Silver oxide mediated palladium-catalyzed cross-coupling reaction of cyclopropylboronic acids with allylic bromides

Full text of DOI:10.1021/jo0000933

4444
J . Org. Chem. 2000, 65, 4444-4446
cyclopropylboronic acid is still one of targets to which
organic chemists pay attention.
Silver Oxid e Med ia ted
P a lla d iu m -Ca ta lyzed Cr oss-Cou p lin g
The Suzuki-Miyaura coupling reactions are very im-
portant transformations of organoboranes for the con-
struction of new carbon-carbon bonds because of their
Rea ction of Cyclop r op ylbor on ic Acid s w ith
Allylic Br om id es
9
many advantages. In our previous papers, we have
Han Chen and Min-Zhi Deng*
reported the palladium-catalyzed cross coupling reactions
of cyclopropylboronic acids with aryl halides,10 heteroaro-
matic halides,11 and bromoacrylates,12 and investigated
the Suzuki-type reactions of chiral cyclopropylboronic
acids.13 Other groups also reported this type of the
reaction under the different conditions.14 For instance,
Marsden reported the palladium-catalyzed cross-coupling
of the cyclopropylboronate esters as partners with aryl
halides, in the presence of potassium tert-butoxide,14a and
Charette also reported the cross-coupling reaction of
cyclopropylboronate esters with iodocyclopropanes.14b
Recently, Oshima reported the generation of the cyclo-
propylzinc compounds and their reactions with allyl bro-
mides in the presence of CuCN‚2LiCl, giving allyl-sub-
stituted cyclopropanes.15 However, the present synthetic
approach to cyclopropylzinc is rather lengthy compared
to cyclopropylboronic acids from alkynes. To expand the
catalytic cross-coupling reactions of cyclopropylboronic
acids, we first studied the cross-coupling reactions of
cyclopropylboronic acids with allyl bromides and herein
wish to report the preliminary experiment results.
Considering the cyclopropyl group has some sp2 char-
acter,16 we initially examined the possibility of the
reaction of cyclopropylboronic acid with allylic bromide
under the coupling condition of 1-alkenylboranes with the
allyl bromides, which was reported by Suzuki long ago,17
but the reaction cannot take place (Table 1, entry 1). In
our previous study of the coupling of the cyclopropylbo-
ronic acids with aryl bromides or bromoacrylates, we
found that K3PO4‚3H2O as the base was effective,10-13 but
in the case of allylic bromide, the desired product was
not detected (Table 1, entry 2). Chartte reported that Kt-
OBu in DME was a good combination for the coupling
reaction of cyclopropylboronate ester with iodocyclopro-
panes;14b however, this condition did not lead to the
Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Academia Sinica, 354 Fenglin Lu,
Shanghai 200032, China
Received J anuary 24, 2000
The structure of cyclopropane ring is present in many
natural products, and the versatility of cyclopropanes and
their derivatives as building blocks in organic synthesis
has attracted increasing interest in recent years.1 The
diverse methods directed toward constructing the cyclo-
propane moiety have been amply demonstrated in the
literature.2 Among them, cyclopropylmetal compounds
are very useful reagents for the preparation of various
cyclopropane derivatives. Generally, they can be prepared
by the metalation of halocyclopropyl derivatives with
metal or organometallic compounds such as lithium,
butylithium,3 or direct cyclopropanation of some 1- alke-
nylmetal compounds.4 However, the synthetic approaches
to halocyclopropanes are quiet inefficient,5 and the
obtaining of some vinylmetallic compounds is very trouble-
some.6 Recently, the cyclopropylboronic acids attracted
the increasing interests of chemists, because they are
easily available by the stereodefined cyclopropanation of
the corresponding alkenyl boronic acids (esters),7 which
are readily prepared by the hydroboration of alkynes.8
Moreover, the cyclopropylboronic acids are very stable
to air and easily purified by recrystallization from water.
Thus, the expansion of the chemical transformations of
* To whom correspondence should be addressed. Fax: 86-21-
64166128.
(1) (a) Wong, H. N. C.; Hon, M.-Y.; Tse, C.-W.; Yip, Y. C.; Tanko, J .;
Hudlicky, T. Chem. Rev. 1989, 89, 165. (b) Reissig, H.-U. Top. Curr.
Chem. 1988, 144, 73-135. (c) Huddicky, T.; Reed, J . W. Rearrange-
ments of Vinylcyclopropanes and Related Systems. In Comprehensive
in Organic Synthesis; Trost, B. M., Fleiming, I., Eds.; Pergamon
Press: New York, 1991; Vol. 5, pp 889-970.
(2) (a) Patai, S., Rappoport, Z., Eds. The Chemistry of Cyclopropyl
Group; Wiley: New York, 1987. (b) Hoveyda, A. H.; Evans, D. A.; Fu,
G. C. Chem. Rev. 1993, 93, 1370. (c) Doyle, M. P.; Forbes, D. C. Chem.
Rev. 1998, 911. (d) Li, A. H.; Dai, L. X.; Aggarwal, V. K. Chem. Rev.
1997, 97, 2341.
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50, 2401. (c) Kubota, K.; Nakamuya, M.; Nakamura, E. J . Am. Chem.
Soc. 1993, 115, 5867-5868. (d) Hiyama, T.; Yamamoto, H.; Nishio,
K.; Kitatani, K.; Nozaki, H. Bull. Chem. Soc. J pn. 1979, 52, 3632-
3637.
(4) Tin: (a) Seyferth, D.; Cohen, H. M.; Inorg. Chem. 1962, 1, 913-
916. (b) Itoh, T.; Emoto, S.; Kondo, M. Tetrahedron 1998, 54, 5225-
5232. Aluminum: Zweifel, G.; Clark, G. M.; Whitney, C. C. J . Am.
Chem. Soc. 1971, 93, 1305-1307. Silicon: Hirabayashi, K.; Mori, A.;
Hiyama, T. Tetrahedron Lett. 1997, 38, 461-464.
(8) (a) Brown, H. C.; Gupta, S. K.; J . Am. Chem. Soc. 1972, 94,
4370-4371. (b) Brown, H. C.; Bhat, N. G.; Somayayi, V. Organome-
tallics 1983, 2, 1311. (c) Tucker, C. E.; Davidson, J .; Knochel, J . J .
Org. Chem. 1992, 57, 3483. (d) Brown, H. C.; Imai, T. Organmetallics
1984, 3, 1392. (e) Kamabuchi, A.; Morya, T.; Miyaura, N.; Suzuki, A.
Synth. Commun. 1993, 23, 2635. (f) Serbnik, M.; Bhat, N. G.; Brown,
H. C. Tetrahedron Lett. 1988, 29, 2635.
(9) (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.
(b) Suzuki, A. J . Organomet. Chem. 1999, 576, 147-168.
(10) Wang, X.-Z.; Deng, M.-Z. J . Chem. Soc., Perkin Trans. 1 1996,
2663-2664.
(11) Ma, H.-R.; Wang, X.-H.; Deng, M.-Z. Synth. Commun. 1999,
2477-2485.
(12) Zhou, S.-M.; Yan, Y.-L.; Deng, M.-Z. Synlett 1998, 198-200.
(13) Zhou, S.-M.; Deng, M.-Z.; Xia, L.-J .; Tang, M.-H. Angew. Chem.,
Int. Ed. 1998, 37, 2845. Also reported by: Luithle, J . E. A.; Pietruszka,
J . J . Org. Chem. 1999, 64, 8287-8297.
(14) (a) Hilderbrand, J . P.; Marsden, S. P. Synlett 1996, 893. (b)
Charette, A. B.; Freitas-Gil, R. P. Tetrahedron Lett. 1997, 38, 2809-
2812.
(15) Yachi, K.; Shnokubo, H.; Oshima, K. Angew. Chem., Int. Ed.
Engl. 1998, 37, 2515.
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V.; Rubin, M. Tetrahedron Lett. 1996, 37, 8933-8936. (b) Groves, J .
T.; Ma, K. W. J . Am. Chem. Soc. 1974, 96, 6527-6529.
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10.1021/jo0000933 CCC: $19.00 © 2000 American Chemical Society
Published on Web 06/20/2000

Notes
J . Org. Chem., Vol. 65, No. 14, 2000 4445
Ta ble 1. Effect of Ba se a n d Solven t on th e
Cr oss-Cou p lin g Rea ction a
cyclopropylboronic acids in the presence of Ag2O sus-
pended in dioxane. Surprisingly, the desired coupling
product formation was not observed, when the methyl
4-bromocrotonate was used as the partner (entry 10). The
methyl 4-bromocrotonate disappeared extremely rapidly
within 10 min (monitored by TLC), but none of the
desired product was formed. The 1H NMR and 2D-1H
NMR spectra of the products in Table 2 showed that the
configuration of the cyclopropyl group of organoboron
partner was retained, as in the other Suzuki-type reac-
tions. Table 2 also illustrated that the reaction was
substrate-controlled regioselective to give only one isomer
yieldb
(%)
entry
conditions
1
2
3
4
5
6
7
8
9
THF, KOH, reflux, 3% Pd(PPh3)4
toluene, K3PO4‚3H2O, 100 °C, 3% Pd(PPh3)4
DME, ButOK, 3% Pd(PPh3)4
0c
0c
DME, CsF, 3% Pd(PPh3)4
0c
trace
trace
51
dioxane, TlOH, 3% Pd(PPh3)4
toluene, Ag2CO3, 3% Pd(PPh3)4
toluene, Tl2CO3, 3% Pd(PPh3)4
toluene, Ag2O, 3% Pd(PPh3)4
dioxane, Ag2O, 3% Pd2(dba)3, CHCl3, 30%AsPh3 30
toluene, Ag2O, KOH, 3%PdCl2(dppf)
dioxane, Ag2O, KOH, 3%PdCl2(dppf)
1
of coupling product, as determined by H NMR.
In conclusion, we have first demonstrated the cross-
coupling reaction of cyclopropyl boronic acids with allyl
bromides, and provided a novel convenient stereocon-
trolled synthetic approach to stereodefined allyl-substi-
tuted cyclopropanes.
47
10
11
54d
64d
a
All the reactions were carried out using a mixture of the trans-
2-phenylcyclopropylboronic acid (1.0 mmol), allyl bromide (2.0
mmol), and base (2 equiv) in 4 mL of solvent, for 16 h, at 80 °C
Exp er im en ta l Section
b
(except for entry 1) under nitrogen atmosphere. Isolated yields.
c The unreacted trans-2-phenylcyclopropylboronic acid was recov-
Sta r tin g Ma ter ia ls. Cinnamyl bromide, 4-bromo-2-methyl-
2-butene, and allyl bromide were commercially available and
used after distillation. 3-Bromocyclohexene and methyl 4-bro-
mocrotonate were prepared from bromination reaction using
NBS in CCl4 as reported in the literature.20 The following
palladium catalysts were prepared by reported methods: Pd-
(PPh3)4,21 PdCl2(dppf),22 Pd2(dba)3‚CHCl3.23 Pd(OAc)2 was pur-
chased from Aldrich. The starting racemic cyclopropylboronic
acid were readily prepared by using a modified Simmon-Smith
reaction as reported.7.9 1H NMR spectra were recorded using
CDCl3 or CD3COCD3 solutions with tetramethylsilane as inter-
nal standard.
Th e Cr oss-Cou p lin g Rea ction of Allyl Br om id es w ith
Cyclop r op ylbor on ic Acid s for P r ep a r a tion of tr a n s-1-
Allyl-2-p h en ylcyclop r op a n e (3f) Is R ep r esen t a t ive. To a
solution of allyl bromide (2.0 mmol, 242 mg) in dioxane (4 mL),
trans-2-phenylcyclopropylboronic acid (1.0 mmol, 162 mg), and
Ag2O (2 mmol, 463 mg) were added KOH (2 mmol, 112 mg) and
PdCl2(dppf) (0.03 mmol, 22 mg) under a nitrogen atmosphere.
The reaction mixture was stirred at 80 °C for 24 h, then cooled
to room temperature and diluted with petroleum ether, washed
with saturated brine, and dried over magnesium sulfate. The
solvents were removed in vacuo and the residue purified by
column chromatography, eluting with petroleum ether (60-90
°C) to yield trans-1-allyl-2-phenylcyclopropane (3f) as a colorless
liquid (112 mg, 71%).
tr a n s-1-Allyl-2-p h en ylcyclop r a n e (3f): 1H NMR δ ppm
7.05-7.27 (m, 5H), 5.91 (m,1H), 5.10 (dd, J ) 17, 1.6 Hz, 1H),
4.99 (dd, J ) 10.2, 1.6 Hz, 1H), 2.15 (t, J ) 6.5 Hz, 2H), 1.66
(ddd, J ) 4.2, 4.8, 9.0 Hz, Ha, 1H), 1.14 (m, Hb, 1H), 0.94 (ddd,
J ) 9.0, 5.0, 5.2 Hz, Hc, 1H), 0.83 (ddd, J ) 8.6, 5.2, 4.8 Hz, Hd,
1H); IR(neat) 912 cm-1; MS m/e 158 (M+, 8.86), 117 (100). In
the 2D-1H NMR, the proton Ha(1.66 ppm) showed strong NOE
interaction with proton Hd (0.83 ppm) but very weak NOE
interaction with Hc (0.94 ppm) and Hb (1.14 ppm). Anal. Calcd
for C12H14: C, 91.08; H, 8.92. Found: C, 90.86; H, 9.01.
The following compounds were prepared similarly using the
conditions listed in Table 2.
d
ered. A similar yield of coupling product was also obtained using
Pd(PPh3)4 as the catalyst.
desired product in our reaction (Table 1, entry 3), and
using CsF as base was also ineffective (entry 4). Failure
to react is probably due to slow transmetalation between
the cyclopropylboronic acids and π-allylpalladium species
because of the low nucleophilicity of cyclopropyl group
on the boron. Since the base is essential for the success
of Suzuki-type couplings, we then turned our attention
to study the effect of other bases. Kishi in his work
toward the synthesis of palytoxin showed that Ag2O and
TlOH provided dramatic rate enhancement of some
vinylboronic acids couplings.18 Other groups also reported
their accelerating affects in the Suzuki coupling reac-
tion.19 So we examined the reaction of trans-2-phenylcy-
clopropylboronic acid with allylic bromide using many
metallic bases, such as Ag2O,Ag2CO3,Tl2CO3, and TlOH.
Using the 10% aqueous TlOH as the base provided
traces of the product (entry 5), and employing Ag2CO3
in the reaction (entry 6) did not work either. Fortunately,
we found that the coupling reaction occurred when Ag2O
was employed as an activator (entry 8). Gillmann found
that adding AsPh3 increased the product yields in the
silver oxide-assisted palladium-catalyzed cross coupling
of methyl 2-halo-2,3-butadienoates with arylboronic
acids,19b but it gave no improvements in our case (entry
9). After further screening, the combination of Ag2O and
KOH as the base gave the best results while using more
polar solvent dioxane (entries 10 and 11). Tl2CO3 can also
accelerate the coupling of cyclopropylboronic acid with
allyl bromide (entry 7).
Considering the high toxicity of Tl2CO3, the conditions
in entry 11 were used as the optimized condition to
investigate the cross-coupling reactions of various trans-
cyclopropylboronic acids with allyl bromides. The results
are shown in Table 2.
t r a n s -1-((E )-3-P h e n yl-2-p r op e n yl)-2-b u t ylcyclop r o-
p a n e (3a ): yield 82%; colorless liquid; 1H NMR δ 7.18-7.39 (m,
5H), 6.44 (d, J ) 16 Hz, 1H), 6.30 (dt, J ) 16, 6.4 Hz, 1H), 2.15
(t, J ) 6.5 Hz, 2H), 1.31-1.4 (m, 4H), 1.24-1.29 (m, 2H), 0.91
(t, J ) 7 Hz, 3H), 0.55 (m, 2H), 0.30 (m, 2H); IR (neat) 964 cm-1
;
MS m/e 214 (M+, 4.19), 117 (100), 129 (80), 104 (61.26). Anal.
Calcd for C16H22: C, 89.65; H, 10.72. Found: C, 89.49; H, 10.47.
It is shown in Table 2 that good yields of the products
can be obtained in the reaction of allyl bromides with
(20) Dejesus, M.; Rosario, O.; Larson, G. L. J . Organomet. Chem.
1970, 132, 301.
(18) Uenishi, Y.; Beau, J .-M.; Armstrong, R. W.; Kishi, Y. J . Am.
Chem. Soc. 1987, 109, 4756-4758.
(19) (a) Delera, A. R.; Yorrado, A.; Lglesias, B.; Lopez, S. Tetrahedron
Lett. 1992, 33, 6205. (b) Gillmann, T.; Weeber, T. Synlett 1996, 649.
(c) Anderson, J . C.; Namli, H.; Roberts, C. A. Tetrahedron 1997, 53,
15123-15134.
(21) Coulson, D. R. Inorg. Synth. 1972, 13, 121-124.
(22) Hayashi, T.; Konishi, M,; Kobori, Y.; Kumada, M.; Higuchi, T,;
Hirotsu, K. J . Am. Chem. Soc. 1984, 106, 158-163.
(23) Ukai, T.; Kawazura, H.; Ishii, Y.; Bonnet, J . J .; Ibers, A. J . J .
Organomet. Chem. 1974, 65, 253-266.

4446 J . Org. Chem., Vol. 65, No. 14, 2000
Notes
Ta ble 2. Silver Oxid e-Assisted P a lla d iu m -Ca ta lyzed Cr oss-Cou p lin g of Allyl Br om id es w ith Cyclop r op ylbor on ic Acid sa
a
All the reactions were carried out using a mixture of cyclopropylboronic acids (1.0 mmol) and allyl bromides, 2 equiv of Ag2O, 2 equiv
b
of KOH (based on boronic acids), and 3 mol % PdCl2(dppf) in 4 mL of dioxane at 80 °C under a nitrogen atmosphere. All the products
were identified by 1H NMR, IR, and mass spectral and elemental analysis. c Isolated yield. The reaction was carried out at 60 °C.
d
t r a n s-1-((E )-3-P h e n yl-2-p r op e n yl)-2-p e n t ylcyclop r o-
p a n e (3b): yield 89%; colorless liquid; 1H NMR δ 7.17-7.37 (m,
5H), 6.43 (d, J ) 16 Hz, 1H), 6.27 (dt, J ) 16, 6.5 Hz, 1H), 2.15
(t, J ) 6.4 Hz, 2H), 1.27-1.44 (m, 8H), 0.89 (t, J ) 6.6 Hz, 3H),
0.54 (m, 2H), 0.29 (m, 2H); IR (neat) 964 cm-1; MS m/e 228 (M+,
2.98), 117 (100), 129 (77), 104 (69). Anal. Calcd for C17H24: C,
89.32; H, 10.68. Found: C, 89.54; H, 10.64.
1.70 (m, 1H, overlapped with CH3), 1.65 (s, 3H), 1.10 (m, 1H),
0.0.79-0.92 (m, 1H + 1H); IR (neat) 1610 cm-1; MS m/e 186
(M+, 2.7), 117 (100), 82 (59). Anal. Calcd for C14H18: C, 90.26;
H, 9.74. Found: C, 90.11; H, 9.40.
tr a n s-1-(3-Meth yl-2-bu ten yl)-2-h exylcyclop r op a n e (3h ):
1
yield 80%; colorless liquid; H NMR δ 5.20 (t, J ) 5.7 Hz, 1H),
1.91 (t, J ) 5.8 Hz, 2H), 1.70 (s, 3H), 1.59(s, 3H), 1.26-1.41 (m,
10H), 0.88 (t, J ) 6.5 Hz, 3H), 0.42 (m, 2H), 0.17 (m, 2H); IR
(neat) 1021 cm-1; MS m/e 194 (M+, 3.8), 69 (100), 82 (64). Anal.
Calcd for C14H26: C, 86.52; H, 13.48. Found: C, 86.75; H, 13.20.
tr a n s-1-(3-Cycloh exen yl)-2-ph en ylcyclopr opan e (3i): yield
40%; colorless liquid; 1H NMR δ 7.06-7.26 (m, 5H), 5.72 (m,
2H), 1.98 (m, 1H), 1.70-1.82 (m, 2H), 1.54-1.68 (m, 4H + 1H),
1.06 (m, 1H), 0.83-0.94 (m, 1H + 1H); IR (neat) 1678 cm-1; MS
m/e 198 (M+, 3.8), 94 (100), 117 (63), 82 (59). Anal. Calcd for
C15H18: C, 90.85; H, 9.15. Found: C,90.51; H, 9.20.
t r a n s-1-((E )-3-P h e n y l-2-p r o p e n y l)-2-h e x ylc y c lo p r o -
p a n e (3d ): yield 80%; colorless liquid; 1H NMR δ 7.15-7.39 (m,
5H), 6.44 (d, J ) 16 Hz, 1H), 6.33 (dt, J ) 16, 6.5 Hz, 1H), 2.14
(t, J ) 6.5 Hz, 2H), 1.26-1.41 (m, 10H), 0.85 (t, J ) 6.8 Hz,
3H), 0.55 (m, 2H), 0.27 (m, 2H); IR (neat) 964 cm-1; MS m/e 242
(M+, 5.7), 117 (100), 129 (82), 104 (50). Anal. Calcd for C18H26
C, 89.19; H, 10.81. Found: C, 89.11; H, 10.69.
:
tr a n s-1-Allyl-2- h exylcyclop r op a n e (3e): yield 89%; color-
less liquid; 1H NMR δ 5.85 (m, 1H), 5.02 (dd, J ) 16, 1.7 Hz,
1H), 4.90 (dd, J ) 10.2, 1.7 Hz, 1H), 1.93 (t, J ) 5.5 Hz, 2H),
1.27-1.38 (m, 10H), 0.86 (t, J ) 6.4 Hz, 3H), 0.46 (m, 2H), 0.20
(m, 2H); IR (neat) 911 cm-1; MS m/e 166 (M+, 4.2), 67 (100), 129
Ack n ow led gm en t. We thank the NNSF of China
and Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Acdemy of
Sciences, for financial support.
(82), 109 (31). Anal. Calcd. for C12H22
Found: C, 86.70; H, 13.61.
: C, 86.77; H, 13.23.
tr a n s-1-(3-Meth yl-2-bu ten yl)-2-p h en ylcyclop r opa n e (3g):
yield 62%; colorless liquid, 1H NMR δ 7.05-7.35 (m, 5H), 5.26
(t, J ) 5.8 Hz, 1H), 2.13 (t, J ) 5.8 Hz, 2H), 1.74 (s, 3H), 1.65-
J O0000933