Palladium-catalyzed cross-coupling reaction of cyclopropylboronic acids with aryl triflates

Article abstract of DOI:10.1055/s-2000-6313

In the presence of appropriate base and NaBr, the Suzuki- type reaction of aryl triflates and trans-cyclopropylboronic acids proceed readily to give pure trans-cyclopropylarenes in good to high yields. For the reaction of general aryl triflates, the base KF·2H₂O is efficient, but in the case of aryl triflates bearing electron donating groups, KF·2H₂O as a base makes the unexpected phenylaryl exchange between the phenyl of Pd(PPh₃)₄ and the aryl of triflate to occur. The use of K₃PO₄·3H₂O instead of KF·2H₂O can inhibit the unexpected phenyl-aryl exchange, but the yield of the product is somewhat decreased. The coupling reaction of aryl triflates with the optically active cyclopropylboronic acids, which were easily obtained in good yield and with good to excellent ee (up to 94%) by the asymmetric cyclopropanation of alkenylboronates with optically pure TMTA auxiliary, was also investigated. During the coupling reaction, the absolute configuration of the cyclopropyl group was retained. Thus, a novel method to prepare aryl- substituted cyclopropanes, including highly optically active cyclopropanes, from phenols or arylamines was provided.

Full text of DOI:10.1055/s-2000-6313

PAPER
1095
Palladium-Catalyzed Cross-Coupling Reaction of Cyclopropylboronic Acids
with Aryl Triflates
Min-Liang Yao, Min-Zhi Deng*
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Academia Sinica, 354 FengLin Lu, Shanghai 200032,
China
Fax: 00862164166128; E-mail: dengmz@pub.sioc.ac.cn
Received 17 December 1999; revised 1 March 2000
(Eq. 2), but the yield was unsatisfactory. At the same time,
Abstract: In the presence of appropriate base and NaBr, the Suzuki-
our group reported6 the palladium catalyzed cross cou-
pling of aryl bromides with cyclopropylboronic acids to
give aryl-substituted cyclopropanes in high yield (Eq. 3).
type reaction of aryl triflates and trans-cyclopropylboronic acids
proceed readily to give pure trans-cyclopropylarenes in good to
high yields. For the reaction of general aryl triflates, the base
KF◊2H2O is efficient, but in the case of aryl triflates bearing electron
donating groups, KF◊2H2O as a base makes the unexpected phenyl-
aryl exchange between the phenyl of Pd(PPh3)4 and the aryl of tri-
flate to occur. The use of K3PO4◊3H2O instead of KF◊2H2O can in-
hibit the unexpected phenyl-aryl exchange, but the yield of the
product is somewhat decreased. The coupling reaction of aryl tri-
flates with the optically active cyclopropylboronic acids, which
were easily obtained in good yield and with good to excellent ee (up
to 94%) by the asymmetric cyclopropanation of alkenylboronates
with optically pure TMTA auxiliary, was also investigated. During
the coupling reaction, the absolute configuration of the cyclopropyl
group was retained. Thus, a novel method to prepare aryl-substitut-
ed cyclopropanes, including highly optically active cyclopropanes,
from phenols or arylamines was provided.
Equation 1
Equation 2
Equation 3
Key words: Suzuki-coupling reaction, cyclopropylboronic acids,
aryl triflates, optically active cyclopropylboronic acids, trans-cy-
clopropylarenes
The stereo defined cyclopropane moiety, especially the
optically active cyclopropane moiety is present in many
natural compounds with biological activities.1 More inter-
estingly, the cyclopropanes derivatives have many versa-
tile synthetic utilities.2 Thus, the exploration of an
efficient method to prepare stereo defined cyclopropane is
still significant. Among the various methodologies of pal-
ladium-catalyzed coupling of organic electrophiles with
organometal compounds to form carbon-carbon bond, the
Suzuki-type reaction3 recently attracted the increasing in-
terests of many chemists due to its attractive features.
Yields are high under mild conditions, functional groups
on either coupling partner are tolerated, and the reaction is
unaffected in the presence of water.
Although aryl bromides can couple smoothly with orga-
nometallic reagents, aryl triflates have been recognized as
especially valuable partners in the cross-coupling reac-
tion,7 in part, due to their easy access from phenols or are-
nediazonium tetrafluoroborate salt precursors.8 In the
palladium catalyzed cross-coupling reactions of orga-
noboron compounds, it has been found that aryl- and alk-
enyl-triflates were good substitutes for the corresponding
halides while triflates showed lower reactivity in the cata-
lytic cycle.9 The Suzuki-type reaction of triflates with
9-primary alkyl-9-BBN9 or methaneboronic acid10 have
been reported, however, to the best of our knowledge, the
coupling reaction of triflate with secondary alkyl orga-
noboron compounds has not been studied.
It is well known that the cyclopropyl group has some sp2
character,11 and the success of cyclopropylboronic acids
with aryl bromides indicates that these special secondary
alkylboronic acids also have some similar chemical prop-
erties with alkenyl boronic acids, at least in the cross-cou-
pling reaction. To extend the scope of the Suzuki-type
reaction of cyclopropylboronic acids, we have firstly stud-
ied the cross-coupling reaction of cyclopropylboronic ac-
The methods applied so far to prepare aryl-substituted cy-
clopropanes by Suzuki-type reaction include: (i) The cou-
pling
reaction
of
arylboronic
acids
with
iodocyclopropanes was reported by Charette4 (Eq. 1). The
preparation of the iodocyclopropanes, however, was an-
noying owing to the use of toxic organotin reagent and
their yields were low, which limited its application. (ii)
The coupling reaction of cyclopropylboron compounds
with organic aryl halides. The reaction of cyclopropylbo-
ronates with aryl bromides to give the anticipated cross-
coupling products was firstly reported by Marsden5
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M.-L. Yao, M.-Z. Deng
PAPER
ids with aryl triflates, and herein, we wish to report the To evaluate the scope of the coupling reaction, we inves-
results.
tigated the reaction of various aryl triflates with cyclopro-
pylboronic acids under the optimized reaction conditions
(Table 1, entry 6). The results are shown in Table 2.
Initially, we examined the cross coupling of trans-2-pen-
tyl-cyclopropylboronic acid 1 with phenyl triflate 2 to es-
tablish the optimized reaction conditions (Table 1).
As can been seen from Table 2, the nature of the substitu-
ent on aryl triflates did affect the reaction greatly. Using
KF◊2H2O as a base (the optimized reaction condition in
Table 1), phenyl triflate and aryl triflates bearing electron
withdrawing functional groups can couple smoothly with
various trans-cyclopropylboronic acids. However, for
aryl triflates bearing electron donating groups, the reac-
tion afforded only a trace amount of the expected cross-
coupling products, with about 25% undesired cross-cou-
pling products 3a or 3h (entries 4, 9 and 11). The produc-
tion of 3a or 3h can be rationalized by an aryl-aryl
exchange between the phenyl of Pd(PPh3)4 and the aryl of
triflate in the intermediate palladium(II) complex
(Scheme 1). This phenyl-aryl exchange phenomenon was
sometimes observed in the cross-coupling reactions of
phenylboronic acid with aryl bromides bearing donating
groups, since in such cases, the migration of aryl group
from palladium to phosphorus was greatly enhanced.13
Firstly, we adopted the cross-coupling reaction conditions
for aryl triflates with organoborons,9a however, the reac-
tion did not take place (entry 1). The coupling reaction
conditions of aryl triflates with organostannanes12 was
first established by Stille, and considering that a base was
necessary for the Suzuki-type reaction, we conducted the
reaction in the presence of K3PO4◊3H2O under the Stille
reaction conditions, unfortunately, the reaction did not oc-
cur (entry 2). When the reaction was conducted in the
presence of the catalytic amount of Pd(PPh3)4, with
K3PO4◊3H2O or KF◊2H2O as the base, and toluene as the
solvent, the expected trans-2-pentyl-(cyclopropyl)ben-
zene was obtained (entries 3, 4). However, the yield was
low and the decomposition of the palladium catalyst to
palladium black was observed at an early stage of the re-
action. Addition of 1 equivalent of NaBr avoided the pre-
mature decomposition of the palladium catalyst and
substantially improved the yield of the coupling product
(entries 5, 6). The effect of polar solvents, DMF and diox-
ane, on the reaction was also investigated and it was found
that both solvents were unsuitable (entries 7, 8). Consid-
ering that Pd(PPh3)2Cl2 is insensitive to the air and can be
stored or handled more easily, we tried to use
Pd(PPh3)2Cl2 to replace Pd(PPh3)4 , but the reaction failed
(entry 9).
Table 1 Coupling Reaction of trans-Pentylcyclopropylboronic
Acid with Phenyl Triflatea
Scheme 1
Yieldb
(%)
Entry Conditions
When the stronger base K3PO4◊3H2O was used instead of
KF◊2H2O, the phenyl-aryl exchange was decreased and
the reaction worked smoothly giving the anticipated prod-
uct in moderate yield. The using of K3PO4◊3H2O might
cause the rate of transmetallation to accelerate in cycle 1
(Scheme 1) . Consequently, for the palladium-catalyzed
cross-coupling reaction of trans-cyclopropylboronic ac-
ids with aryl triflates, KF◊2H2O is the efficient base for
general aryl triflates, however, for aryl triflates bearing
electron-donating groups, the use of K3PO4◊3H2O instead
of KF◊2H2O as a base, is necessary.
1
2
3
4
5
6
7
8
9
1,4-Dioxane, K3PO4 3H2O, Pd(PPh3)4
0
0
DMF, NaBr, K3PO4 3H2O, Pd(PPh3)2Cl2
toluene, K3PO4 3H2O, Pd(PPh3)4
43
54
61
75
trace
0
toluene, KF 2H2O, Pd(PPh3)4
toluene, K3PO4 3H2O, NaBr, Pd(PPh3)4
toluene, KF 2H2O, NaBr, Pd(PPh3)4
DMF, KF 2H2O, NaBr, Pd(PPh3)4
1,4-Dioxane, KF 2H2O, NaBr, Pd(PPh3)4
The results of Table 2 also demonstrated that the cross-
coupling conditions were mild, the sensitive groups, such
as, carbonyl and nitro being unaffected during the reaction
(entries 2, 3, 5, 7, 10-14). The yields of these cross-cou-
pling products were good to high. The 2D-1H NMR
spectrum14 of product 3j showed clearly that it was the
toluene, KF 2H2O, NaBr, Pd(PPh3)2Cl2
0
o
a Reactions were carried out at 100 C for 24 h using 3% mmol of cat-
alyst, trans-pentylcyclopropylboronic acid (0.55 mmol), phenyl tri-
flate (0.5 mmol) in 3 mL solvent.
b Isolated yield based on phenyl triflate.
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Palladium-Catalyzed Cross-Coupling Reaction of Cyclopropylboronic Acids with Aryl Triflates
Table 2 Cross-Coupling Reaction of Aryl Triflates with trans-Cyclopropylboronic Acidsa
1097
a Reactions were carried out at 100 oC using 3% mmol of Pd(PPh3)4, cyclopropylboronic acid (1.1 mmol), aryl
triflate (1.0 mmol), KF◊2H2O (3.3 equiv), NaBr (1 equiv) in toluene (4 mL).
b All the products gave satisfactory elemental analysis, 1H NMR, MS and IR spectra. The configuration of prod-
ucts were determined by 1H NMR (400 MHz).
c Isolated yields based on aryl triflates.
d K3PO4◊3H2O was used instead of KF◊2H2O.
e About 28% 3a was obtained.
f About 23% 3h was obtained.
pure trans-isomer, indicating that the configuration of the hydrolysis, gave the (1R,2R)-2-phenylcyclopropylboronic
cyclopropyl group was retained during the reaction. acid (6b).
Then we studied the corresponding reaction of optically The results of the reaction of optically active cyclopropy-
active cyclopropylboronic acids. According to our previ- lboronic acids and aryl triflates are shown in Table 3. The
ous procedure,15 the optically active cyclopropylboronic cross-coupling product (Table 3, 3br) of optically active
acids
was obtained (Scheme 2) using chiral cyclopropylboronic acids 6b and phenyl triflate was of
auxiliary N,N,N’,N’-tetramethyltartaric acid diamide (1R,2R)-configuration, since it had the same specific rota-
(TMTA). For example, asymmetrical cyclopropanation of tion sign as that of reported (1R,2R)-1,2-diphenyl-cyclo-
the (E)-styrylboronic ester of (+)-TMTA 4b, followed by propane.16 In addition, it was found that the reactions of
cyclopropylboronic acids bearing the same optical purity
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M.-L. Yao, M.-Z. Deng
PAPER
In conclusion, the cross-coupling reaction of aryl triflates
and cyclopropylboronic acids was studied. The base se-
lected for the reaction is important, for general aryl tri-
flates KF◊2H2O is efficient, but for aryl triflates bearing
electron donating groups, the use of K3PO4◊3H2O instead
of KF◊2H2O, is necessary. In addition, using available
pure TMTA as the auxiliary, alkenylborate esters could be
easily asymmetrically cyclopropanated to give the corre-
sponding optical cyclopropylboronic acids with high opti-
cal activity. The cross-coupling of these optically active
cyclopropylboronic acids with aryl triflates led to the op-
tically active aryl-substituted cyclopropanes, which have
the same configuration as that of the cyclopropylboronic
acids used. Thus, a novel method to prepare stereo defined
aryl-substituted cyclopropanes, including optically active
aryl-substituted cyclopropanes from phenols or ary-
lamines, is provided.
Scheme 2
with different aryl triflates gave the corresponding cou-
pling products with similar optical purities (Table 3, en-
tries 1 and 2, 3 and 4, 6 and 7). These facts indicated that
the absolute configuration of the cyclopropyl group was
retained during the coupling reaction.
All reactions were performed under Ar atmosphere. The aryl tri-
flates were prepared according to the literature procedure.12 Cyclo-
propylboronic acids and the optically active cyclopropylboronic
acids were prepared according to our previous procedure.6,15 Mps
are uncorrected. 1H NMR spectra were recorded on Brucker AMX-
300 (300 MHz), using CDCl3 as the solvent with TMS as an internal
Table 3 Coupling Reactions of Optically Active Cyclopropylboronic Acids with Aryl Triflatesa
o
aReations were carried out at 100 C using 3% mmol of Pd(PPh3)4, cyclopropylboronic acid (1.1 equiv), aryl
triflate (1.0 equiv), KF◊2H2O (3.3 equiv), NaBr (1 equiv) in toluene (4 mL).
b Isolated yields based on aryl triflates.
c Determined by HPLC (Chiralcel AD).
d Determined by HPLC (Chiralcel OJ).
e Determined by HPLC (Chiralcel OD).
Synthesis 2000, No. 8, 1095–1100 ISSN 0039-7881 © Thieme Stuttgart · New York

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Palladium-Catalyzed Cross-Coupling Reaction of Cyclopropylboronic Acids with Aryl Triflates
1099
standard. Mass spectra were obtained on a HP5989A spectrometer.
Elemental analyses were conducted using a Foss-Heraeus Vario
EL instrument. IR spectra were recorded on a Shimadzu IR-440 in-
frared spectrometer. Optical rotations were measured using a Per-
kin-Elmer 241 MM polarimeter with a thermally jacketed 10 cm
MS (EI): m/z = 244 (M+, 31.22), 230 (23.39), 229 (100), 145
(31.34), 117 (26.14), 91 (12.01), 57 (43.72), 41 (18.43).
Anal. calcd for C18H28: C, 88.45; H, 11.55. Found: C, 88.60; H,
11.60.
3e: White solid; mp = 88-90oC.
IR (KBr): n = 3026, 1749, 1597, 1510, 1494, 916, 823 cm-1.
1H NMR: d = 8.14-8.19 (d, J= 9.0 Hz 2H), 7.15-7.36 (m, 7H),
2.23-2.32 (m, 2H, H, H), 1.53-1.68 (m, 2H, H, H).
MS (EI): m/z = 239 (M+, 93.35), 222 (61.13), 193 (35.66), 192
(100), 191 (51.69), 178 (48.14), 115 (77.08), 91 (40.83).
o
cell at 20 C. The ee values were determined by chiral HPLC on
Chiralcel AD column, Chiralcel OJ column and Chiralcel OD col-
umn.
Coupling Reaction; General Procedure
Aryl triflate (1 mmol), cyclopropylboronic acid (1.1 mmol),
Pd(PPh3)4 (35 mg, 3% mmol), KF◊2H2O (310 mg, 3.3 mmol), NaBr
(102 mg, 1 mmol) were placed in a flask under Ar atmosphere. De-
gassed toluene (4 mL) was added, the reaction mixture was stirred
at 100 oC, and was monitored by TLC. After the reaction was com-
pleted, the reaction mixture was cooled to r.t., and H2O (10 mL) was
added. The mixture was then extracted with petroleum ether
(2¥10 mL). The combined organic layer was washed with brine
(3¥10 mL) and dried (MgSO4). Removal of petroleum in vacuo, fol-
lowed by silica gel chromatography (0-20% Et2O in petroleum)
gave the corresponding trans-cyclopropylarenes 3a-3n. Their mi-
croanalyses and spectral data are given below.
Anal. calcd for C15H13NO2: C, 75.30; H, 5.48; N, 5.85. Found: C,
75.42; H, 5.46; N, 5.92.
3er: ee: 89%; [a]D20 -541.3 (c 1.02, CHCl3).
3es: ee: 94%; [a]D20 +555.9 (c 0.38, CHCl3).
3f: Colorless oil.
IR (film): n = 3051, 1604, 1500, 1452, 1031, 778, 736, 697 cm-1.
1H NMR: d = 7.18-7.37 (br, 10H), 2.19-2.24 (m, 2H, H, H), 1.48-
1.53 (m, 2H, H, H).
MS (EI): m/z = 195 (MH+, 15.44), 194 (M+, 100), 193 (71.38), 179
3a: Colorless oil.
IR (film): n = 2915, 1605, 1500, 1460, 1025, 755, 700 cm-1.
(41.38), 178 (33.90), 117 (11.15), 116 (19.34), 115 (31.32).
1H NMR: d = 7.06-7.29 (m, 5H), 1.62-1.65 (ddd, J = 8.9, 4.8, 4.3
Hz 1H), 1.31-1.47 (m, 8H, 4 ¥ CH2), 1.01-1.13 (m, 1H), 0.88-0.94
(m, 4H, CH3, H), 0.85-0.87 (m, 1H).
MS (EI): m/z = 188 (M+, 11.18), 118 (9.43), 117 (63.58), 116
(10.03), 115 (21.38), 105 (18.14), 104 (100), 91 (32.53).
Anal. calcd for C15H14: C, 92.74; H, 7.26. Found: C, 92.40; H, 7.31.
3fr: ee: 89%; [a]D20 -356.2(c 0.78, CHCl3).
3fs: ee: 94%; [a]D20 +392.0(c 0.87, CHCl3).
3g: Colorless oil.
IR (film): n = 3022, 1661, 1602, 1449, 1318, 1278, 751, 739, 697
Anal. calcd for C14H20: C, 89.30; H, 10.70. Found: C, 89.33; H,
10.52.
cm-1.
1H NMR: d = 7.14-7.80 (m, 14H), 2.16-2.29 (m, 2H, H, H), 1.50-
1.60 (m, 2H, H, H).
MS (EI): m/z = 298 (M+, 36.12), 297 (100), 221 (31.23), 193
(46.11), 178 (26.84), 115 (29.81), 105 (78.08), 77 (30.49).
3b: Colorless oil.
IR (film): n = 2930, 1602, 1518, 1345, 1115, 858, 748, 692 cm-1.
1H NMR: d = 8.07-8.12 (d, J= 8.7 Hz, 2H), 7.10-7.15 (d, J= 8.7
Hz, 2H), 1.67-1.73 (ddd, J= 8.5, 4.7, 4.5 Hz, 1H), 1.29-1.44 (m,
8H, 4 ¥ CH2), 1.11-1.18 (m, 1H), 0.86-1.04 (m, 5H, CH3, H, H).
Anal. calcd for C22H18O: C, 88.56; H, 6.08. Found: C, 88.58; H,
6.20.
MS (EI): m/z = 234 (MH+, 42.57), 150 (19.29), 149 (100), 137
(19.51), 119 (49.00), 116 (43.57), 91 (30.28), 15 (45.10).
3h: Colorless oil.
IR (film) n = 3028, 2973, 1600, 1497, 1458, 752, 689 cm-1.
1H NMR: d = 7.10-7.26 (m, 5H), 1.63-1.66 (ddd, J= 8.9, 4.8, 4.2
Hz, 1H), 1.43-1.62 (m, 6H, 3 ¥ CH2), 1.01-1.13 (m, 1H), 0.88-
0.94 (m, 4H, CH3, H), 0.85-0.87 (m, 1H).
Anal. calcd for C14H19NO2: C, 72.07; H, 8.21; N, 6.00. Found: C,
72.10; H, 8.43; N, 6.17.
3br: ee: 85%; [a]D20 -105.9 (c 0.23, CHCl3).
3c: Colorless oil.
IR (film): n = 2901, 1660, 1605, 1448, 1315, 1275, 940, 698 cm-1.
MS (EI): m/z =174 (M+, 18.43), 188 (11.00), 117 (70.75), 115
(20.54), 105 (10.33), 104 (100), 103 (9.39), 91 (26.57).
1H NMR: d = 7.70-7.79 (m, 4H), 7.46-7.59 (m, 3H), 7.09-7.12 (d,
J= 8.3 Hz, 2H), 1.65-1.70 (ddd, J= 8.5, 4.6, 4.4 Hz, 1H), 1.26-1.43
(m, 8H, 4 ¥ CH2), 1.09-1.15 (m, 1H), 0.95-1.01 (m, 1H), 0.85-
0.91 (m, 4H, CH3, H).
MS (EI): m/z = 292 (M+, 24.38), 215 (8.58), 210 (11.49), 209
(16.15), 208 (42.96), 131 (51.61), 105 (100), 77 (26.91).
Anal. calcd for C13H18: C, 89.59; H, 10.41. Found: C, 89.64; H,
10.47.
3i: Colorless oil.
IR (film): n = 3012, 1618, 1518, 1470, 1245, 1039, 824 cm-1.
1H NMR: d = 6.95-7.04 (d, J= 9.4 Hz, 2H), 6.76-6.81 (d, J= 9.4
Hz, 2H), 3.76 (s, 3H, OCH3), 1.51-1.57 (ddd, J=8.8, 4.7, 4.1 Hz,
1H), 1.25-1.47 (m, 6H, 3 ¥ CH2), 0.86-0.97 (m, 4H, CH3, H),
0.75-0.81 (ddd, J= 8.6, 4.9, 4.7 Hz, 1H), 0.64-0.70 (ddd, J= 8.7,
5.1, 4.6 Hz, 1H).
Anal. calcd for C21H24O: C, 86.26; H, 8.27. Found: C, 86.42; H,
8.56.
3cr: ee: 87%; [a]D20 -102.6 (c 0.49, CHCl3).
3cs: ee: 87%; [a]D20 +102.0(c 0.35, CHCl3).
3d: Colorless oil.
MS (EI): m/z = 204 (M+, 23.03), 147 (78.10), 91 (21.00), 69 (18.85),
57 (25.52), 45 (100), 44 (43.65), 43 (21.36).
IR (film): n = 2996, 2914, 1519, 1467, 1361, 822, 564 cm-1.
Anal. calcd for C14H20O: C, 82.29; H,9.87. Found: C, 81.92; H,
10.13.
1H NMR: d = 7.28-7.33 (d, J= 8.8 Hz, 2H), 7.00-7.04 (d, J= 8.8
Hz, 2H), 1.58-1.64 (ddd, J= 8.8, 4.6, 4.3 Hz, 1H), 1.31-1.49 (m,
17H, 4 ¥ CH2, 3¥CH3), 1.02-1.07 (m, 1H), 0.85-0.95 (m, 4H, CH3,
H), 0.72-0.78 (ddd, J= 8.7, 4.9, 4.1 Hz, 1H).
3j: Colorless oil.
IR (film): n = 2979, 1602, 1518, 1405, 1114, 858, 751, 697 cm-1.
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M.-L. Yao, M.-Z. Deng
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1H NMR (400 MHz): d = 8.09 (d, J= 8.8 Hz, 2H), 7.13 (d, J= 8.8
Hz, 2H), 1.68-1.72 (ddd, J= 8.6, 4.8, 4.5 Hz, 1H), 1.34-1.42 (m,
6H, 3 ¥ CH2), 1.11-1.15 (m, 1H), 0.97-1.03 (m, 1H), 0.94-0.96
(m, 1H), 0.88-0.92 (t, J= 7.1 Hz, 3H, CH3).
MS (EI): m/z = 219 (M+, 12.11), 150 (15.04), 149 (100), 119
(22.54), 116 (26.14), 115 (18.15), 103 (8.49), 91 (11.18).
References and Notes
(1) Levy, B. D.; Petasis, N. A.; Serhan, C. N. Nature 1997, 389,
985.
Mohapatra, D. K.; Datta, A. J. Org. Chem. 1998, 63, 642; and
references cited therein.
Connor, D. T.; Strindtmann, M. J. Org. Chem. 1978, 43, 4603.
(2) Wong, H. N. C.; Hon, M. -Y.; Tse, C. -W.; Yip, Y. -C.; Tanko,
J.; Hudlicky, T. Chem. Rev. 1989, 89, 165.
Anal. calcd for C13H17NO2: C, 71.20; H, 7.81; N, 6.39. Found: C,
71.30; H, 7.91; N, 6.60.
Feldman, K.; Berven, H. M.; Winreb, P. N. J. Am. Chem. Soc.
1993, 115, 11364.
3k: Colorless oil.
IR (film): n = 2978, 1520, 1464, 1363, 1275, 1028, 831, 564 cm-1.
1H NMR: d = 7.28-7.32 (d, J = 8.7 Hz, 2H), 6.99-7.04 (d, J = 8.7
Hz, 2H), 1.57-1.65 (ddd, J = 8.9, 4.7, 4.4 Hz, 1H), 1.31-1.49 (m,
15H, 3 ¥ CH2, 3 ¥ CH3), 1.03-1.07 (m, 1H), 0.85-0.94 (m, 4H,
CH3, H), 0.73-0.79 (ddd, J = 8.9, 4.8, 4.1 Hz, 1H).
(3) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
Suzuki, A. J. Organomet. Chem. 1999, 576, 147.
(4) Charette, A. B.; Giroux, A. J. Org. Chem. 1996, 61, 8718.
(5) Hildebrand, J. P.; Marsden, S. P. Synlett 1996, 893.
(6) Wang, X. -Z.; Deng, M. -Z. J. Chem. Soc., Perkin. Trans 1.
1996, 2663.
(7) Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1986, 108, 3033.
Saulnier, M. G.; Kadow, J. F.; Tun, M. M.; Langley, D. R.;
Vyas, D. M. J. Am. Chem. Soc. 1989, 8320.
MS (EI): m/z = 230 (M+, 18.51), 216 (18.32), 215 (100), 145
(24.15), 117 (29.64), 104 (14.41), 91 (14.30), 57 (73.96).
Anal. calcd for C17H26: C, 88.63; H, 11.37. Found: C, 88.34; H,
11.85.
(8) Stang, P. J.; Hanack, M.; Subramanian, L. R. Synthesis 1982,
85.
3l: Colorless oil.
IR (film): n = 2951, 1659, 1605, 1318, 1279, 741, 701 cm-1.
1H NMR: d = 7.42-7.77 (m, 7H), 7.08-7.11 (d, J = 8.4 Hz, 2H),
1.63-1.69 (ddd, J = 8.5, 4.7, 4.4 Hz, 1H), 1.30-1.44 (m, 6H, 3 ¥
CH2), 1.07-1.12 (m, 1H), 0.94-1.00 (ddd, J = 8.4, 4.6, 4.2 Hz, 1H),
0.83-0.91 (m, 4H, CH3, H).
Ritter, K. Synthesis 1993, 735.
(9) (a) Ohe, T.; Miyaura, N.; Suzuki, A. Synlett 1990, 221.
(b) Ohe, T.; Miyaura, N.; Suzuki, A. J. Org. Chem. 1993, 58,
2201.
(10) Mu, Y. -Q.; Gibbs, R. S. Tetrahedron Lett. 1995, 36, 5669.
(11) Wiberg, K. B. Acc. Chem. Res. 1996, 29, 229.
(12) Echavarren, A. M.; Stille, J. K. J. Am. Chem. Soc. 1987, 109,
5478.
MS (EI): m/z = 278 (M+, 27.34), 209 (12.67), 208 (33.35), 131
(46.68), 115 (13.18), 105 (100), 91 (15.60), 77 (55.21).
(13) Kong, K. -C.; Cheng, C. -H. J. Am. Chem. Soc. 1991, 113,
6313.
Anal. calcd for C20H22O: C, 86.29; H, 7.96. Found: C, 86.64; H,
7.81.
O’Keef, D. F.; Dannock, M. C.; Marcuceio, S. M.
Tetrahedron Lett. 1992, 33, 6679.
3m: Colorless oil.
IR (film): n = 2927, 1696, 1601, 1492, 1456, 823, 755 cm-1.
1H NMR: d = 10.56 (s, 1H), 7.79-7.81 (d, J = 7.7 Hz, 1H), 7.44-
7.49 (m, 1H), 7.26-7.31 (m, 1H), 7.05-7.08 (d, J = 7.6 Hz, 1H),
2.37-2.43 (ddd, J = 8.5, 4.8, 4.3 Hz, 1H), 1.33-1.58 (m, 7H, 3 ¥
CH2, H), 1.09-1.13 (m, 1H), 0.84-1.00 (m, 4H, CH3, H).
(14) The 2D-1H NMR (400 MHz, CDCl3, TMS) spectrum of
product 3j: d = 0.88-0.92 (t, 3H, CH3), 0.94-0.96 (m, 1H,
Hd), 0.97-1.03 (m, 1H, Hc), 1.11-1.15 (m, 1H, Hb), 1.34-
1.42 (m, 6H, 3 ¥ CH2), 1.68-1.72 (ddd, 1H, Ha), 7.13 (d, 2H,
He, Hf), 8.09 (d, 2H, Hi, Hj). Two of the aryl protons (d = 7.13,
He, Hf) showed very strong NOE interactions with three of the
cyclopropyl protons [d = 1.68-1.72 (Ha), 1.11-1.15 (Hb),
0.97-1.03 (Hc)], but no NOE interactions with the fourth
proton [d = 0.94-0.96 (Hd)]. Furthermore, the proton Ha
showed strong NOE interaction with the proton Hd, but none
with the protons Hb and Hc. All these facts suggested that 3j is
pure trans-2-butylcyclopropylarene.
MS (EI): m/z = 202 (M+, 0,58), 145 (11.18), 132 (11.73), 131
(46.68), 119 (13.01), 118 (100), 115 (19.77), 91 (19.45), 41 (18.68).
Anal. calcd for C14H18O: C, 83.12; H,8.97. Found: C, 82.70; H,
9.20.
3n: Colorless oil.
IR (film) n = 2928, 1697, 1601, 1491, 1457, 822, 758 cm-1.
(15) Zhou, S. -M.; Deng, M. -Z. Xia, L. -J.; Tang, M. -H. Angew.
Chem., Int. Ed. 1998, 37, 2845.
1H NMR: d = 10.57 (s, 1H), 7.79-7.82 (d, J = 7.7 Hz, 1H), 7.44-
7.49 (m, 1H), 7.26-7.31 (m, 1H), 7.06-7.09 (d, J = 7.8 Hz, 1H),
2.37-2.43 (ddd, J = 8.5, 4.8, 4.4 Hz, 1H), 1.29-1.60 (m, 9H, 4 ¥
CH2, H), 1.10-1.14 (m, 1H), 0.86-1.00 (m, 4H, CH3, H).
MS (EI): m/z = 216 (M+, 0.16), 132 (12.72), 131 (30.66), 119
(12.66), 118 (100), 115 (18.28), 104 (13.27), 91 (18.39), 41 (18.62).
Anal. calcd for C15H20O: C, 83.29; H,9.32. Found: C, 83.57; H,
9.59.
(16) Mintas, M.; Mannschreck, A. J. Chem. Soc., Chem. Commun.
1979, 602.
Acknowledgement
Article Identifier:
1437-210X,E;2000,0,08,1095,1100,ftx,en;F07999SS.pdf
We are grateful to the National Science Foundation of China for
financial support.
Synthesis 2000, No. 8, 1095–1100 ISSN 0039-7881 © Thieme Stuttgart · New York