Multiple arylation of alkyl aryl ketones and α,β-unsaturated carbonyl compounds via palladium catalysis

Article abstract of DOI:10.1016/S0040-4020(01)00555-5

Alkyl (ethyl to butyl) aryl ketones have been found to undergo multiple arylation on the alkyl chains accompanied by oxidative unsaturation upon treatment with excess aryl bromides in the presence of a palladium catalyst and a base. In the case of phenyl propyl ketones, for example, the arylation occurs up to five times on the α-and γ-positions as well as the ortho-position of the phenyl ring to give 1-(biphenyl-2-yl)-2,4,4,4-tetraphenyl-2-buten-1-ones along with other arylation products. A number of α,β-unsaturated carbonyl compounds are also arylated multiply on the α- and γ-positions.

Full text of DOI:10.1016/S0040-4020(01)00555-5

TETRAHEDRON
Pergamon
Tetrahedron 57 %2001) 5967±5974
Multiple arylation of alkyl aryl ketones and a,b-unsaturated
carbonyl compounds via palladium catalysis
Yoshito Terao, Yoko Kametani, Hiroyuki Wakui, Tetsuya Satoh, Masahiro Miurap
and Masakatsu Nomura
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
Received 23 April 2001; accepted 16 May 2001
AbstractÐAlkyl %ethyl to butyl) aryl ketones have been found to undergo multiple arylation on the alkyl chains accompanied by oxidative
unsaturation upon treatment with excess aryl bromides in the presence of a palladium catalyst and a base. In the case of phenyl propyl
ketones, for example, the arylation occurs up to ®ve times on the a-and g-positions as well as the ortho-position of the phenyl ring to give
1-%biphenyl-2-yl)-2,4,4,4-tetraphenyl-2-buten-1-ones along with other arylation products. A number of a,b-unsaturated carbonyl
compounds are also arylated multiply on the a- and g-positions. q 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
groups accompanied by oxidative unsaturation and among
the ketones, the propyl derivatives also undergo ortho-
arylation. Consequently, the reaction of a number of a,b-
unsaturated carbonyl compounds with excess aryl bromides
has also been undertaken. The results are reported herein.
Palladium-catalyzed arylation reactions using aryl halides
are now recognized to be highly useful for making aromatic
®ne compounds.1,2 For example, the reaction of alkenes %the
Mizoroki±Heck reaction) and that of organoboron
compounds %the Suzuki±Miyaura reaction) are very often
employed.
Meanwhile, it was recently reported by several groups
including ours that ketones and a,b-unsaturated carbonyl
compounds can effectively undergo arylation at their a-3±6
and g-positions,3d,e,7,8 respectively, under the conditions
similar to those for the Mizoroki±Heck reaction. The reac-
tion is considered to involve the coupling of enolates or
dienolates with arylpalladium species generated in situ.
We also demonstrated that benzyl phenyl ketones %2) as
well as acetophenone %3) undergo not only a-arylation,
but also ortho-arylation to give diphenylmethyl 2,6-
diphenylphenyl ketone and its derivatives 4 as the predomi-
nant products %Scheme 1).3c The latter arylation is con-
sidered to involve the coordination of enolate oxygen to
arylpalladium species and the subsequent ortho-palladation
as the key steps %Scheme 2).9
Scheme 1.
Since the sequential multiple arylation appears to be useful
as a synthetic method of oligophenyl compounds,10 we
examined the reaction of other alkyl phenyl ketones with
excess aryl bromides. It was found that ethyl, propyl and
butyl phenyl ketones are multiply arylated on the alkyl
Keywords: aryl halides; arylation; carbonyl compounds; palladium and
compounds.
p
Corresponding author. Tel.: 181-6-6879-7361; fax: 181-6-6879-7362;
e-mail: miura@ap.chem.eng.osaka-u.ac.jp
Scheme 2.
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020%01)00 555-5

5968
Y. Terao et al. / Tetrahedron 57 ,2001) 5967±5974
The reaction of butyrophenone %7a) with 1a was found to
produce a number of products. Thus, treatment of 7a with
6 equiv. of 1a in the presence of Pd%OAc)2, PPh3 and
Cs2CO3 for 2 h gave a mixture of mono- 8, tri- 9a and 10,
tetra- 11 and pentaphenylated compounds 12a in
comparable yields %Scheme 4 and entry 6).
The %E)-stereochemistry of 11 and 12a was determined by
NOE experiments in the measurement of their H NMR
1
spectra. It is also noted that the double bond in 9a does
not conjugate with the carbonyl group, which may be due
to the fact that it is thermodynamically more favorable than
its double bond isomer. The reaction with 7.5 equiv. of 1a
for 23 h gave 11 and 12a as the major products together with
Scheme 3.
Table 1. Arylation of aromatic ketones or aldehydes with aryl bromides
Entry
Bromide %mmol)
Ketone or aldehyde
Pd%OAc)2 %mmol)
PR3
Time %h)
Product%s); % yielda
c
1b
2b
3
4
5
1a %4)
1a %4)
1a %4)
1a %5)
1a %4)
1a %6)
2a
2b
2c
3
5
7a
±
±
±
±
±
±
±
±
PPh3
PPh3
20
6
71
49
20
2
4 %XˆYˆZˆH); 61 %40)
4 %XˆZˆH, YˆCl); 65 %59)
4 %XˆZˆH, YˆOMe); 18
4 %XˆYˆZˆH); 26
6; 59 [%E)/%Z)ˆ2:1]
8; 20 ,9a; 23, 10; 12 %12), 11; 30
%26), 12a; %15)
c
c
d
0.05
0.1
6
7
8
9
1a %7.5)
1a %6)
1a %6)
1a %4)
1b %4)
1c %4)
1a %7.5)
1b %7.5)
1b %7.5)
1a %7.5)
1a %4)
7a
7a
7a
7a
7a
7a
7b
7a
7b
13
16
18f
18f
0.1
0.1
0.1
0.075
0.075
0.075
0.1
0.1
0.1
0.075
0.025
0.05
0.05
PPh3
23
2
2
4.5
2
2
10; 11 %8), 11; 37 %29), 12a; %21)
8;14, 9a; 78
P%o-tolyl)3
P%t-Bu)3
P%o-tolyl)3
P%o-tolyl)3
P%o-tolyl)3
PPh3
P%4-F±C6H4)3
P%4-F±C6H4)3
PPh3
8; 78 %58), 9a; 19
8;12, 9a; 81 %48)
9b; 64 %41)e
10
11
12
13
14
15
16
17
18
19g
9c; 50%34) e
2
12b; %52)e
23
23
23
5
1.5
0.5
12c; %26) e
12d; %49)e
14; %28), 15; %21)
17; %47)
19; 45
PPh3
PPh3
PPh3
1a %1)
1a %1)
19; 61 %44)
The reaction was carried out using 1 mmol of ketone in the presence of Cs2CO3 as base in re¯uxing o-xylene at a bath temperature of 1608C under nitrogen.
[Bromide]ˆ[Cs2CO3], [PR3]/[Pd%OAc)2]ˆ4.
a
Determined by GLC analysis. Value in parentheses indicates isolated yield.
Taken from the data in Ref. 8.
Pd%PPh3)4 %0.005 mmol) was used.
Pd%PPh3)4 %0.01 mmol) was used.
Other products were not characterized.
1.5 mmol of 18 was used.
Reaction in DMF at 1408C.
b
c
d
e
f
g
2. Results and discussion
a minor amount of 10, 8 and 9a being almost completely
disappeared %entry 7). It was of considerable interest that
treatment of 7a with 6 equiv. of 1a using P%o-Tolyl)3 and
P%t-Bu)3 in place of PPh3 for 2 h afforded 9a and 8, respec-
tively, as the predominant products %entries 8 and 9).
When propiophenone %5) %1 mmol) was treated with bromo-
benzene %1a) %4 mmol) in the presence of Pd%OAc)2
%0.05 mmol) and PPh3 %0.2 mmol) using Cs2CO3 %4 mmol)
as base in re¯uxing o-xylene for 20h, 1,2,3-triphenyl-2-
propen-1-one %6) was produced in 59% yield with a
%E)/%Z) ratio of 2:1 %Scheme 3 and entry 5 in Table 1).
The above results indicate that the reaction of 7a involves
%a) a-phenylation leading to 8, %b) oxidative unsaturation of
8, %c) g-diphenylation to 9a, %d) further g-phenylation of 9a
to 11, %e) oxidative cyclization of 9a to 10 and %f) ortho-
phenylation of 9a followed by g-phenylation to 12a
%Scheme 5).
The formation of 6 may be reasonably explained by the
mechanism involving oxidative unsaturation.11 After
a-phenylation of 5, the enolate from the primary product
reacts with phenylpalladium bromide to form an alkyl-
phenylpalladium intermediate. Then, elimination of
PhPdH occurs to give 1,2-diphenyl-2-propen-1-one with
the liberation of Pd%0) species and benzene. The a,b-
unsaturated ketone undergoes second phenylation as in the
usual reaction via carbopalladation.
The lack of a,g-diphenylated product implies that the
g-diphenylation [step %c)] is signi®cantly fast. Compounds
10±12a seem to be the end products, since they have no
more active hydrogens that lead to enolates. The steps %b)
and %d)±%f) can be suppressed selectively by selecting

Y. Terao et al. / Tetrahedron 57 ,2001) 5967±5974
5969
well as that with 1a, using P%o-Tolyl)3 as ligand were
produced the corresponding triarylated products 9a±c in
substantial yields %Scheme 6 and entries 10±12).
To obtain some insight into factors affecting the penta-
arylation leading to 12, the reactions of 4-chlorophenyl
propyl ketone %7b) with 1a using PPh3 and of 7a and b
13
with 1b using P%4-FC6H4)3 were carried out %Scheme 7
and entries 13±15).
It was observed that 7b affords considerably enhanced
yields of 12 %entries 13 and 15 vs 7 and 14). This implies
that the 4-chloro substituent enhances step %f) in Scheme 5
%ortho-arylation). It should be noted that in the reactions of
benzyl phenyl ketones %2) with 1a, the 4-chloro derivative
2b %YˆCl) also reacted considerably faster than 2a %YˆH),
Scheme 4.
Scheme 6.
Scheme 7.
Scheme 5.
ligands appropriately. The steric bulkiness of ligands
appears to be the major factor affecting the rate of the
steps.12
In expectation, from the reactions of 7a with 4 equiv. of
4-¯uoro- and 4-methylbromobenzenes, %1b) and %1c), as
Scheme 8.

5970
Y. Terao et al. / Tetrahedron 57 ,2001) 5967±5974
whereas 2c %YˆOMe) was consumed very slowly %Scheme
1 and entries 1±3). These results suggest that an electron-
withdrawing substituent on alkyl phenyl ketones enhances
ortho-arylation, possibly by promoting enolate formation.
The reaction of valerophenone %13) with 1a using PPh3 as
ligand gave a mixture of g,g-diphenylated product 14 and
a,g,g-triphenylated one 15 %Scheme 8 and entry 16).
Scheme 9.
It is reasonable to consider that the initial unsaturation of 13
followed by g,g-diphenylation leads to 14. The triphenyl-
ated compound 15 could be formed by either a-phenylation
followed by unsaturation and g,g-diphenylation as in steps
%a)±%c) in Scheme 5 or initial unsaturation followed by
a,g,g-triphenylation. Therefore, in the reaction of 7, an
alternative route involving initial unsaturation [step %a0) in
Scheme 5] should also be considered to participate. Indeed,
this was supported by the reaction of %E)-1-phenyl-2-buten-
1-one %20) as the intermediate %vide infra, Scheme 11).
Scheme 10.
Two substrates, anthrone %16) and diphenylacetaldehyde
%18), which are structural relatives of benzyl phenyl ketones
%2), were also reacted with 1a.
multiple arylation. Consequently, a number of the
compounds are treated with excess 1a %Table 2).
The reaction of %E)-1-phenyl-2-buten-1-one %20) with 1a
gave a mixture of 10±12a as in the reaction using 7a
%Scheme 11 and entry 1). This indicates that as described
above, the arylation of 7 may, in part, proceed after unsa-
turation of the propyl group.
The ketone 16 underwent triphenylation at the 1-, 8- and
10-positions, which parallels the reaction of 2 %Scheme 9
and entry 17). It was, however, observed that the 10-position
was unexpectedly hydroxylated. The hydroxyl group would
come from the base or adventitious water, but the mode of
its addition is not de®nitive at the present stage. The reaction
of 18 with 4 equiv. of 1a gave a complex mixture involving
mono- to triphenylated products along with other unidenti-
®ed compounds, which was con®rmed by GC±MS.
However, ortho-monophenylated compound 19 could be
obtained by using 1.5 equiv. of 18 %Scheme 10and entry
18). The reaction in DMF gave a better yield %entry 19). The
formation of 19 suggests that ortho-arylation of benzyl
carbonyl compounds is possible, while it favorably occurs
in benzoyl compounds as indicated by the results using 2.
It was of interest that the reaction using P%t-Bu)3 gave 9a as
the single major product along with trace amounts of 10 and
11 %entry 2). The conditions employed were similar to those
for the reaction of 7a in entry 9 of Table 1 in which the
monophenylated product 8 was produced as the major one.
These results suggest that the bulky ligand can effectively
enhance a,g,g-triphenylation of the a,b-unsarurated ketone
to 9a, while its further transformations to 10±12a as well as
the unsaturation of 8 are suppressed.12
Treatment of %E)-2-octenal %21) with 4 equiv. of 1a using
Pd%OAc)2±PPh3 gave a mixture of g,g-diphenylated product
The results of the reactions of 7 and 13 may suggest that
various a,b-unsaturated carbonyl compounds can undergo
Table 2. Arylation of a,b-unsaturated carbonyl compounds with bromobenzene
Entry
Substrate
1a %mmol)
Pd%OAc)2 %mmol)
PR3
Solvent
Temperaturea %8C)
Time %h)
Product%s); % yieldb
c
1
2
3
4
5
6
7
8
20
20
21
24a
24a
24a
24b
24c
27
7.5
7.5
4
3
3
3
3
3
2
0.125
0.075
0.025
0.1
0.1
0.1
0.05
0.05
0.05
0.05
0.05
0.075
PPh3
o-Xylene
o-Xylene
o-Xylene
o-Xylene
DMF
DMF
DMF
DMF
DMF
1602
1602
1603
16024
8024
8024
607
603
805
8045
1604
16040
10; 10%8), 11; 18 %12), 12a; %34)
9a; 85
22; 34 %29), 23; 44 %34)
25a; 15
25a; 53 %53)
26;d 54
25b; %59)
25c; %36)
28; 79 %56)
c
P%t-Bu)3
PPh3
PPh3
P%t-Bu)3
PPh3
P%t-Bu)3
P%t-Bu)3
PPh3
9e
10f
11
12
27
30
32
4
4
4
P%t-Bu)3
P%t-Bu)3
PPh3
DMF
o-Xylene
o-Xylene
29; 64 %48)
31; 60%55)
33; %21), 34; %27)
c
The reaction was carried out using 1 mmol of substrate in the presence of Cs2CO3 as base. [PhBr]ˆ[Cs2CO3], [PR3]/[Pd%OAc)2]ˆ2.
a
Bath temperature.
Determined by GLC analysis. Value in parentheses indicates isolated yield.
b
c
[PR3]/[Pd%OAc)2]ˆ4.
d
%E)-2-ethyl-4-phenyl-2-hexenal.
Taken from the data in Ref. 7.
6 mmol of Cs2CO3 was used.
e
f

Y. Terao et al. / Tetrahedron 57 ,2001) 5967±5974
5971
%24c) using P%t-Bu)3 in DMF gave the corresponding g,g-
diphenylated products, 25b and c, as expected %entries 7 and
8). In the reaction of isophorone %27), the use of PPh3 and
P%t-Bu)3 resulted in the selective formation of g,g-diphenyl-
ated product 28 and a,g,g-triphenylated one 29, respec-
tively %Scheme 14 and entries 9 and 10).
The reaction of %E)-N-phenyl-2-butenamide %30) using
P%t-Bu)3 in o-xylene unexpectedly gave b,g,g-triphenylated
product 31 %Scheme 15 and entry 11), while using PPh3 was
formed a complex mixture. In this special case, b-phenyl-
ation via carbopalladation could initially occur.
Scheme 11.
22 and a,g,g-triphenylated one 23 in comparable yields
%Scheme 12 and entry 3). This parallels the reaction of 13
%Scheme 8).
It was also interesting that two kinds of diphenylated and
cyclized products 33 and 34 were obtained from the reaction
of %Z)-1,3-diphenyl-2-buten-1-one %32) %Scheme 16 and
entry 12).
The reaction of %E)-2-ethyl-2-hexenal %24a) under similar
conditions gave the expected g,g-diphenylated product 25a,
but the yield was poor %Scheme 13 and entry 4). Using
P%t-Bu)3 as ligand in DMF at a lower temperature of 808C
was found to considerably improve the yield %entry 5).
The furan 33 may be formed by a,g-diphenylation followed
by oxidative cyclization with the aid of phenylpalladium
species. However, the modes of phenylation and addition
of an external oxygen %as in the case of 16) leading to 34 are
unclear.
It is noted that as reported previously,7 the reaction of 24a
using PPh3 in DMF selectively gave g-monophenylated
product, %E)-2-ethyl-4-phenyl-2-hexenal %26), even in the
presence of 3 equiv. of 1a %entry 6). The reactions of
%E)-2-methyl-2-pentenal %24b) and %E)-2-phenyl-2-pentenal
In summary, we have demonstrated that alkyl aryl ketones
as well as a,b-unsaturated carbonyl compounds can be
multiply arylated upon treatment with excess aryl bromides
using palladium catalysts. This appears to provide a
straightfoward method for preparing a number of oligoaryl
compounds.
Scheme 12.
Scheme 15.
Scheme 13.
Scheme 14.
Scheme 16.

5972
Y. Terao et al. / Tetrahedron 57 ,2001) 5967±5974
3. Experimental
Jˆ248.2 Hz), 162.33 %d, Jˆ248.2 Hz), 162.47 %d,
Jˆ248.2 Hz), 198.57; MS m/z 428 %M1). Anal. calcd for
3.1. General
C28H19F3O: C, 78.49; H, 4.47. Found: C, 78.10; H, 4.68.
1H and 13C NMR spectra were recorded at 400 and
100 MHz, respectively, for CDCl3 solutions. MS analysis
was made by EI. GLC analysis was carried out using a
Silicone OV-17 glass column %i.d. 2.6 mm£1.5 m). Benzyl
phenyl ketones 2b and c were prepared by the Friedel±
Crafts reaction of the corresponding substituted benzenes
with phenylacetyl chloride in the presence of AlCl3.
Amide 30 was prepared by the reaction of trans-crotonyl
chloride with aniline. Other starting materials were
commercially available. The solvents employed were
puri®ed by standard methods before use. The following
experimental procedure may be regarded as typical in
methodology and scale.
3.2.3. 1-Phenyl-2,4,4-tri+4-methylphenyl)-3-buten-1-one
+9c). Mp 115±1178C; H NMR d 2.29 %s, 3H), 2.30%s,
1
3H), 2.41 %s, 3H), 5.39 %d, Jˆ10.3 Hz, 1H), 6.59 %d,
Jˆ10.3 Hz, 1H), 7.01±7.19 %m, 12H), 7.32 %t, Jˆ7.7 Hz,
2H), 7.45 %t, Jˆ7.7 Hz, 1H), 7.75 %d, Jˆ7.7 Hz, 2H); 13C
NMR d 21.03, 21.05, 21.30, 53.41, 126.29, 127.41, 128.11,
128.40, 128.73, 128.73, 129.05, 129.60, 129.72, 132.85,
136.39, 136.60, 136.66, 137.08, 137.13, 139.20, 142.79,
199.29; MS m/z 416 %M1). Anal. calcd for C31H28O: C,
89.38; H, 6.77. Found: C, 89.15; H, 6.77.
3.2.4. 2,4,4-Triphenyl-1+4H)-naphthalenone +10). Mp
223±2248C; H NMR d 7.23±7.40%m, 14H), 7.41 %dt,
1
Jˆ1.5, 7.3 Hz, 1H), 7.42 %s, 1H), 7.44 %dd, Jˆ1.5, 7.7 Hz,
1H), 7.49 %dd, Jˆ1.5, 8.2 Hz, 2H), 8.34 %dd, Jˆ1.8, 7.3 Hz,
1H); 13C NMR d 55.39, 127.28, 127.28, 127.58, 128.00,
128.08, 128.63, 128.89, 128.97, 130.78, 131.87, 132.30,
135.66, 135.91, 144.14, 146.00, 152.37, 183.61; MS m/z
372 %M1). Anal. calcd for C28H20O: C, 90.29; H, 5.41.
Found: C, 90.30; H, 5.60.
3.1.1. Reaction of butyrophenone +7a) with bromo-
benzene +1a). In a 100 cm3 two-necked ¯ask was placed
Cs2CO3 %7.5 mmol, 2.45 g), which was then dried at
1508C in vacuo for 2 h. Then, Pd%OAc)2 %0.1 mmol,
22.4 mg), PPh3 %0.4 mmol, 105 mg), 1a %7.5 mmol,
1.18 g), 7a %1 mmol, 148 mg), 1-methylnaphthalene %ca.
100 mg) as internal standard and o-xylene %5 cm3) were
added. The resulting mixture was stirred under N2 at
1608C %bath temperature) for 23 h. After cooling, the
reaction mixture was extracted with diethyl ether and
dried over sodium sulfate. The product mixture was
fractionated by column chromatography on silica gel
using hexane±toluene as eluent. Compounds 10 %30mg,
8%), 11 %131 mg, 29%) and 12a %111 mg, 21%) were
isolated in this order. Their characterization data as well
as other products are given below.
3.2.5. +E)-1,2,4,4,4-Pentaphenyl-2-buten-1-one +11). Mp
1
148±1518C; H NMR d 6.74 %d, Jˆ7.3 Hz, 2H; H1), 6.81
%t, Jˆ7.3 Hz, 2H; H2), 6.89 %t, Jˆ7.3 Hz, 1H; H3), 7.07±
0
0
7.15 %m, 15H; H1 ±H3 ), 7.40%t, Jˆ7.3 Hz, 2H; Hb), 7.42 %s,
1H; Hv), 7.51 %t, Jˆ7.3 Hz, 1H; Hc), 7.90%d, Jˆ7.3 Hz, 2H;
Ha); 13C NMR d 61.35, 126.37, 126.50, 127.14, 127.69,
128.30, 128.89, 130.08, 130.19, 132.45, 135.05, 137.69,
142.88, 145.25, 146.29, 198.08; MS m/z 450%M 1). Anal.
calcd for C34H26O: C, 90.63; H, 5.82. Found: C, 90.46; H,
5.89.
3.2. Products
3.2.6. +E)-1-+1,10-Biphenyl-2-yl)-2,4,4,4-tetraphenyl-2-
buten-1-one +12a). Mp 136±1388C; H NMR d 6.41 %d,
1
Compounds 4 %XˆYˆZˆH),8 4 %XˆZˆH, YˆCl),8 %E)-
6,14 %Z)-6,14 8,15 9a,16 17,17 26,7 28,7 3318 and 3419 are
known. The characterization data of new compounds are
given below.
0
Jˆ7.6 Hz, 2H; H1), 6.62 %dd, Jˆ1.8, 6.9 Hz, 6H; H1 ),
6.73 %t, Jˆ7.6 Hz, 2H; H2), 6.803 %t,0 Jˆ7.3, 7.6 Hz, 1H;
0
H3), 6.97±7.06 %m, 11H; Ha , H2 , H3 ), 7.30%t, Jˆ7.6 Hz,
0
2H; Hb ), 7.34 %dd, Jˆ1.5, 7.6 Hz, 1H; Hd), 7.40%t, Jˆ7.3,
0
7.6 Hz, 1H; Hc ), 7.47 %t, Jˆ7.3, 7.6 Hz, 1H; Hc), 7.48 %s,
1H; Hv), 7.52 %t, Jˆ7.3, 7.6 Hz, 1H; Hb), 7.58 %dd, Jˆ1.8,
7.3 Hz, 1H; Ha); 13C NMR d 61.28, 126.14, 126.29, 126.57,
127.26, 127.49, 127.59, 128.68, 128.73, 129.24, 129.43,
129.60, 129.89, 130.03, 133.89, 139.88, 140.05, 140.62,
144.11, 144.92, 155.48, 201.77; MS m/z 526 %M1). Anal.
calcd for C40H30O: C, 91.22; H, 5.74. Found: C, 91.08; H,
5.74. The NOE peak enhancements in 11 and 12a were as
follows:
3.2.1. 2-Phenyl-1-+4-methoxy-1,10:3,10-terphenyl-2-yl)-2-
ethanone +4; XˆZˆH, YˆOMe). Oil; 1H NMR d 3.84 %s,
3H), 4.70%s, 1H), 6.70%d, Jˆ7.3 Hz, 4H), 6.79 %s, 2H), 6.98
%t, Jˆ6.8, 7.3 Hz, 4H), 7.04 %t, Jˆ6.8 Hz, 2H), 7.15 %d,
Jˆ7.3 Hz, 4H), 7.22 %t, Jˆ7.3, 7.6 Hz, 4H), 7.25 %t,
Jˆ7.6 Hz, 2H); 13C NMR d 55.40, 65.45, 114.95, 126.40,
127.12, 127.50, 127.94, 128.08, 128.80, 129.60, 138.26,
140.41, 142.60, 159.07, 20288; MS m/z 454 %M1). Anal.
calcd for C33H26O2: C, 87.20; H, 5.77. Found: C, 86.92;
H, 6.05.
3.2.2. 1-Phenyl-2,4,4-tri+4-¯uorophenyl)-3-buten-1-one
1
+9b). Oil; H NMR d 5.34 %d, Jˆ10.3 Hz, 1H), 6.59 %d,
Jˆ10.3 Hz, 1H), 6.92±7.01 %m, 4H), 7.07±7.11 %m, 4H),
7.15±7.22 %m, 4H), 7.36 %t, Jˆ7.3, 8.1 Hz, 2H), 7.50%t,
Jˆ7.3 Hz, 1H), 7.73 %dd, Jˆ1.5, 8.1 Hz, 2H); 13C NMR d
52.82, 115.09 %d, Jˆ21.1 Hz), 115.67 %d, Jˆ21.1 Hz),
115.97 %d, Jˆ21.1 Hz), 127.23, 128.63, 128.63, 129.03 %d,
Jˆ7.4 Hz), 129.66 %d, Jˆ7.3 Hz), 131.34 %d, Jˆ8.3 Hz),
133.33, 134.89 %d, Jˆ3.7 Hz), 135.06 %d, Jˆ3.7 Hz),
135.91, 137.44 %d, Jˆ2.8 Hz), 141.33, 161.91 %d,
3.2.7. +E)-1-+5-Chloro-1,10-biphenyl-2-yl)-2,4,4,4-tetra-
phenyl-2-buten-1-one +12b). Mp 179±1818C; H NMR d
1

Y. Terao et al. / Tetrahedron 57 ,2001) 5967±5974
5973
6.39 %dd, Jˆ1.1, 8.4 Hz, 2H), 6.62 %dd, Jˆ1.8, 8.4 Hz, 6H),
6.72 %t, Jˆ7.7 Hz, 2H), 6.83 %t, Jˆ7.3 Hz, 1H), 6.99 %t,
Jˆ1.5, 8.4 Hz, 6H), 7.02±7.07 %m, 5H), 7.31 %t, Jˆ7.7,
8.4 Hz, 2H), 7.32 %s,1H), 7.41 %d, Jˆ7.3 Hz, 1H), 7.45
%dd, Jˆ1.8, 8.1 Hz, 1H), 7.47 %s, 1H), 7.52 %d, Jˆ8.1 Hz,
1H); 13C NMR d 61.38, 126.25, 126.42, 126.62, 127.56,
127.70, 127.82, 128.87, 129.08, 129.40, 129.51, 130.02,
130.21, 133.64, 135.70, 138.29, 139.29, 141.83, 143.86,
144.77, 155.49, 200.62; MS m/z 560, 562 %M1). Anal.
calcd for C40H29ClO: C, 85.62; H, 5.21; Cl, 6.32. Found:
C, 85.77; H, 5.28; Cl, 6.49.
NMR d 5.04 %d, Jˆ1.4 Hz, 1H), 7.05 %d, Jˆ6.8 Hz, 2H),
7.19±7.41%m, 12H), 9.86 %d, Jˆ1.4 Hz, 1H); 13C NMR d
60.65, 127.31, 127.43, 127.77, 128.26, 128.76, 128.98,
129.03, 129.29, 129.54, 130.76, 133.66, 137.05, 140.71,
143.32, 198.96; MS m/z 272 %M1). Anal. calcd for
C20H16O: C, 88.20; H,5.92. Found: C, 87.80; H, 6.02.
1
3.2.13. +E)-4,4-Diphenyl-2-octenal +22). Oil; H NMR d
0.85 %t, 3H, Jˆ7.3 Hz, 3H), 1.08±1.14 %m, 2H), 1.29±1.35
%m, 2H), 2.29±2.34 %m, 2H), 5.94 %dd, Jˆ7.7, 16.1 Hz, 1H),
7.13±7.33 %m, 10H), 7.38 %d, Jˆ16.1 Hz, 1H), 9.63 %d,
Jˆ7.7 Hz, 1H); 13C NMR d 13.91, 23.27, 26.91, 38.30,
54.12, 126.71, 128.30, 128.34, 131.46, 144.85, 163.78,
194.11; HRMS m/z %M1) calcd for C20H22O 278.1671,
found 278.1673.
3.2.8. +E)-1-+40-Fluoro-1,10-biphenyl-2-yl)-2,4,4,4-tetra+4-
¯uorophenyl)-2-buten-1-one +12c). Mp 187±1898C; 1H
NMR d 6.30±6.34 %m, 2H), 6.51 %t, Jˆ8.8 Hz, 2H), 6.55±
6.59 %m, 6H), 6.72±6.77 %m, 6H), 6.98±7.06 %m, 4H), 7.31
%d, Jˆ7.3 Hz, 1H), 7.40%s, 1H), 7.47±7.56 %m, 3H); 13C
3.2.14. +E)-2,4,4-Triphenyl-2-octenal +23). Oil; 1H NMR d
0.67 %t, Jˆ6.9 Hz, 3H), 0.86±0.92 %m, 4H), 1.90±1.96 %m,
2H), 6.71 %dd, Jˆ1.3, 7.9 Hz, 2H), 7.12±7.28 %m, 13H), 7.52
%s, 1H), 9.71 %s, 1H); 13C NMR d 13.83, 22.81, 27.08, 38.25,
53.86, 126.41, 127.63, 127.67, 128.13, 128.23, 129.03,
133.10, 143.26, 146.97, 161.07, 194.92; HRMS m/z %M1)
calcd for C26H26O 354.1984, found 354.1980.
NMR d 59.59, 113.80%d,
Jˆ22.1 Hz), 114.65 %d,
Jˆ21.1 Hz), 115.67 %d, Jˆ21.1 Hz), 127.93, 128.71,
129.43 %d, Jˆ3.7 Hz), 129.57, 130.30, 130.85 %d,
Jˆ8.3 Hz), 130.99 %d, Jˆ8.3 Hz), 131.27 %d, Jˆ8.3 Hz),
136.63 %d, Jˆ3.7 Hz), 138.58, 139.40, 140.27 %d,
Jˆ3.7 Hz), 143.23, 154.50, 161.26 %d, Jˆ248.2 Hz),
161.58 %d, Jˆ248.2 Hz), 162.54 %d, Jˆ248.2 Hz), 201.06;
MS m/z 616 %M1). Anal. calcd for C40H25F5O: C, 77.91; H,
4.09. Found: C, 77.74; H, 4.21.
3.2.15. +E)-2-Ethyl-4,4-diphenyl-2-hexenal +25a). Mp
62±638C; 1H NMR d 0.48 %t, Jˆ7.3 Hz, 3H), 0.80 %t,
Jˆ7.3 Hz, 3H), 1.83 %q, Jˆ7.3 Hz, 2H), 2.43 %q,
Jˆ7.3 Hz, 2H), 7.16 %s, 1H), 7.20±7.32 %m, 10H), 9.05 %s,
1H); 13C NMR d 9.61, 11.23, 18.67, 34.18, 53.78, 126.42,
128.24, 128.24, 145.73, 146.41, 159.73, 196.37; MS m/z 278
%M1). Anal. calcd for C20H22O: C, 86.29; H, 7.97. Found: C,
86.23; H, 7.94.
3.2.9. +E)-1-+5-Chloro-40-¯uoro-1,10-biphenyl-2-yl)-2,4,4,
4-tetra+4-¯uorophenyl)-2-buten-1-one +12d). Mp 190±
1
1938C; H NMR d 6.30%dd, Jˆ5.4, 8.6 Hz, 2H), 6.51 %t,
Jˆ8.6 Hz, 2H), 6.58 %dd, Jˆ5.3, 8.4 Hz, 6H), 6.76 %t,
Jˆ8.4 Hz, 6H), 6.96±6.99 %m, 2H), 7.05 %t, Jˆ8.4 Hz,
2H), 7.30%d, Jˆ1.8 Hz, 1H), 7.40%s, 1H), 7.45±7.50%m,
2H); 13C NMR d 59.67, 113.87 %d, Jˆ22.1 Hz), 114.72 %d,
Jˆ21.1 Hz), 115.88 %d, Jˆ21.1 Hz), 128.08, 128.32, 129.20
%d, Jˆ3.7 Hz), 129.50, 130.25, 130.80 %d, Jˆ7.4 Hz),
130.97 %d, Jˆ8.3 Hz), 131.26 %d, Jˆ8.3 Hz), 135.30%d,
Jˆ3.7 Hz), 136.22, 137.76, 140.13 %d, Jˆ3.7 Hz), 142.96,
154.44, 161.30%d, Jˆ248.2 Hz), 161.62 %d, Jˆ248.2 Hz),
162.80%d, Jˆ278.2 Hz), 199.91; MS m/z 650, 652 %M1).
Anal. calcd for C40H21ClF5O: C, 73.79; H, 3.72. Found: C,
74.15; H, 4.06.
3.2.16. +E)-2-Methyl-4,4-diphenyl-2-pentenal +25b). Oil;
1H NMR d 1.35 %d, Jˆ1.5 Hz, 3H), 1.97 %s, 3H), 7.10%q,
Jˆ1.5 Hz, 1H), 7.21±7.34 %m, 10H), 9.49 %s, 1H); 13C NMR
d 10.39, 28.79, 50.08, 126.60, 127.53, 128.45, 140.07,
146.90, 162.36, 196.31; MS m/z 250%M 1). Anal. calcd for
C18H18O: C, 86.36; H, 7.25. Found: C, 86.07; H, 7.22.
3.2.17. +E)-2,4,4-Triphenyl-2-pentenal +25c). Oil; 1H
NMR d 1.51 %s, 3H), 6.82 %dd, Jˆ1.5, 7.8 Hz, 2H), 7.14±
7.31 %m, 13H), 7.37 %s, 1H), 9.69 %s, 1H); 13C NMR d 28.42,
50.81, 126.60, 127.56, 127.68, 127.76, 128.41, 129.28,
133.14, 143.23, 147.89, 162.07, 194.92; HRMS m/z %M1)
calcd for C23H20O: 312.1514, found 312.1516.
1
3.2.10. +E)-1,4,4-Triphenyl-2-penten-1-one +14). Oil; H
NMR d 1.93 %s, 3H), 6.70%d, Jˆ15.8 Hz, 1H), 7.20±7.26
%m, 6H), 7.31 %t, Jˆ7.0, 7.7 Hz, 4H), 7.44 %t, Jˆ7.3, 7.7 Hz,
2H), 7.53 %t, Jˆ7.3 Hz, 1H), 7.61 %d, Jˆ15.8 Hz, 1H), 7.86
%dd, Jˆ1.5, 7.7 Hz, 2H); 13C NMR d 27.21, 50.24, 124.05,
126.58, 127.79, 128.33, 128.53, 128.53, 132.74, 137.94,
146.54, 155.99, 190.83; HRMS m/z %M1) calcd for
C23H20O 312.1514, found 312.1515.
3.2.18. 5,5-Dimethyl-2-phenyl-3-+diphenylmethyl)-2-cyclo-
hexen-1-one +29). Mp 105±1068C; 1H NMR d 1.05 %s, 6H),
2.31 %s, 2H), 2.40%s, 2H), 5.21 %s, 1H), 7.01±7.36 %m, 15H);
13C NMR d 28.18, 33.10, 41.06, 51.85, 54.68, 126.80,
127.47, 128.24, 128.41, 129.13, 129.56, 135.79, 138.95,
140.98, 157.05, 198.77; MS m/z 366 %M1). Anal. calcd for
C27H26O: C, 88.48; H, 7.15. Found: C, 88.09; H, 7.11.
3.2.11. +E)-1,2,4,4-Tetraphenyl-2-penten-1-one +15). Oil;
1H NMR d 1.49 %s, 3H), 6.99±7.01 %m, 2H), 7.07 %s, 1H),
7.11±7.14 %m, 4H), 7.18±7.21 %m, 5H), 7.23±7.28 %m, 4H),
7.39 %t, Jˆ7.7, 7.3 Hz, 2H), 7.49 %t, Jˆ7.3 Hz, 1H), 7.79
%dd, Jˆ1.5, 7.7 Hz, 2H); 13C NMR d 28.63, 50.55, 126.29,
127.32, 127.59, 127.64, 128.21, 128.23, 129.44, 129.87,
132.25, 135.75, 137.90, 140.76, 148.75, 149.50, 197.64;
HRMS m/z %M1) calcd for C29H24O 388.1827, found
388.1826.
3.2.19. N-Phenyl-3,4,4-triphenyl-3-butenamide +31). Mp
1
207±2088C; H NMR d 3.62 %s, 2H), 6.93±6.96 %m, 2H),
7.04±7.40 %m, 19H); 13C NMR d 44.95, 119.66, 124.22,
126.57, 127.13, 127.51, 127.65, 128.54, 128.55, 128.91,
129.54, 129.60, 130.67, 132.50, 137.71, 141.58, 142.07,
142.21, 144.32, 168.64; MS m/z 329 %M1). Anal. calcd for
C28H23ON: C, 86.34; H, 5.95; N, 3.59. Found: C, 85.99; H,
5.67; N, 3.70.
3.2.12. 2-+Biphenyl-2-yl)phenylacetaldehyde +19). Oil; 1H

5974
Y. Terao et al. / Tetrahedron 57 ,2001) 5967±5974
7. Terao, Y.; Satoh, T.; Miura, M.; Nomura, M. Tetrahedron
Lett. 1998, 39, 6203.
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13. Use of the corresponding triarylphosphine can avoid the
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