A novel lanthanum metal-assisted reaction of diaryl ketones and electrophiles

Article abstract of DOI:10.1016/j.tet.2014.12.089

A novel and efficient lanthanum metal-assisted carbon-carbon bond formation of diaryl ketones and various electrophiles, such as carbonyl compounds, esters, nitriles, and epoxides, has been developed. When diaryl ketones were allowed to react with dialkyl ketones in the presence of lanthanum metal and a catalytic amount of iodine, the cross pinacol coupling reaction proceeded to give the corresponding unsymmetrical 1,2-diols in moderate to good yields. α-Hydroxy ketones were prepared by the lanthanum metal-assisted reaction of diaryl ketones with esters or nitriles, followed by hydrolysis with aq HCl. It is interesting to note that for the epoxides, the coupling reaction proceeded via the Meinwald rearrangement of epoxides to give the corresponding 1,2-diols.

Full text of DOI:10.1016/j.tet.2014.12.089

Tetrahedron 71 (2015) 1287e1291
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
A novel lanthanum metal-assisted reaction of diaryl ketones and
electrophiles
Rui Umeda, Masashi Ninomiya, Toshiaki Nishino, Makoto Kishida, Shunsuke Toiya,
*
Tomoki Saito, Yutaka Nishiyama , Noboru Sonoda
Department of Chemistry and Material Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680,
Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel and efficient lanthanum metal-assisted carbon-carbon bond formation of diaryl ketones and
various electrophiles, such as carbonyl compounds, esters, nitriles, and epoxides, has been developed.
When diaryl ketones were allowed to react with dialkyl ketones in the presence of lanthanum metal and
a catalytic amount of iodine, the cross pinacol coupling reaction proceeded to give the corresponding
Received 1 September 2014
Received in revised form 20 December 2014
Accepted 23 December 2014
Available online 31 December 2014
unsymmetrical 1,2-diols in moderate to good yields. a-Hydroxy ketones were prepared by the lanthanum
metal-assisted reaction of diaryl ketones with esters or nitriles, followed by hydrolysis with aq HCl. It is
interesting to note that for the epoxides, the coupling reaction proceeded via the Meinwald rearrange-
ment of epoxides to give the corresponding 1,2-diols.
Keywords:
Lanthanum
Diaryl ketone
Electrophile
Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction
ketones were obtained. It is interesting to note that for the
epoxides, the coupling reaction proceeded via the Meinwald rear-
The utilization of lanthanoid metal salts and organolanthanoid
compounds as synthetic reagents or catalysts in organic synthesis
has been steadily increasing due to their unique chemical proper-
ties. In particular, low-valent, trivalent, and tetravalent lanthanoid
compounds have been widely used in organic reactions.1 On the
hand, although it is expected that zero-valent lanthanoid metals
bear a potential reducing ability could be used as the reducing
agent in organic synthesis, the direct use of lanthanoid metals in
organic synthesis is still rare due to their low solubility in an or-
ganic solvent or to their instability under aerobic conditions.2e5
We have recently succeeded in the direct use of lanthanum
metal as a reagent in the presence of a catalytic amount of iodine in
organic synthesis.6 During the course of our study on the direct use
of lanthanum metal in organic synthesis, it was found that various
electrophiles were efficiently introduced onto the carbonyl carbon
of diaryl ketones in the presence of lanthanum metal and a catalytic
amount of iodine.7 When diaryl ketones were treated with dialkyl
ketones in the presence of lanthanum metal and a catalytic amount
of iodine, the corresponding unsymmetrical 1,2-diols, the cross
pinacol coupling products, were formed in moderate to good
rangement of epoxides to give the corresponding 1,2-diols (Scheme
1).14 Fujiwara et al. have already reported ytterbium metal pro-
moted the cross-coupling reaction of diaryl ketones with a various
electrophiles to give the corresponding products.4aec However, in
the case of Yb, two-step procedures (time integration15), including
(i) the reaction of diaryl ketones with Yb metal and (ii) the addition
of electrophiles to the resulting solution of (i), were used on the
reaction. On the other hand, in the case of La metal, the cross
pinacol coupling products were formed in good yields by a simple
yields.10,11 For the reaction of nitriles12 and esters,13
a-hydroxy
* Corresponding author. Tel.: þ81 6 6368 0902; fax: þ81 6 6339 4026; e-mail
Scheme 1.
address: nishiya@kansai-u.ac.jp (Y. Nishiyama).
http://dx.doi.org/10.1016/j.tet.2014.12.089
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.

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R. Umeda et al. / Tetrahedron 71 (2015) 1287e1291
Table 1
procedure. Furthermore, in the case of epoxide, it is interesting to
note that the reaction proceeded via the Meinwald rearrangement
of epoxides.
La-assisted reaction of diaryl ketones with carbonyl compoundsa
2. Results and discussion
Entry
1
Diaryl ketone
Carbonyl compound
Yieldb (%)
When benzophenone (1a) was allowed to react with lanthanum
metal in a presence of a catalytic amount of iodine in THF solvent at
25 ꢀC, the solution initially showed a ketyl-like blue color that
gradually turned brown. After stirring for 3 h, 3-pentanone (2a)
was added to the resulting solution, and the solution was stirred for
additional 3 h. Subsequent hydrolysis of the reaction mixture with
aq HCl formed 2-ethyl-1,1-diphenyl-1,2-butanediol (3a), a cross-
coupling product between 1 and 2, in 73% yield along with benz-
hydrol (4a), the reduction product of 1a (17%) (Scheme 2). This
cross-coupling reaction could be conducted by a convenient one-
step procedure (time and space integration15). As shown in
Scheme 3, in the case of the one-pot procedure (time and space
integration), cross-coupling between 1a and 2a produced a higher
selectivity than that of the two-step procedures (time integration),
and the yield of 3a had increased to 84%.
3a 84
2
3
4
Ar¼4-CH3C6H4
Ar¼3-CH3C6H4
Ar¼2-CH3C6H4
Ar¼4-CH3OC6H4
Ar¼4-ClC6H4
3b 67
3c 90
Trace
3d 90
3e 37
3f 74
c
5
6
7
Ar¼2-Naphthyl
8
9
10
Ar¼4-CH3C6H4
Ar¼4-CH3OC6H4
Ar¼4-ClC6H4
3g 74
3h 74
trace
11d
3i 61
4a 87
12d,e
Scheme 2.
13
3j 47
14f
3k 44
4a 64
Scheme 3.
15e
To elucidate the scope and limitation of the lanthanum metal-
assisted coupling reaction of diaryl ketones and carbonyl com-
pounds, various diaryl ketones were treated with carbonyl com-
pounds in the presence of lanthanum metal and a catalytic
amount of iodine, and these results are shown in Table 1. The
coupling of 4-methyl-, 3-methyl-, 4-methoxy-, 4,40-dimethyl-, and
4,40-dimethoxybenzophenone, in which the electron donating
group was substituted on the aromatic ring, gave the corre-
sponding unsymmetrical 1,2-diols 3b,c,d,g,h in 67e90%
yield (entries 2, 3, 5, 8, and 9). In the case of 4-chloro- and 4,40-
dichlorobenzophenones bearing an electron withdrawing group,
the yields of the corresponding unsymmetrical 1,2-diols were
significant decreased (entries 6 and 10). For the sterically hindered
diaryl ketone, such as 2-methylbenzophenone, the cross-coupling
product was not obtained at all (entry 4). 2-Ethyl-1-(2-naphthyl)-
1-phenyl-1,2-butanediol (3f) was obtained in 74% yield by the
reaction between 2-naphthyl phenyl ketone and 3-pentanone
(entry 7). When cyclohexanone was used as an aliphatic ketone
instead of 2a, the cross pinacol coupling reaction also proceeded to
form 1,2-diol 3j in 47% yield (entry 13). In the case of a sterically
hindered dialkyl ketone, such as 2,4-dimethyl-3-pentanone, the
coupling reaction did not proceed at all and benzhydrol (4a), the
reduction product of 1a, was formed in 87% yield (entry 12). For
the reaction of 3-methyl-2-butanone and acetophenone, the yields
of the cross-coupling products decreased, however, the product
a
Reaction conditions: La (1.5 mmol), diaryl ketone (1.0 mmol), carbonyl com-
pound (1.0 mmol), I2 (0.3 mmol), THF (5 mL) at 25 ꢀC for 3 h.
b
Isolated yield.
3-Pentanone (2.0 mmol) was used.
At 67 ꢀC for 9 h.
The yield of benzhydrol.
At 67 ꢀC for 15 h.
c
d
e
f
yields 3i,k were improved by extending the reaction time at
a higher reaction temperature (67 ꢀC) (entries 11 and 14). In the
case of benzaldehyde, 4a was formed in 64% yield along with the
formation of various complicated by-products (entry 15). When an
imine was used as the electrophile instead of carbonyl com-
pounds,
a-amino alcohol was also synthesized by this protocol
(Scheme 4).16,17
Scheme 4.

R. Umeda et al. / Tetrahedron 71 (2015) 1287e1291
1289
In order to determine the applicability of the lanthanum metal-
assisted carbonecarbon bond formation of diaryl ketones, the re-
action of benzophenone (1a) with esters or nitriles was next ex-
amined in the presence of lanthanum metal and a catalytic amount
of iodine. These results are shown in Table 2. When 1a was allowed
to react with ethyl benzoate in the presence of lanthanum metal at
25 ꢀC, a benzoyl group was efficiently introduced onto the carbonyl
carbon of 1a to give 2-hydroxy-1,2,2-triphenylethanone (5a) in 60%
yield along with the formation of diphenylmethyl benzoate (6%)
(entry 1). Compound 5a was also prepared by the treatment of 1a
with benzonitrile followed by hydrolysis with HCl aq in 60% yield
(entry 5). For the reaction with benzoyl chloride, the yield of 5a was
low (2%) due to preparation of various complicated by-products.
Similarly, 1a was coupled with various esters or nitriles to give
the corresponding
a-hydroxy ketones in moderate yields, however,
for the -disubstituted ester, the reaction did not proceed (entries
a
Scheme 5.
2e4 and 6e9). On the other hand, for the reaction with 2-
octyloxirane, the 1,3-diol, such as 1,1-diphenylundecane-1,3-diol
or 2-octyl-1,1-diphenyl-propane-1,3-diol, was not formed. It is in-
teresting to note that the reaction proceeded via the Meinwald
rearrangement of epoxides to give the corresponding 1,2-diol, 1,1-
diphenyldecane-1,2-diol (3l), was formed in 52% yield
(Scheme 5). In order to determine the scope and limitation of the
reaction, the treatment of 1a and 2,3-dialkyl substituted and cyclic
oxiranes in the presence of lanthanum metal formed the corre-
sponding 1,2-diols 3m and 3j, respectively, in which 1a was coupled
with the Meinwald rearrangement products of the epoxides, in
moderate yields.
shown that the treatment of benzophenone (1a) with lanthanum
metal followed by quenching with HCl/H2O afforded benzhydrol
(4a). In addition, when the reaction mixture was quenched with
DCl/D2O instead of HCl/H2O, the corresponding C-deuterated
benzhydrol (6a) was formed (Scheme 6).6a Based on these results,
at the present time, while the reaction pathway is not clearly
shown, the reaction pathway including the addition of electro-
philes to the lanthanumediaryl ketone dianion intermediate
formed by the reduction of diaryl ketone with lanthanum metal
was suggested.
Table 2
La-assisted synthesis of a
-hydroxy ketonesa
Entry
Electrophile
Product
Yieldb (%)
Scheme 6.
3. Conclusion
1
2
3
4
R¼Ph
5a 60
5b 60
5c 59
trace
In summary, we developed a lanthanum metal-assisted cross-
coupling method of diaryl ketones with ketones, esters, nitriles, and
epoxides. The present method has the following noteworthy fea-
tures: (i) direct introduction method of electrophiles onto the car-
bonyl carbon of the diaryl ketones, (ii) simple procedure, and (iii)
moderate to good yields of the products.
R¼Bn
R¼n-C6H13
R¼(CH3)2CH
5
R¼Ph
5a 60
5d 58
5e 88
5f 53
5b 63
6
R¼4-CH3C6H4
R¼2-Naphthyl
R¼CH3
4. Experimental section
4.1. Reagents
7c
8
9
R¼Bn
a
Reaction conditions: La (1.5 mmol), 1a (1.0 mmol), ester or nitrile (2.0 mmol) I2
Benzophenone, 4-methylbenzophenone, 4-chlorobenzophenone,
4-methoxybenzophenone, 2-benzoyl naphthalene, 3-pentanone,
cyclohexanone, esters, nitriles, and iodine were commercially avail-
able high-grade products and used without purification. The lan-
thanum metal was a commercially available high-grade product and
used as a fine powder grained by metal file in a glove box. THF was
purified by the usual methods before use. 2-Methylbenzophenone
and 3-methylbenzophenone were prepared by the reaction of ben-
zene with aroyl chlorides in the presence of AlCl3. N-Benzylidenea-
niline was prepared by the reaction of benzaldehyde with aniline.
The other chemical agents were commercially obtained and purified
by distillation prior to use if necessary.
(0.3 mmol), THF (5 mL) at 25 ꢀC for 3 h.
b
Isolated yield.
c
At 67 ꢀC.
Fujiwara et al. reported that the ytterbiumediaryl ketone
complex, which was prepared by the treatment of an diaryl ke-
tone with ytterbium metal, reacted with various electrophiles to
give the corresponding coupling products.4aec After then, Hou
and co-workers succeeded in the isolation of the Yb(II) benzo-
phenone dianion complex by the reaction of benzophenone with
ytterbium metal in the presence of HMPA.4e,18 We have already

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R. Umeda et al. / Tetrahedron 71 (2015) 1287e1291
4.2. General procedure for the reaction of diaryl ketones with
electrophiles
3H), 1.75e1.83 (m, 4H), 1.99 (br s, 1H), 2.75 (br s, 1H), 7.23e7.31 (m,
3H), 7.36e7.46 (m, 2H), 7.67e7.83 (m, 6H), 8.19 (s, 1H); 13C NMR
d
9.0, 29.0, 79.3, 84.2, 126.0, 126.1, 126.9, 127.0, 127.1, 127.2, 127.4,
Lanthanum powder (1.5 mmol, 208 mg) was placed in a two-
necked flask. The diaryl ketone (1.0 mmol), iodine (0.3 mmol,
76 mg), electrophile (1.0 or 2.0 mmol), and THF (5 mL) were added to
the flask, and the mixture was stirred at 25 ꢀC or 67 ꢀC for 3 h under
nitrogen atmosphere. After the reaction, aq HCl (1 M) was added to
the reaction mixture, and the resulting solution was extracted with
diisopropyl ether (five times). The organic layer was dried over
MgSO4. The resulting mixture was filtered, and the organic solvent
was removed under reduced pressure. Purification of the residue by
column chromatography on silica gel afforded the corresponding
coupling products. Products (2-ethyl-1,1-diphenyl-1,2-butanediol
(3a),19 1-(diphenylhydroxymethyl)cyclohexanol (3j),4b,19 1,1,2-
127.9, 128.4, 128.5, 128.6, 132.4, 132.9, 142.5, 144.9; IR 3568, 3056,
2966, 2937, 2879,1744,1598,1492,1446,1381, 1152,1121,1032, 963,
820, 704 cmꢁ1; MS (EI) m/z 320 (Mþ). HRMS (FAB) m/z: [MþNa]þ
calcd for C22H24O2Na: 343.1674. Found 343.1677.
4.2.6. 2-Ethyl-1,1-di(4-methylphenyl)-1,2-butanediol
solid; mp 64e65 ꢀC; 1H NMR
0.86 (t, J¼7.6 Hz, 6H), 1.67e1.74 (m,
4H), 2.00 (s, 1H), 2.30 (s, 6H), 2.69 (s, 1H), 7.07e7.09 (m, 4H),
7.50e7.52 (m, 4H); 13C NMR
8.8, 20.9, 28.5, 78.9, 83.7, 128.0, 128.3,
(3g). White
d
d
136.3, 142.0; IR 3565, 2968, 2939, 2880,1509, 1457, 1379, 1156, 1037,
1022, 964, 811, 784 cmꢁ1; MS (EI) m/z 298 (Mþ). HRMS (ESI) m/z:
[MþNa]þ calcd for C20H26O2Na: 321.1831. Found 321.1846.
triphenyl-1,2-propanediol
butanediol (3m),19 2-hydroxy-1,2,2-triphenylethanone (5a),4b 1-
hydroxy-1,1,3-triphenylpropan-2-one 1-hydroxy-1,1-
(5b),4b
diphenyloctan-2-one 1-hydroxy-1,1-diphenyl-2-(4-
(5c),4b,20
(3k),19
2-methyl-1,1-diphenyl-1,2-
4.2.7. 2-Ethyl-1,1-di(4-methoxyphenyl)-1,2-butanediol (3h). White
solid; mp 77e78 ꢀC; 1H NMR
d
0.85 (t, J¼7.6 Hz, 6H), 1.66e1.72 (m,
4H), 2.05 (s, 1H), 2.70 (s, 1H), 3.77 (s, 6H), 6.79e6.82 (m, 4H),
7.53e7.55 (m, 4H); 13C NMR
8.8, 28.5, 55.1, 79.0, 83.4, 128.0, 129.3,
methylphenyl)ethanone (5d),21 2-hydroxy-2,2-diphenyl-1-(2-
naphthyl)-1-ethanone (5e),22 and 1-hydroxy-1,1-diphenyl-2-
propanone (5f)23) were characterized by comparison of their
spectra data (1H and 13C NMR and IR) to those of authentic samples.
d
137.3, 158.2; IR 3526, 2965, 2835, 1608, 1508, 1457, 1297, 1249, 1179,
1034, 823, 584 cmꢁ1; MS (EI) m/z 330 (Mþ). HRMS (ESI) m/z:
[MþNa]þ calcd for C20H26O4Na: 353.1729. Found 353.1746.
4.2.1. 2-Ethyl-1-(4-methylphenyl)-1-phenyl-1,2-butanediol
4.2.8. 2,3-Dimethyl-1,1-diphenyl-1,2-butanediol (3i). Colorless oil;
(3b). Colorless oil; 1H NMR
d
0.86 (t, J¼7.6 Hz, 3H), 0.88 (t, J¼7.6 Hz,
1H NMR
d
0.81 (d, J¼6.8 Hz, 3H), 0.91 (d, J¼6.8 Hz, 3H), 1.23 (s, 2H),
2.02 (s, 1H), 2.05e2.16 (m, 1H), 2.80 (s, 1H), 7.21e7.31 (m, 6H),
7.63e7.65 (m, 2H), 7.71e7.73 (m, 2H); 13C NMR
18.5, 19.3, 20.4,
3H), 1.69e1.75 (m, 4H), 1.98 (br s, 1H), 2.31 (s, 3H), 2.70 (br s, 1H),
7.09e7.11 (m, 2H), 7.20e7.30 (m, 3H), 7.52e7.54 (m, 2H), 7.63e7.65
d
(m, 2H); 13C NMR
d
8.9, 21.1, 28.7, 79.1, 83.9, 126.9, 127.7, 128.2,
34.0, 79.4, 83.8, 126.8, 126.9, 127.5, 127.7, 127.9, 128.1, 144.1, 145.3; IR
3540, 3056, 2962, 2876, 1491, 1446, 1388, 1158, 1079, 1024, 749, 704,
636 cmꢁ1; MS (EI) m/z 270 (Mþ). HRMS (ESI) m/z: [MþNa]þ calcd
for C18H22O2Na: 293.1517. Found 293.1531.
128.5, 128.5, 136.6, 142.1, 145.2; IR 3544, 2967, 2938, 2879, 1726,
1509, 1446, 1379, 1256, 1155, 1033, 964, 808 cmꢁ1; MS (EI) m/z 284
(Mþ). HRMS (ESI) m/z: [MþNa]þ calcd for C19H24O2Na: 307.1674.
Found 307.1689.
4.2.9. 2-Methyl-1,1-diphenyl-1,2-undecanediol (3l). Colorless oil; 1H
4.2.2. 2-Ethyl-1-(3-methylphenyl)-1-phenyl-1,2-butanediol
NMR
1.66e1.69 (m, 1H), 2.10 (br s, 1H), 2.87 (br s, 1H), 7.22e7.29 (m, 6H),
7.59e7.63 (m, 4H); 13C NMR
14.1, 22.6, 22.9, 23.5, 29.2, 29.7, 30.3,
31.8, 37.4, 78.1, 83.1, 126.8, 126.9, 127.5, 127.6, 128.3, 128.4, 144.5,
144.6; IR 3476, 2923, 2853, 1491, 1446, 1388, 1158, 1079, 1024, 749,
704, 636 cmꢁ1; MS (EI) m/z 340 (Mþ). HRMS (ESI) m/z: [MþNa]þ
calcd for C24H34O2Na: 377.2457. Found 377.2475.
d
0.87 (t, J¼6.8 Hz, 3H), 1.23e1.26 (m, 14H), 1.46e1.48 (m, 2H),
(3c). Colorless oil; 1H NMR
d
0.87 (t, J¼7.2 Hz, 6H), 1.70e1.76 (m,
4H), 1.94 (br s, 1H), 2.32 (s, 3H), 2.72 (br s, 1H), 7.03e7.05 (m, 1H),
7.15e7.30 (m, 4H), 7.45 (s, 2H), 7.64e7.66 (m, 2H); 13C NMR
8.8,
d
d
8.9, 21.8, 21.8, 28.7, 78.9, 83.8, 125.2, 126.7, 127.4, 127.5, 128.0, 128.6,
137.1, 144.7, 144.8; IR 3546, 2968, 2939, 2880, 1602, 1491, 1459,
1446, 1380, 1321, 1148, 1034, 965, 850 cmꢁ1; MS (EI) m/z 284 (Mþ).
HRMS (FAB) m/z: [MþNa]þ calcd for C19H24O2Na: 307.1674. Found
307.1678.
4.3. Two-step procedure for the reaction of benzophenone
with 3-pentanone
4.2.3. 2-Ethyl-1-(4-methoxyphenyl)-1-phenyl-1,2-butanediol
(3d). Colorless oil; 1H NMR
d
0.85 (t, J¼7.6 Hz, 3H), 0.87 (t, J¼7.6 Hz,
Lanthanum powder (1.5 mmol, 208 mg) was placed in a two-
necked flask. Benzophenone (1.0 mmol, 182 mg), iodine
(0.3 mmol, 76 mg), and THF (5 mL) were added to the flask, and the
mixture was stirred at 25 ꢀC for 3 h under nitrogen atmosphere. 3-
Pentanone (1.0 mmol, 86 mg) was added to the resulting solution,
and the mixture was stirred at 25 ꢀC for 3 h. After the reaction,
aq HCl (1 M) was added to the reaction mixture, and the resulting
solution was extracted with diisopropyl ether (five times). The or-
ganic layer was dried over MgSO4. The resulting mixture was fil-
tered, and the organic solvent was removed under reduced
pressure. Purification of the residue by column chromatography on
silica gel afforded 2-ethyl-1,1-diphenyl-1,2-butanediol (3a).
3H), 1.68e1.73 (m, 4H), 1.98 (br s, 1H), 2.67 (br s), 1H 3.78 (s, 3H),
6.81e6.86 (m, 2H), 7.23e7.30 (m, 3H), 7.56e7.64 (m, 4H); 13C NMR
d
8.9, 8.9, 28.6, 28.7, 55.2, 79.0, 83.6, 112.8, 126.7, 127.5, 128.0, 129.4,
137.1, 144.9, 158.2; IR 3520, 2966, 2938, 2880, 1608, 1510, 1462,
1445, 1296, 1251, 1182, 1035, 965, 824, 748, 705 cmꢁ1; MS (EI) m/z
300 (Mþ). HRMS (FAB) m/z: [MþNa]þ calcd for C19H24O3Na:
323.1623. Found 323.1624.
4.2.4. 2-Ethyl-1-(4-chlorophenyl)-1-phenyl-1,2-butanediol
(3e). Colorless oil; 1H NMR
d
0.86 (t, J¼7.6 Hz, 3H), 0.87 (t, J¼7.6 Hz,
3H), 1.65e1.89 (m, 4H), 1.89 (br s, 1H), 2.74 (br s, 1H), 7.23e7.31 (m,
5H), 7.60e7.92 (m, 4H); 13C NMR
8.915.4, 28.7, 79.2, 83.7, 127.2,
d
127.9, 127.9, 128.2, 129.9, 132.9, 143.8, 144.6; IR 3567, 2969, 2939,
2880, 1598, 1490, 1446, 1398, 1319, 1159, 1094, 1013, 965, 815,
703 cmꢁ1; MS (EI) m/z 304 (Mþ). HRMS (FAB) m/z: [MþNa]þ calcd
for C19H2135ClO2Na and C19H2137ClO2Na: 327.1128 and 329.1098.
Found 327.1133 and 329.1092.
4.4. General procedure for the reaction of benzophenone
with N-benzylideneaniline
Lanthanum power (1.5 mmol, 208 mg) was placed in a two-
necked flask. Benzophenone (1.0 mmol, 182 mg), iodine
(0.3 mmol, 76 mg), N-benzylideneaniline (1.0 mmol, 181 mg), and
THF (5 mL) were added to the flask, and the mixture was stirred at
25 ꢀC for 3 h under nitrogen atmosphere. After the reaction, aq HCl
4.2.5. 2-Ethyl-1-(2-naphthyl)-1-phenyl-1,2-butanediol
(3f). Colorless oil; 1H NMR
d
0.89 (t, J¼7.6 Hz, 3H), 0.90 (t, J¼7.6 Hz,

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1291
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(1 M) was added to the reaction mixture, and the resulting solution
was extracted with diisopropyl ether (five times). The organic layer
was dried over MgSO4. The resulting mixture was filtered, and the
organic solvent was removed under reduced pressure. Purification
of the residue by column chromatography on silica gel affor-
ded 1,1,2-triphenyl-2-(N-phenylamino)ehtanol. 1,1,2-Triphenyl-2-
(N-phenylamino)ehtanol17h,i was characterized by comparison of
their spectra data (1H and 13C NMR and IR).
Acknowledgements
We thank the Santoku Corporation for supplying the lanthanum
metal. This study was financially supported by the MEXT-Sup-
ported Program for the Strategic Research Foundation at Private
Universities, Grant-in-Aid for Scientific Research, and the Kansai
University Research Grants: Grant-in-Aid for Encouragement of
Scientists.
Supplementary data
7. In order to increase the reactivity of lanthanoid metal, the reaction was carried
out in the presence of some additives, such as a catalytic amount of iodine1-
or methyl iodide,4 excess amount of HMPA,3i,l and HCl aq3m or under
m,2a,3k
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2014.12.089.
photoirradiation,5d,f sonication,8 and DMF solvent9 conditions.
8. (a) Concellon, J. M.; Rodriguez-Solla, H.; Bardales, E.; Huerta, M. Eur. J. Org.
Chem. 2003, 1775; (b) Concellon, J. M.; Bernad, P. L.; Huerta, M.; Garcia-Granda,
S.; Diaz, M. R. Chem.dEur. J. 2003, 9, 5343; (c) Teprovich, J. A., Jr.; Antharjanam,
P. K. S.; Prasad, E.; Pesciotta, E. N.; Flowers, R. A., II. Eur. J. Inog. Chem. 2008,
5015.
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