (m, 1H), 1.24-1.40 (m, 1H), 1.32 (t, J ) 7.2 Hz, 3H).
13C NMR (75 MHz, CDC13) trans-isomer: δ 173.8, 137.9, 137.8,
1
129.8, 126.6, 125.8, 60.6, 24.6, 22.3, 19.5, 15.3, 14.3. H NMR
(300 MHz, CDC13) cis-isomer: δ 7.06-7.19 (m, 4H), 3.78 (q, J
) 7.2 Hz, 2H), 2.55 (m, 1H), 2.27 (s, 3H), 2.09 (m, 1H), 1.68
(m, 1H), 1.28 (m, 1H), 0.86 (t, J ) 7.2 Hz, 3H). 13C NMR (75
MHz, CDC13) cis-isomer: δ 171.1, 138.0, 134.8, 129.3, 129.0,
126.7, 125.3, 59.9, 24.4, 21.0, 19.3, 13.9, 11.1. HRMS-EI ([M]+):
calcd for C13H16O2 204.1150, found 204.1141 with an isotope
distribution pattern that is the same as the calculated one.
Eth yl 2-(3-m eth ylp h en yl)cyclopr op a n e-1-ca r boxyla te24
was synthesized from 3-methylstyrene. 1H NMR (300 MHz,
CDC13) trans-isomer: δ 6.92-7.23 (m, 4H), 4.21 (q, J ) 7.2
Hz, 2H), 2.52 (ddd, J ) 9.3, 6.3, 4.2 Hz, 1H), 2.36 (s, 3H), 1.93
(ddd, J ) 8.4, 5.1, 3.9 Hz, 1H), 1.62 (m, 1H), 1.28-1.39 (m, 1
H), 1.31 (t, J ) 7.2 Hz, 3H). 13C NMR (75 MHz, CDC13) trans-
isomer: δ 173.4, 140.0, 138.0, 128.3, 127.2, 126.9, 123.1, 60.6,
26.1, 24.1, 21.3, 17.0, 14.2. 1H NMR (300 MHz, CDC13) cis-
isomer: δ 6.94-7.19 (m, 4 H), 3.93 (q, J ) 7.2 Hz, 2H), 2.58
(m, 1H), 2.35 (s, 3H); 2.10 (ddd, J ) 9.6, 8.1, 6.0 Hz, 1H), 1.73
(m, 1H), 1.28-1.39 (m, 1H), 1.02 (t, J ) 7.2 Hz, 3H). 13C NMR
(75 MHz, CDC13) cis-isomer: δ 171.0, 137.3, 136.4, 130.0,
127.7, 126.2, 60.1, 25.4, 21.6, 14.0, 11.0. HRMS-EI ([M]+):
calcd for C13H16O2 204.1150, found 204.1155 with an isotope
distribution pattern that is the same as the calculated one.
Eth yl 2-[4′-(ter t-bu tyl)p h en yl]cyclop r op a n e-1-ca r box-
yla te22 was synthesized from 4-tert-butylstyrene. 1H NMR (300
MHz, CDC13) trans-isomer: δ 7.34 (d, J ) 8.4 Hz, 2H), 7.09
(d, J ) 8.1 Hz, 2H), 4.21 (q, J ) 7.2 Hz, 2H), 2.54 (ddd, J )
9.0, 6.9, 4.5, 1H), 1.94 (ddd, J ) 8.4, 5.1, 4.2 Hz, 1H), 1.63 (m,
Syn th esis of 5,10,15,20-Tetr a k is(2′,6′-bis(ca m p h a n yl-
oxy)p h en yl)-21H,23H-p or p h in e (3).17 A solution of (1S)-
(-)-camphanic chloride (0.8672 g, 20-fold) in dried THF (10
mL) was added dropwise into a solution of 2 (0.1484 g) in dried
THF (40 mL) in an ice-water bath under a nitrogen atmo-
sphere. After a solution of p-(dimethylamino)pyridine (0.4888
g) in dried THF (10 mL) was added, the reaction mixture was
heated under reflux. After 14 h, it was allowed to cool to room
temperature and the solvent was removed by rotary evapora-
tion. The residue was extracted with CHCl3. The organic phase
was washed with 0.1 N HCl (2×), 5 w% Na2CO3 (1×) and water
(1×), and dried over anhydrous Na2SO4. After concentration,
it is subjected to chromatography (CHCl3:MeOH ) 30:1) to
afford the title compound (0.3765 g, 86%). 1H NMR (300 MHz,
1H), 1.34-1.38 (m, 1H), 1.35 (s, 9H), 1.32 (t, J ) 7.2, 3 H). 13
C
NMR (75 MHz, CDC13) trans-isomer: δ 173.4, 149.3, 137.0,
1
125.7, 125.3, 60.5, 34.4, 31.3, 25.8, 24.1, 16.9, 14.2. H NMR
(300 MHz, CDC13) cis-isomer: δ 7.28 (d, J ) 8.1 Hz, 2H), 7.19
(d, J ) 8.4 Hz, 2H), 3.86 (AB of ABX3, J ) 7.2, 3.3 Hz, 2H),
2.54 (m, 1H), 2.05 (ddd, J ) 9.2, 7.8, 5.7 Hz, 1H), 1.70 (m,
1H), 1.30 (m, 1H), 1.29 (s, 9H), 0.92 (t, J ) 7.2 Hz, 3H). 13C
NMR (75 MHz, CDC13) cis-isomer: δ 171.0, 149.3, 133.4, 128.8,
124.7, 60.0, 34.3, 31.2, 25.0, 21.7, 13.8, 11.0. HRMS-EI ([M]+):
(24) Hixson, S. S.; Franke, L. A.; Gere, J . A.; Xing, Y. D. J . Am.
Chem. Soc. 1988, 110, 3601.
J . Org. Chem, Vol. 68, No. 21, 2003 8183