Nickel(0)/imidazolium carbene catalyst system for efficient cross-coupling of aryl bromides and chlorides with organomanganese reagents

Article abstract of DOI:10.1002/adsc.200505409

N,N′-Bis(2,6-diisopropylphenyl)imidazolium chloride associated with nickel(II) acetylacetonate (3-5 mol%) was used as catalyst to efficiently cross-couple functionalized aryl bromides with organomanganese reagents. The reactions were performed between 0°C and room temperature, giving unsymmetrical biaryls in 0.25 to 24 h with 52 to 100% yields for isolated materials. Aryl chlorides showed slightly diminished reactivity in Ni/2 IPr-catalyzed cross-couplings and good yields could only be attained with activated or neutral substrates.

Full text of DOI:10.1002/adsc.200505409

FULL PAPERS
DOI: 10.1002/adsc.200505409
Nickel(0)/Imidazolium Carbene Catalyst System for Efficient
Cross-Coupling of Aryl Bromides and Chlorides with Organo-
manganese Reagents
Anne Leleu,a Yves Fort,a and Raphal Schneiderb,*
a
Laboratoire de Synth›se OrganomØtallique et RØactivitØ, UMR CNRS-UHP 7565, UniversitØ Henri PoincarØ, Nancy 1,
FacultØ des Sciences, BP 239, 54506 Vandoeuvre les Nancy Cedex, France
LCPME, Groupe Thiols, UMR CNRS-UHP 7564, UniversitØ Henri PoincarØ, Nancy 1, FacultØ de Pharmacie, BP 80403,
b
54001 Nancy Cedex, France
Fax : (+33)-3-83-68-21-54; e-mail: Raphael.Schneider@pharma.uhp-nancy.fr
Received: October 17, 2005; Accepted: April 6, 2006
Abstract: N,N’-Bis(2,6-diisopropylphenyl)imidazoli- 100% yields for isolated materials. Aryl chlorides
um chloride associated with nickel(II) acetylaceto- showed slightly diminished reactivity in Ni/2 IPr-cat-
nate (3–5 mol%) was used as catalyst to efficiently alyzed cross-couplings and good yields could only be
cross-couple functionalized aryl bromides with orga- attained with activated or neutral substrates.
nomanganese reagents. The reactions were per-
formed between 08C and room temperature, giving Keywords: aryl halides; cross-coupling; N-heterocy-
unsymmetrical biaryls in 0.25 to 24 h with 52 to clic carbenes; nickel; organomanganese reagents
Introduction
action mixture are, however, required to produce high
yields for unactivated aryl halides using this method-
Unsymmetrical biaryls represent an important class of ology.
compounds in drug discovery,[1] natural product[2] and
Nucleophilic N-heterocyclic carbenes (NHCs) have
material science.[3] These biaryls have been typically attracted considerable attention as possible alterna-
prepared via cross-coupling of aryl metal compounds tives for the widely used phosphine ligands in homo-
with aryl halides or pseudohalides mediated by transi- geneous catalysis.[11] The primary advantage of these
tion metal catalysts. Classical methodologies used are ligands appears to be that they do not dissociate from
the palladium coupling of organic halides or halide the metal center, as a result an excess of the ligand is
equivalents with Grignard (Kumada–Corriu reac- not required to prevent aggregation of the catalyst to
tion),[4] organotin (Stille reaction),[5] organozinc (Ne- yield the bulk metal.[12] Recently, we and others have
gishi reaction)[6] or organoboron reagents (Suzuki– demonstrated that the combination of Ni(0) or Pd(0)
Miyaura reaction)[7] where monodentate phosphines with NHCs was highly efficient in the amination of
are usually employed as ancillary ligands. Nickel(0)/ aryl chlorides,[13] Kumada couplings,[14] Suzuki–
phosphines complexes have also found useful applica- Miyaura couplings[15] and reduction reactions.[16]
tions but appear to have a less general scope.[8]
Therefore it was of interest to expand the scope of
The use of manganese-derived compounds as trans- these catalytic systems to organomanganese reagents
metallation reagents has only attracted little attention as the coupling partner. We now report the use of the
in spite of their high reactivity, their increase chemo- Ni(0)/2 IPr catalyst system in the cross-coupling reac-
selectivity compared to Grignard reagents and their tion of aryl halides with organomanganese reagents.
low cost. Indeed, manganese can catalyze the substi-
tution of activated aryl halides (X=Br, Cl and F) and
aryl methyl ethers by organomagnesium reagents.[9] Results and Discussion
Cahiez et al. demonstrated also that PdCl2(PPh3)2 or
A
PdCl
A
(dppp=diphenylphosphinopropane) Arylmanganese reagents were prepared in THF at
complexes catalyze the cross-coupling reaction of or- 08C from Grignard reagents by exchange with the
ganomanganese reagents with various aryl bromides MnCl2·2 LiCl ate complex as previously described.[17]
and iodides in THF.[10] High catalyst and phosphine Ni(0)/NHC complexes were generated in situ by si-
loadings and addition of co-solvent (DME) to the re- multaneous reduction of an Ni(+2) salt and deproto-
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Cross-Coupling of Aryl Bromides and Chlorides with Organomanganese Reagents
FULL PAPERS
nation of the NHC precursor using the organomanga- more s-donating than IPr,[18] was found to be less ef-
nese reagent (0.8M solution in THF). ficient and exhibited lower conversions under similar
Different Ni(0)/NHC complexes were initially reaction conditions (entry d). Consistent with previ-
tested as possible candidates and their catalytic activi- ous findings, the IMes and ITol ligands, possessing a
ty was studied in a model reaction between 3-bromo- smaller steric bulk, were less efficient than IPr and
toluene and 4-methoxyphenylmanganese chloride SIPr (entries b and c). A modest 37% yield was final-
(Figure 1). Control experiments showed first that (i) ly obtained with the pincer ligand ICyPic (entry e).
without the Ni(0)/NHC complex, no reaction occur-
Based on previous studies on palladium- or nickel/
red, (ii) employing Ni(0) without the NHC ligand NHC complexes, initial experiments were performed
gave only 4,4’-dimethoxybiphenyl (42%) arising from using an IPr/Ni ratio of 1:1. After 3 h reaction at
homocoupling of the starting organomanganese re- 258C, the biaryl was isolated in a modest 53% yield.
agent. As shown in Table 1, the use of the sterically After some experimentation, we found that with car-
hindered IPr ligand is highly effective in the coupling bene precursor 1, a 2:1 ratio of carbene to Ni is the
reaction (85%, entry a). The structurally related SIPr, best catalyst combination (85% yield after 3 h). In-
creasing the ratio further is highly deleterious, and a
strong decrease of catalytic activity (39% yield) was
observed when a 3:1 ratio of IPr/Ni was used. This
tends to imply that the optimum active catalysts,
when NHCs are used, are low-coordinate and that
overcoordination effectively “switches off” the cataly-
sis.
The same behavior was observed with different
Ni(0) precursors (Table 2). No catalytic activity was
observed starting from NiCl
was obtained with the phosphine-less NiCl2 complex
(47%). A good yield was attained with Ni(OAc)2
(76%) but Ni(acac)2 was found to be the most effi-
2(PPh3)2. A better result
ACHTREUNG
AHCTREUNG
cient affording the desired biaryl in 85% yield.
The nickel-catalyzed cross-coupling protocol that
we have developed was found to be applicable to a
wide range of aryl halides and sulfonates as evident
from Table 3.
With iodobenzene (entry a), the coupling proceed-
ed very rapidly and afforded quantitatively 4-methoxy-
biphenyl. The most attractive candidates for industri-
al applications, namely bromo- and chlorobenzene,
were also found to be effective coupling partners (en-
Figure 1. NHC precursors.
Table 1. Influence of the ligand in the Ni(0)-catalyzed cou-
pling reaction of 3-bromotoluene with 4-methoxyphenyl-
manganese chloride.[a]
Table 2. Influence of the Ni(0) precursor in the reaction of
3-bromotoluene with 4-methoxyphenylmanganese chlor-
ide.[a]
Entry
Ligand Precursor
Yield [%][b]
Entry
Ni(0) Source
Yield [%][b]
a
b
c
d
e
IPr·HCl (1)
85
29
23
69
37
IMes·HCl (2)
ITol·HCl (3)
SIPr·HCl (4)
ICyPic·HCl (5)
a
b
c
NiCl2
NiCl2
A
0
47
76
85
Ni
Ni
ACHTREUNG
d
ACHTREUNG
[a]
[a]
All reactions were conducted in THF between 0 and
258C for 3 h using 1.0 equiv of 3-bromotoluene and 1.5
equivs. of the arylmanganese reagent.
All reactions were conducted in THF between 0 and
258C for 3 h using 1.0 equiv of 3-bromotoluene and 1.5
equivs. of the arylmanganese reagent.
[b] Isolated yields.
[b] Average isolated yield of at least two runs.
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Anne Leleu et al.
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Table 3. Cross-coupling of 4-methoxyphenylmanganese chlo-
As can be seen in Table 4, aryl bromides substituted
by electron-donating groups were well tolerated (en-
tries b–d, f and g). Substrates with electron-withdraw-
ing groups reacted faster and generated the coupling
products in good to excellent yields.
ride with various aryl halides and sulfonates.[a]
The Ni(0)/2 IPr catalyst was found to sensitive to
an ortho substitution of the aryl bromide. 2-Bromoto-
luene reacted with 4-methoxyphenylmanganese chlo-
ride in 71% yield (entry b) while 3- and 4-bromoto-
luene coupled without difficulty (entries c and d). In
the attempted coupling of the sterically more hin-
dered 2-bromo-1-trifluoromethylbenzene with the
same organomanganese reagent, only starting materi-
als were observed after prolonged reaction times
(entry j). By contrast, an ortho-substitution is much
better tolerated on the organomanganese derivative
and couplings performed using the Ni(0)/2 IPr cata-
lyst system proceeded effectively even with an ortho-
substituted aryl bromide (entries e and i).
Entry
X
Time [h]
Yield [%][b]
a
b
c
d
e
f
I
Br
Cl
F
OTf
OTs
OMs
1
3
7
18
5
99
91
73
0
87
18[c]
0
15
24
g
[a]
10 mmol ArX, 15 mmol ArMnCl, 5 mol% Ni, 10 mol%
IPr, THF, 0–258C.
[b] Isolated yields.
[c]
Obtained with 37% 4-methoxy-4’-methylbiphenyl.
As shown in Table 4, a great variety of functional
groups like fluorine, trifluoromethyl, methyl ester,
tries b and c) but in the latter case, the reaction failed non-enolizable ketones, acetal or dimethylamino are
to proceed to completion under our reaction condi- tolerated. The coupling of organomanganese reagents
tions. It is therefore not surprising that fluorobenzene with bromobenzoates (entries m–q) readily goes with
(entry d) could not be transformed even though aryl 5 mol% of the catalyst and produces the desired biar-
fluorides were recently found to be efficiently coupled yls in good yields. These couplings were generally
with the more reactive Grignard reagents using Ni(0)/ stopped before complete consumption of the starting
NHC catalysts.[14b] It is worth noting that all attempts aryl bromide to ensure a clean reaction at the halide
to conduct the couplings at higher temperatures (40 function and not at the ester. Attack of the organo-
or 658C) lead to complex mixtures of products with manganese reagent at the ester function was observed
all aryl halides. Among the arenesulfonates, phenyl when the couplings were allowed to run for more
trifluoromethanesulfonate showed better reactivity than 1.5 h at room temperature. For example, the re-
than the corresponding tosylate or mesylate (entries action of methyl 2-bromobenzoate and 4-methoxy-
e–g) as would be expected given that triflates have phenylmanganese chloride (entry m) gave 14% of the
successfully been used in nickel-catalyzed carbon- double addition product after 5 h at 258C. With all
carbon couplings.[19] Phenyl 4-methyl-1-benzenesulfo- aryl bromides bearing a carbonyl group (entries m–s),
nate (entry f) gave the expected 4-methoxybiphenyl a two-fold excess of the organomanganese derivative
in a poor (18%) yield. The coupling product was ac- was necessary to reach a good conversion of the start-
companied by 37% of 4-methoxy-4’-methylbiphenyl ing aryl bromide. 3-Bromobenzoic acid could also be
arising from an ipso-nucleophilic aromatic substitu- used as coupling partner using 3.0 of equivs. organo-
tion classically observed with aryl tosylates.[20] Finally, manganese reagent. Reactions performed with bro-
no reaction was observed with phenyl methanesulfo- mobenzonitriles gave no product (data not shown in
nate (entry g).
Table 4). When the coupling of bromobenzene with 4-
The utility of the Ni(0)/2 IPr catalyst for general methoxyphenylmanganese chloride (entry e) was per-
cross-coupling reaction of aryl bromides with organo- formed in the presence of 1 equiv. of benzophenone
manganese reagents was further investigated to deter- or benzonitrile, a strong decrease of the reaction rate
mine its scope and limitations (Table 4). In general, 5 was observed (respectively 40 and 11% conversion
mol% Ni were applied in these reactions; however, after 5 h). It is therefore likely that coordination of
the amount of catalyst could be reduced to 3 mol% the carbonyl or the nitrile groups with the Ni(0)/2 IPr
(relative to ArBr) with activated aryl bromides with- catalyst interferes with the Ni-catalyzed cross-cou-
out significantly decreasing the yield.
plings. Such coordination of the nickel center at
Noteworthy is the fact that, in all reactions, reduc- oxygen or nitrogen atoms has already been observed
tion of the starting aryl bromide has never been de- in carbon-nitrogen couplings or reductions mediated
tected. In most cases, the biaryl arising from the Ni- by Ni(0)/NHC complexes.[13b,16d] 2- or 3-bromopyri-
catalyzed homocoupling of the organomanganese re- dines are also excellent substrates giving coupling
agent was the sole by-product observed (<20% products in quantitative yields (entries u and v). How-
yield).
ever, both the basicity and the nucleophilicity of the
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Cross-Coupling of Aryl Bromides and Chlorides with Organomanganese Reagents
FULL PAPERS
Table 4. Ni(0)/2 IPr-mediated cross-coupling of aryl bromides with organomanganese reagents.[a]
Entry
a
Aryl bromide
ArMnCl
Time [h][b]
Cross-coupled product 6
Yield [%][c]
92
7
b
c
d
o-Me
m-Me
p-Me
24
11
10
71
85
89
e
13
85
f
15
10
76
95
g
h
i
10
7
63
79
j
k
l
o-CF3
m-CF3
p-CF3
24
8
7
0
93
95
m
0.25
0.25
65[d]
n
72[d]
o
p
0.5
91[d]
89[d]
0.25
q
r
0.25
13
98[d]
76[d]
s
t
18
9
52[e]
89
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Anne Leleu et al.
Yield [%][c]
FULL PAPERS
Table 4. (Continued)
Entry
Aryl bromide
ArMnCl
Time [h][b]
9
Cross-coupled product 6
u
v
2-Br
3-Br
1
1
100
100
[a]
All reactions were carried out under the following conditions: 10 mmol ArCl, 15 mmol ArMnCl, 5 mol% Ni, 10 mol%
IPr, THF, 0–258C.
[b] Determined by GC/MS analysis.
[c]
Isolated yields.
[d] 20 mmol ArMnCl were used.
[e]
30 mmol ArMnCl were used.
organomanganese reagents limit the functional group mides with organomanganese reagents. The procedure
tolerance of the process: enolizable ketones are de- is very mild (from 08C to room temperature) and ap-
protonated, nitroarenes decompose and the attack of pears to have a broad applicability, being useful for
the organomanganese reagent on the carbonyl group the coupling of both electron-deficient and electron-
was observed with aldehydes.
rich aromatic bromides. A great variety of functional-
Finally, aryl chlorides are less reactive than aryl ized biaryls have been efficiently prepared using this
bromides using the Ni(0)/2 IPr catalyst system methodology. The method described herein may be a
(Table 5). Electronically neutral (entries a and b) or valuable alternative to Kumada–Corriu and Negishi
electron-deficient aryl chlorides (entries c and d) are cross-couplings.
efficiently transformed; however, all reactions with
electron-rich aryl chlorides (chlorotoluenes or chloro-
anisoles) gave poor results.
Experimental Section
General Remarks
Conclusions
Manganese(II) chloride tetrahydrate and lithium chloride
were dried at 1108C under reduced pressure before use. All
In conclusion, we have demonstrated that the combi-
nation of Ni(0) with the sterically hindered and elec-
tron-donating N-heterocyclic carbene IPr provides an
other reagents were obtained commercially and used with-
1
out further purification. H NMR spectra were recorded at
effective catalyst for the cross-coupling of aryl bro- 400 or 200 MHz. 13C NMR spectra were recorded at 100 or
Table 5. Cross-coupling of 4-methoxyphenylmanganese chloride with aryl chlorides.
Entry
a
Aryl chloride
Time [h]
7
Cross-coupled product
Yield [%][b]
76
b
c
6
90
15
15
72
66
d
[a]
10 mmol ArCl, 15 mmol ArMnCl, 5 mol% Ni, 10 mol% IPr, THF, 0–258C.
[b] Isolated yields.
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FULL PAPERS
50 MHz. IR spectra were recorded using NaCl cells or mix-
tures of compounds/KBr. Mass spectra were obtained on a
GC/MS Shimadzu QP-5050 (EI, 70 eV). Melting points were
determined on a Tottoli capillary melting point apparatus
and are uncorrected. Each compound prepared herein was
8.05 (d, J=6.0 Hz, 1H), 7.80 (d, J=6.0 Hz, 1H), 7.59–7.39
(m, 4H), 7.16 (d, J=7.8 Hz, 2H), 3.93 (s, 3H), 2.42 (s, 3H);
13C NMR (50 MHz, CDCl3): d=167.6, 159.5, 142.8, 134.4,
133.3, 131.9, 131.7, 130.1, 129.9, 129.4, 128.8, 127.6, 124.6,
52.4, 21.2. IR (NaCl): n=3053, 3029, 2950, 2920, 1723, 1602,
1589, 1472, 1433, 1291, 1279, 1251, 1126, 1110, 774, 758,
699 cmÀ1; MS: m/z=226; anal. calcd. for C15H14O2: C 79.62,
H 6.24; found: C 79.4, H 6.1.
1
characterized by GC-MS, IR and H and 13C NMR spectros-
copy. All reported yields are based on the weight of the iso-
lated product.
2-Carbomethoxy-4’-dimethylaminobiphenyl (6o): Isolated
as a pale yellow oil; yield: 91%. 1H NMR (200 MHz,
CDCl3) d=7.79 (dd, J=6.8, 3.2 Hz, 1H), 7.67 (dd, J=6.8,
3.2 Hz, 1H), 7.45–7.38 (m, 2H), 7.23 (d, J=8.2 Hz, 2H),
6.75 (d, J=8.2 Hz, 2H), 3.93 (s, 3H), 2.94 (s, 6H); 13C NMR
(50 MHz, CDCl3): d=167.6, 147.9, 134.8, 133.4, 133.1, 131.7,
129.6, 129.5, 127.6, 122.1, 117.8, 113.1, 113.0, 52.9, 41.1; IR
(NaCl): n=3064, 3027, 2996, 2951, 2280, 2804, 1736, 1601,
1591, 1507, 1433, 1294, 1253, 1128, 1111, 1028, 746,
692 cmÀ1; MS: m/z=255. anal. calcd. for C16H17NO2: C
75.27, H 6.71, N 5.49; found: C 75.0, H 6.5, N 5.6.
Gas chromatographic analyses were performed on a Shi-
madzu GC-17 capillary gas chromatograph fitted with an
“Optima 5” column (22 m ” 0.25 mm, ID ” 0.25 mm). All
quantifications of reaction constituents were achieved by
gas chromatography using a known quantity of decane or
dodecane as reference standard.
2- and 4-bromobenzoates were prepared according to a
previously reported procedure[21] and isolated by flash chro-
matography on silica gel.
1-(3’-Carbomethoxyphenyl)naphthalene (6q): Isolated as
a pale yellow solid; mp 738C; yield: 98%. 1H NMR
(200 MHz, CDCl3): d=8.18 (dd, J=1.6, 1.6 Hz, 1H), 8.12
(dd, J=7.6, 0.6 Hz, 1H), 7.95–7.78 (m, 3H), 7.72–7.67 (m,
1H), 7.61–7.39 (m, 5H), 3.93 (s, 3H); 13C NMR (50 MHz,
CDCl3): d=167.5, 141.6, 139.6, 135.0, 134.3, 131.9, 131.6,
130.9, 129.0, 128.9, 128.6, 127.6, 126.8, 126.4, 126.1, 125.9,
52.6; IR (KBr): n=3059, 2950, 1723, 1578, 1508, 1435, 1394,
1305, 1280, 1260, 1241, 1191, 1124, 1104, 1082, 999, 960, 801,
General Procedure for the Ni(0)/2 IPr-Catalyzed
Coupling Reactions
The MnCl4 Li2 “ate complex” was prepared from anhydrous
MnCl2 (1.98 g; 15.75 mmol) and LiCl (1.33 g; 31.5 mmol) in
THF as previously described.[17]
The organomanganese reagent was preformed from the
MnCl4 Li2 complex (15.75 mmol) and from a Grignard re-
agent (15.1 mmol, 0.8m solution in THF).
778, 756, 699 cmÀ1
; MS: m/z=262; anal. calcd. for
C18H14O2: C 82.42, H 5.38; found: C 82.3, H 5.1.
In a 50 mL Schlenk reactor equipped with a condenser
and a magnetic stirrer, were charged under a nitrogen at-
3-Carboxy-4’-methoxybiphenyl (6s): Isolated as a white
solid; mp 2088C; yield: 52%. 1H NMR (400 MHz,
CD3COCD3): d=8.05 (d, J=8.4 Hz, 1H), 7.96 (d, J=
8.0 Hz, 2H), 7.68 (d, J=8.0 Hz, 2H), 7.72 (d, J=8.4 Hz,
1H), 7.69–7.67 (m, 1H), 7.04 (d, J=8.4 Hz, 1H), 3.86 (s,
3H); 13C NMR (100 MHz, CD3COCD3): d=167.9, 159.2,
145.0, 133.5, 132.6, 130.8, 130.5, 129.2, 114.6, 55.6; IR (KBr):
n=3394, 3081, 2957, 2840, 1678, 1600, 1586, 1423, 1395,
1317, 1289, 1272, 1241, 1197, 1172, 1124, 1062, 1009, 931,
756 cmÀ1; MS: m/z=228; anal. calcd. for C14H12O3: C 73.67,
H 5.30; found: C 73.6, H 5.5.
mosphere Ni(acac)2 (0.128 g; 0.5 mmol) and IPr·HCl
R
(0.424 g, 1 mmol) in 5 mL anhydrous THF. A solution of the
organomanganese reagent (15.1 mmol) was then added be-
tween À5 and 08C and the black mixture obtained was fur-
ther stirred at 08C for 0.5 h. The aryl bromide (10 mmol)
and the internal standard (decane or dodecane) were then
added dropwise at 08C. After stirring for 1 h at 08C, the
mixture was allowed to warm up to room temperature. The
reaction was followed by GC or GC/MS analysis. When
completion was reached, the reaction mixture was quenched
with methanol. Solvents were evaporated under reduced
pressure and the crude material obtained was purified by
silica gel column chromatography.
2-(4’-Methoxy[1,1’-biphenyl]-4-yl)-1,3-dioxolane (6t): Iso-
1
lated as an off-white solid; mp 988C; yield: 89%. H NMR
(400 MHz, CDCl3): d=7.58–7.51 (m, 4H), 7.47 (d, J=
8.4 Hz, 2H), 7.35 (d, J=8.4 Hz, 2H), 5.76 (s, 1H), 4.17–4.01
(m, 4H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
158.9, 145.2, 136.6, 134.1, 133.7, 131.9, 128.6, 128.1, 127.2,
127.1, 114.5, 104.1, 103.4, 65.7, 55.7; IR (KBr): n=3059,
2997, 2950, 1603, 1591, 1578, 1518, 1465, 1384, 1280, 1241,
4-Methoxybiphenyl (6a),[22] 4-methoxy-2’-methylbiphenyl
(6b),[23] 4-methoxy-3’-methylbiphenyl (6c),[24] 4-methoxy-4’-
methylbiphenyl (6d),[25] 2-methoxybiphenyl (6e),[26] 4-dime-
thylamino-4’-methoxybiphenyl (6f),[27] 4-fluoro-4’-methoxy-
biphenyl (6h),[28] 2-fluoro-2’-methoxybiphenyl (6i),[29] 4-me-
thoxy-3’-trifluoromethylbiphenyl (6k),[30] 4-methoxy-4’-tri-
fluoromethylbiphenyl (6l),[24] 2-carbomethoxy-4’-methoxybi-
1191, 1021, 960 cmÀ1
; MS: m/z=256; anal. calcd. for
C16H16O3: C 74.98, H 6.29; found: C 74.8, H 6.4.
phenyl
(6m),[31]
4-carbomethoxy-4’-methoxybiphenyl
(6p),[32] 4-(4’-methoxyphenyl)benzophenone (6r),[33] 2-(4-
methoxyphenyl)pyridine (6u)[14a] and 3-(4-methoxyphenyl)-
pyridine (6v)[34] have previously been described.
References
[1] P. J. Hajduk, M. Bures, J. Praestgaard, S. W. Fesik, J.
Med. Chem. 2000, 43, 3443.
[2] G. Bringmann, D. Menche, Acc. Chem. Res. 2001, 34,
615.
Analytical Data of New Compounds
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