Highly α-regioselective neodymium-mediated allylation of diaryl ketones

Article abstract of DOI:10.1039/c6ra18378f

The first utility of neodymium as a mediating-metal in the highly α-regioselective Barbier reaction of diaryl ketones with allyl halides is reported in this paper. This reaction was conveniently carried out under mild conditions in a one-pot fashion with

Full text of DOI:10.1039/c6ra18378f

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ARTICLE
Highly α-Regioselective Neodymium-Mediated Allylation of Diaryl
Ketones
Fang Zhang, Ru Wang, San Wu, Peipei Wang and Songlin Zhang*a
Received 00th January 20xx,
Accepted 00th January 20xx
The first utility of neodymium as a mediating-metal in the highly α-regioselective Barbier reaction of diaryl ketones with
allyl halides was reported in this paper. This reaction was conveniently carried out under mild conditions in a one-pot
fashion with moderate to good yields. The protocol constituted an availability of starting material, wide substrate scope,
operational simplicity and powerful alternative approach.
DOI: 10.1039/x0xx00000x
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organic synthesis. Inspired by Evans’s research, the reaction of
allyl halides and carbonyl compounds mediated by neodymium
metal was investigated in this paper.
Introduction
Since pioneering studies by Kagan and co-workers
demonstrated the particular effectiveness of samarium (
In principle, the metal-mediated allylation of carbonyl compounds is
one of the reliable methods to construct homoallylic alcohols.
However, most of these metal-mediated or –catalyzed reactions are
γ-selective to give γ-adducts.14 And α-adducts of crotyl bromide and
prenyl bromide with aldehyde or ketone play an important role in
organic synthesis.15 Many endeavor has been made to realized α-
selective allylation of carbonyl compounds. Yamamoto’s group
reported the first alpha-regioselective allylation of allylbarium
reagents. They first direct preparation of allylbarium reagents by
reaction of in situ generated reactive barium with various allylic
chlorides and their new and unexpected selective allylation
reactions with carbonyl compounds are disclosed. Loh’s group
subsequently reported α-selective crotylation of aldehyde which
was medated by indium or tin16 (Scheme 1). Wang’s group realized
the regioselective allylation of aldehyde by the use of NaBF4 and
metal.17 And the α-selective allylation of ketone was first reported
by Zhao and co-workers.18 Due to high temperature lead to increase
of α-addition products, high boiling solvents were essential in their
Ⅱ
)
diiodide as a strong one-electron transfer reducing agent,1 the
utilization of SmI2 reagent in synthetic organic chemistry has
been dramatically documented.2 Then, some “new” soluble
divalent lanthanide reagents, LnX2 (Ln = Nd,3 Dy,4 Tm,5 X = I, Br,
Cl) have been reported. Compared with SmI2 6, NdX2 has a
Ln(III)/Ln(II) reduction potential vs NHE of -2.6 V which was
much smaller. And the first utility of NdI2 as a reductant was
reported by Evans.3 In their research, alkyl halides reacted with
ketone or aldehyde in the presence of 2.2 equiv.
neodymium(II) diiodide. The elegant result indicated that the
NdI2 can be a single electron transfer reagent which is similar
to SmI2. However, NdI2 is moisture- and air-sensitive, which is
instable in solvent at room temperature. And the preparation
is much more difficult than SmI2. For above reasons, the
application of NdI2 in organic chemistry is still scarcely
reported.
As known to us, the zerovalent lanthanoid metals could also
bear strong reduction potential.7 In particular, Ce,8 Sm,9 Dy,10
Yb11 and La12 have been employed as useful reagents or
catalysts in organic synthesis. They show great advantages not
only nontoxic and cheap, but also stability in the air. However,
never a successful application of reduction of zerovalent
neodymium metal has been reported. More recently, our
group have been deeply interested in lanthanide reagents13
and wanted to explore new application of lanthanide metals in
research. In this paper,
a neodymium-mediated α-selective
allylation of ketone and easter was developed without any other
additves. This strategy provided a broad scope and moderate to
good yields of the α-addition products.
a.Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
China
Scheme 1. Regioselective of metal-mediated Barbier reaction
E-mail: zhangsl@suda.edu.cn
†Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Results and discussion
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Table 1. Optimization of Reaction Conditionsa
When benzophenone (1a) was treated with allyl bromide and
Nd in THF under a nitrogen atmosphere at room temperature,
1,1-diphenylbut-3-en-1-ol (2a) were obtained (Scheme 2).
Temp
(oC)
25
Yield
(%)c
75
Entry
Ratiob
Solvent
1
6:2:1
THF
THF
2
4:2:1
25
78
3
2:2:1
THF
25
76
Scheme 2. One-pot reaction of benzophenone in the presence
of neodymium metal
4
1.5:1.2:1
1.5:0.6:1
1.5:1.2:1
1.5:1.2:1
1.5:1.2:1
1.5:1.2:1
1.5:1.2:1
1.5:1.2:1
1.5:1.2:1
THF
25
84
5
THF
25
53
Encouraged by this reaction, we selected it as a model reaction
for optimizing reaction conditions. A systematic study was
carried out for evaluating the molar ratio of Nd and allyl
bromide, temperature and the solvent. The results were
summarized in Table 1. The use of 1.2 equiv. of neodymium
and 1.5 equiv. of allyl bromide was found to be optimal (Table
1, entries 1-5). Furthermore, the reaction efficiency was found
to be affected by the solvent system, solvent had a marked
influence on the product formation, when the reaction was
performed at room temperature in DME, toluene, MTBE,
diethyl ether or H2O instead of THF as the solvent, no product
was obtained (Table 1, entries 6-10). In regard to the influence
of temperature on the reaction, it was found that the yield of
2a decreased to 50% at -20 o C (Table 1, entries 11-12). Thus,
product 2a could be obtained in excellent yield when the
reaction was conducted at room temperature and THF as the
solvent with a 1.5/1.2/1 molar ratio of halide, neodymium and
6
DMF
toluene
MTBE
Et2O
H2O
25
None
None
None
None
None
67
7
25
8
25
9
25
10
11
25
THF
0
12
THF
-20
50
a
To
a suspension of benzophenone (0.5 mmol) and
neodymium in THF (3 mL) was added allylicbromide and
catalytic amounts of I2 under a nitrogen atmosphere at room
b
temperature, and the mixture was stirred for 2h. Ratio =
c
allylbromide:metal:benzophenone
Isolated yield based on
benzophenone after silica gel chromatography.
Table 2. One-pot reaction of ketones and bromides in the presence
of neodymium metal and catalytic amounts of iodine in THFa
1a.
With the above optimized reaction conditions (1.2 equiv. of
neodymium and 1.5 equiv. of halide at 25 o C in THF) in hand,
the reactions of a variety of bromide with ketone were
subsequently explored and the results were summarized in
Table 2. As shown in Table 2, when allyl bromide was treated
with various ketones, good yields were obtained with aromatic
ketones bearing electron-donating on the aryl ring, such as 4-
methyl-, 4- phenyl-, 4,4'-dimethoxy-benzophenone (Table 2,
entries 2-5). With aromatic ketones bearing electron-
withdrawing groups on the aryl ring, such as 4-fluoro-, 4-
chloro-, and 3,4-dichloro-benzophenone, the products were
obtained in moderate yields (Table 2, entries 6-8). The above
results showed that electron-donating groups on the aryl ring
were more favorable for the reaction than electron-
withdrawing groups. To our dismay, the reactions with
benzaldehyde, an unsaturated aldehyde, 1-phenylbutan-1-one
and (E)-chalcone with allyl bromide were messy and no titled
products were obtained. (Table 2, entries 9-12).
Yield
Entry Bromide
Substrate
Product
(%)b
1
84
To study the regioselectivity of this allylation, 3,3-dimethylallyl
2
3
80
94
bromide, cinnamyl bromide and crotyl bromide were tested.
To our delight, the reactions could also proceed smoothly and
afford corresponding α-addition alcohols exclusively in good
yields (Table 2, entries 13-23). When the secondary alkyl halide
was treated with benzophenone, and methallyl halide with
benzophenone,
phenyl(p-tolyl)methanone
and
bis(4-
chlorophenyl)methanone, no title products were obtained
(Table 2, entries 24-27).
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4
92
13
88
5
6
88
14
85
78
75
77
15
7
8
75
16
71
17
80
9
0
18
66
75
77
10
0
19
11
12
0
OH
2k
20
0
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Experiments to further explore the scope of halides were then
conducted, 3,3-dimethylallyl chloride and allyl iodide were
subjected to this reaction and the results were summarized in
Table 3. As we can see, when 3,3-dimethylallyl chloride was
applied with various ketones, it could undergo reaction
smoothly to afford the desired α-adducts with moderate to
good yields (Table 3, entries 1-6). Then, we turned our
attention to the reaction of allyl iodide with ketones 1a, 1c, 1d
and 1e. Fortunately, they showed quite good performance
giving the desired products in excellent yields (Table 3, entries
7-10). 9-Fluorenone 1n could also be well tolerated and the
product was obtained in good yield (Table 3, entry 11).
Heterocyclic ketones 1o-1p could also react with allyl iodide
21
77
HO
22
70
2v
providing the products 2e'-2f' in moderate yields (Table 3,
entries 12-13). Then, we were pleased to find that the reaction
was successfully extended to acetophenone with a moderate
yield (Table 3, entry 14).
23
24
69
Table 3. One-pot reaction of ketones and halides in the presence of
neodymium metal and catalytic amounts of iodine in THFa
0
OH
2x
Entry Halide
Substrate
Product
Yield (%)b
25
0
0
0
1
70
OH
26
2
55
2z
3
4
93
50
27
a
To a suspension of carbonyl compounds (0.5 mmol) and
neodymium（0.6 mmol）in THF (3 mL) was added bromide (0.75
mmol) and catalytic amounts of I2 under a nitrogen atmosphere,
b
and the mixture was stirred for 2 h. Isolated yield based on the
substrates after silica gel chromatography.
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5
70
13
65
6
75
14
55
a To a suspension of carbonyl compounds (0.5 mmol) and neodymium
（0.6 mmol）in THF (3 mL) was added halide (0.75 mmol) and
catalytic amounts of I2 under a nitrogen atmosphere, and the mixture
was stirred for 2 h. b Isolated yield based on the substrates after silica
gel chromatography.
7
8
90
90
O
1c
9
94
88
10
HO
11
70
2d'
HO
N
12
50
2e'
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Although a detailed mechanism requires further investigation,
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from commercial source, without further purification before use.
The flash column chromatography was carried out on Merck silica
gel (300–400 mesh). 1H and 13C NMR spectra were recorded on a
Varian-Inova-400 spectrometer. Solvent for NMR is CDCl3, unless
the otherwise noted. Chemical shifts are reported in delta (δ) units
in parts per million (ppm) relative to the singlet (0 ppm) for
tetramethylsilane (TMS). Data are reported as follows: chemical
shift, multiplicity (s = single, d = doublet, t = triplet, m = multiplet,
dd = doublet of doublets), coupling constants (Hz), and integration.
13C NMR spectra were recorded on 100 MHz. Chemical shifts are
reported in parts per million relatived to the central line of the
multiplet at 77.5 ppm for CDCl3. High-resolution mass spectra were
obtained with a GCT-TOF instrument. All chemicals were purchased
from Aldrich, Alfa or Acros chemical company and used thus,
without further purification. Petroleum ether (PE) used refers to the
60–90oC boiling point fraction of petroleum.
a plausible reaction mechanism was proposed in Scheme 3. Firstly,
the allyl neodymium reagents were generated in situ by the
reaction of neodymium and allyl halides. The allyl neodymium
reagents interconverted between primary allyl species I and tertiary
allyl species II.19 Consequently, there were two possible pathways
for the reaction of allyl neodymium reagents with ketones. Of the
two possible transition states A and B, TS-A would be more
favorable because of the absence of steric interactions between the
phenyl group and the methyl group of the terminal olefin, which
was presence in TS-B. Consequently, the TS-A thus formed would
undergo the addition reaction to give the α-addition products with
highly regioselectivity.
Br
General procedure for synthesis of alcohol(2a-2g').
To
a suspension of carbonyl compounds (0.5 mmol) and
Nd
neodymium（0.6 mmol）in THF (3 mL) was added halide (0.75
mmol) and catalytic amounts of I2 under a nitrogen atmosphere at
room temperature. The mixture was stirred for 2 h and then was
quenched with dilute hydrochloric acid. The resulting mixture was
extracted with diethyl ether (3×10 mL), and dried over anhydydrous
Na2SO4. The solvent was removed by evaporation under reduced
pressure. Purification by column chromatography on silica gel
afforded olefins (300–400 mesh, petroleum ether as eluent).
1,1-diphenylbut-3-en-1-ol (2a).20
NdBr
BrNd
O
O
The title compound was obtained according to the general
procedure. Yellow oil: 101 mg，90%; IR (KBr): 3555, 3056, 2919,
2843, 1944, 1770, 1641, 1560, 1469, 1386, 1168, 992, 810, 765,
698cm-1; 1H NMR (CDCl3, 400 MHz, TMS): δ 7.37-7.15 (m, 10H),
5.61-5.53 (m, 1H), 5.17-5.07 (m, 2H), 2.96 (d, J = 7.06 Hz, 2H), 2.49
(s, 1H). 13C NMR (100 MHz, CDCl3, TMS): 146.90, 133.86, 128.63,
127.32, 126.41, 121.02, 77.30, 47.12. HRMS (ESI) m/z (M+Na+)
calcd for C16H16O, 224.1202, found: 224.1203.
Ph
Ph
Nd
Nd
Ph
Ph
O
O
Br
Br
TS-A: favored
TS-B: disfavored
1-phenyl-1-p-tolylbut-3-en-1-ol (2b).
The title compound was obtained according to the general
procedure. Yellow oil: 95 mg, 80%; IR (KBr): 3557, 3063, 3025,
2972, 2921, 1950, 1639, 1511, 1445, 1383, 991, 815, 763, 699cm-1;
1H NMR (CDCl3, 400 MHz, TMS): δ 7.34 (d, J = 7.6 Hz, 2H), 7.24-7.18
(m, 4H), 7.12-7.09 (m, 1H), 7.02 (d, J = 7.6 Hz, 2H), 5.62-5.52 (m,
1H), 5.15-5.05 (m, 2H), 2.96 (d, J = 7.1 Hz, 2H), 2.44 (s, 1H), 2.21 (s,
3H). 13C NMR (100 MHz, CDCl3, TMS): δ 147.13, 144.07, 136.88,
134.01, 129.32, 128.58, 127.21, 126.52, 126.37, 120.77, 77.23,
47.16, 21.42. HRMS (ESI) m/z (M+H+) calcd for C17H18O: 238.1358;
found: 238.1354.
OH
OH
not formed
formed
1-phenyl-1-(4’-phenyl)phenylbut-3-en-1-ol(2c).21
Scheme 3. plausible reaction mechanism
The title compound was obtained according to the general
procedure. Yellow oil: 141 mg, 94%; IR (KBr): 3550, 3070, 2919,
2836, 1950, 1773, 1626, 1516, 1458, 1385, 1174, 929, 810, 766,
686cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.45-7.35 (m, 8H), 7.27
(d, J = 7.2 Hz, 2H), 7.21-7.18 (m, 3H), 7.11-7.08 (m, 1H), 5.60-5.54
(m, 1H), 5.14-5.04 (m, 2H), 2.97 (d, J = 7.1 Hz, 2H), 2.50 (s, 1H). 13C
NMR (100 MHz, CDCl3, TMS): δ 146.84, 146.01, 141.09, 140.06,
133.81, 129.16, 128.66, 127.66, 127.45, 127.34, 127.32, 126.87,
Experimental
General Methods. THF was distilled from sodium benzophenone
under nitrogen. All reactions were conducted under a nitrogen
atmosphere. Metallic neodymium and all solvents were purchased
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126.40, 121.00, 77.18, 47.11. HRMS (ESI) m/z (M+H+) calcd for 700, 642cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.37-7.09 (m, 10H),
C22H20O: 300.1514; found: 300.1514.
4.96 (t, J = 7.2 Hz, 1H), 2.92 (d, J = 7.3 Hz, 2H), 2.47 (s, 1H), 1.58 (s,
6H). 13C NMR (75 MHz, CDCl3, TMS): δ 147.41, 138.31, 128.55,
1-(naphthalen-3-yl)-1-phenylbut-3-en-1-ol (2d).
The title compound was obtained according to the general 127.15, 126.49, 118.89, 78.10, 77.82, 77.50, 77.18, 41.27, 26.56,
procedure. Yellow oil: 252 mg, 92%; IR (KBr): 3538, 3046, 2912, 18.74. HRMS (ESI) m/z (M+H+) calcd for C18H20O: 252.1514, found:
2844, 1905, 1765, 1629, 1516, 1468, 1386, 1107, 929, 822, 736, 252.1512.
659cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.88 (s, 1H), 7.72 (d, J = 4-methyl-1-phenyl-1-(4’-phenyl)phenylpent-3-en-1-ol (2n).
7.6 Hz, 1H), 7.68-7.64 (m, 2H), 7.39-7.33 (m, 5H), 7.20 (t, J = 7.2 Hz, The title compound was obtained according to the general
2H), 7.13-7.09 (m, 1H), 5.18-5.13 (m, 1H), 5.08-5.05 (m, 2H), 3.09- procedure. Yellow oil: 117 mg, 93%; IR (KBr): 3550, 3058, 3045,
3.05 (m, 2H), 2.58(s, 1H). 13C NMR (75 MHz, CDCl3, TMS): δ 146.74, 2912, 1955, 1668, 1601, 1464, 1381, 1255, 1168, 1056, 906, 745,
144.24, 133.81, 133.46, 132.76, 127.93, 124.60, 121.03, 77.82, 700, 645cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.47-7.39 (m, 8H),
77.50, 46.92. HRMS (ESI) m/z (M+H+) calcd for: 274.1358, found: 7.30 (t, J = 7.6 Hz, 2H), 7.24-7.20 (m, 3H), 7.14-7.08 (m, 1H), 4.98 (s,
274.1356.
1H), 2.95 (d, J = 7.1 Hz, 2H), 2.51 (s, 1H), 1.59(s, 6H). 13C NMR (100
MHz, CDCl3, TMS): δ 147.30, 146.48, 141.21, 139.93, 138.48,
1,1-bis(4-methoxyphenyl)but-3-en-1-ol (2e).22
The title compound was obtained according to the general 128.61, 127.47, 127.21, 126.46, 118.82, 77.99, 77.82, 77.50, 77.18,
procedure. Yellow oil: 125 mg, 88%; IR (KBr): 3499, 3073, 2934, 41.27, 26.59, 18.79. HRMS (ESI) m/z (M+H+) calcd for C24H24O:
2835, 2546, 2049, 1893, 1610, 1513, 1463, 1385, 991, 828, 736cm-1; 328.1827, found: 2328.1829.
1H NMR (CDCl3, 400 MHz, TMS): δ 7.25 (d, J = 8.4 Hz, 2H), 6.74 (d, J 1-(4-methoxyphenyl)-4-methyl-1-phenylpent-3-en-1-ol (2o).
= 8.4 Hz, 2H), 5.63-5.53 (m, 1H), 5.14-5.05 (m, 2H), 3.67(s, 6H), 2.92 The title compound was obtained according to the general
(d, J = 6.9 Hz, 2H), 2.44 (s, 1H). 13C NMR (100 MHz, CDCl3, TMS): δ procedure. Yellow oil: 110 mg, 78%; IR (KBr): 3517, 3029, 2912,
158.72, 139.46, 134.21, 134.10, 127.89, 127.39, 120.54, 114.01, 2833, 2041, 1887, 1765, 1610, 1510, 1445, 1383, 1248, 1178, 902,
113.61, 76.86, 55.73, 55.49, 47.38. HRMS (ESI) m/z (M+H+) calcd for 828, 763, 701cm-1; 1H NMR (CDCl3, 400 MHz, TMS): δ 7.42 (d, J = 7.6
C
18H20O3: 284.1412, found: 284.1410.
Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.28 (t, J = 7.6 Hz, 2H), 7.20-7.17 (m,
1H), 6.82 (d, J = 8.8 Hz, 2H), 5.06-5.03 (m, 1H), 3.74 (s, 3H), 2.97 (d, J
1,1-bis(4-fluorophenyl)but-3-en-1-ol (2f). 22
The title compound was obtained according to the general = 7.2 Hz, 2H), 2.53 (s, 1H), 1.66 (s, 1H). 13C NMR (100 MHz, CDCl3,
procedure. Yellow oil: 100 mg, 77%; IR (KBr): 3554, 3086, 2912, TMS): δ 158.71, 147.79, 139.68, 137.96, 128.47, 127.02, 126.42,
2844, 1956, 1726, 1637, 1560, 1486, 1356, 1107, 987, 820, 769, 119.06, 113.83, 77.87, 77.82, 77.50, 77.18, 55.59, 41.39, 26.52,
689cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.29 (dd, J =14.0 Hz, J = 18.71. HRMS (ESI) m/z (M+H+) calcd for C19H22O2: 282.1620, found:
3.1 Hz, 4H), 6.90 (t, J = 8.6 Hz, 4H), 5.57-5.50 (m, 1H), 5.17-5.09 (m, 282.1618.
2H), 2.93 (d, J = 7.18 Hz, 2H), 2.50 (s, 1H). 13C NMR (100 MHz, CDCl3, 1,1-bis(4-chlorophenyl)-4-methylpent-3-en-1-ol (2p).
TMS): δ 163.41, 161.00, 160.99, 160.96, 142.60, 133.40, 133.31, The title compound was obtained according to the general
128.46, 128.38, 127.95, 127.88, 121.50, 121.46, 115.78, 115.57, procedure. Yellow oil: 120 mg, 75%; IR (KBr): 3540, 3026, 1896,
115.34, 115.13, 76.71, 47.32. HRMS (ESI) m/z (M+H+) calcd for 1762, 1600, 1447, 1405, 1380, 1156, 971, 832, 748, 696cm-1;1H
C16H14F2O: 260.1013, found: 260.1010.
1,1-bis(4-chlorophenyl)but-3-en-1-ol (2g). 23
NMR (CDCl3, 300 MHz, TMS): δ 7.27-7.24 (m, 4H), 7.18-7.16 (m, 4H),
4.90 (t, J = 6.8 Hz, 1H), 2.85 (d, J = 7.2 Hz, 2H), 2.48 (s, 1H), 1.59-1.57
The title compound was obtained according to the general (m, 6H). 13C NMR (100 MHz, CDCl3): δ 145.51, 139.18, 133.24,
procedure. Yellow oil: 110 mg, 75%; IR (KBr): 3550, 3080, 2977, 128.78, 127.90, 118.08, 77.45, 41.09, 26.57, 18.75. HRMS (ESI) m/z
2850, 1907, 1776, 1639, 1593, 1490, 1400, 1093, 927, 820, 756, (M+H+) calcd for C18H18Cl2O: 320.0735, found: 320.0733.
671cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.23 (d, J = 8.4 Hz, 4H), (E)-1,1,4-triphenylbut-3-en-1-ol (2q).25
7.16 (d, J = 8.4 Hz, 4H), 5.51-5.49 (m, 1H), 5.14-5.07 (m, 2H), 2.89 (d, The title compound was obtained according to the general
J = 7.2 Hz, 2H), 2.51(s, 1H). 13C NMR (100 MHz, CDCl3, TMS): δ procedure. Yellow solid: 120 mg, 80%; mp 82-83.4 °C. IR (KBr):
145.02, 133.35, 133.00, 128.82, 127.82, 121.64, 76.65, 46.88. HRMS 3537, 3080, 2884, 1955, 1751, 1595, 1491, 1353, 1199, 968, 867,
1
(ESI) m/z (M+H+) calcd for C16H14Cl2O: 294.0392; found: 294.0393.
1-(3,4-dichlorophenyl)-1-phenylbut-3-en-1-ol (2h).24
776, 694cm-1; H NMR (CDCl3, 400 MHz, TMS): δ 7.53-7.51 (m, 4H),
7.39-7.35 (m, 3H), 7.30-7.24 (m, 7H), 6.61 (d, J = 15.8 Hz, 1H), 6.11-
The title compound was obtained according to the general 6.07 (m, 1H), 3.26 (d, J = 7.3 Hz, 2H), 2.64 (s, 1H). 13C NMR (100
procedure. Yellow oil: 104 mg, 71%; IR (KBr): 3545, 3068, 2921, MHz, CDCl3, TMS): δ 147.00, 137.33, 135.77, 128.94, 128.67,
2844, 1950, 1762, 1637, 1561, 1468, 1382, 1170, 992, 822, 766, 127.95, 127.37, 126.70, 126.47, 125.06, 77.83, 77.50, 77.18, 46.46.
699cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.49 (s, 1H), 7.32 (d, J = HRMS (ESI) m/z (M+H+) calcd for C22H20O: 300.1514, found:
7.2 Hz, 2H), 7.25-7.21 (m, 3H), 7.16-7.12 (m, 2H), 5.54-5.50 (m, 1H), 300.1517.
5.16-5.09 (m, 2H), 2.99-2.85 (m, 2H), 2.52 (s, 1H). 13C NMR (100 (2r).
(E)-1-([1,1'-biphenyl]-4-yl)-1,4-diphenylbut-3-en-1-ol
MHz, CDCl3, TMS): δ 147.35, 145.83, 132.73, 130.58, 128.90, The title compound was obtained according to the general
127.81, 125.97, 121.69, 77.82, 77.50, 77.18, 76.69, 46.83. HRMS procedure. Yellow solid: 141 mg, 75%; mp 73-74.8 °C. IR (KBr):
(ESI) m/z (M+H+) calcd for C16H14Cl2O: 292.0422;
4-methyl-1,1-diphenylpent-3-en-1-ol (2m).22
3540, 3025, 2830, 1944, 1796, 1603, 1486, 1342, 1064, 968, 841,
695cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.46-7.05 (m, 19H), 6.44
The title compound was obtained according to the general (d, J = 15.9 Hz, 1H), 5.98-5.94 (m, 1H), 3.11 (d, J = 7.2 Hz, 2H), 2.53
procedure. Yellow oil: 144 mg, 88%; IR (KBr): 3545, 3085, 3029, (s, 1H). 13C NMR (100 MHz, CDCl3, TMS):146.91, 146.08, 140.10,
2921, 1950, 1663, 1600, 1446, 1381, 1260, 1167, 1054, 905, 754, 135.84, 129.18, 128.72, 127.96, 127.69, 127.47, 127.42, 127.36,
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126.92, 126.71, 126.45, 124.97, 77.82, 77.72, 77.50, 77.18, 46.47. 1941, 1802, 1674, 1600, 1511, 1446, 1383, 1167, 1058, 1001, 879,
HRMS (ESI) m/z (M+H+) calcd for C28H24O: 376.1827, found: 814, 761, 701, 642cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.45-7.42
376.1826.
(m, 2H), 7.34-7.27 (m, 4H), 7.11 (d, J = 8.0 Hz, 2H), 5.07-5.03 (m,
1H), 2.99 (d, J = 7.2 Hz, 2H), 2.51 (s, 1H), 2.30 (s, 3H), 1.67 (s, 6H).
(E)-1-(naphthalen-3-yl)-1,4-diphenylbut-3-en-1-ol (2s).
The title compound was obtained according to the general 13C NMR (100 MHz, CDCl3, TMS): δ 147.62, 144.54, 138.18, 136.72,
procedure. Yellow solid: 135 mg, 77%; mp 93-94.5 °C. IR (KBr): 129.27, 128.52, 127.06, 126.44, 119.02, 78.00, 41.30, 26.56, 21.44,
3528, 3020, 2830, 1950, 1779, 1600, 1491, 1359, 1121, 967, 826, 18.76. HRMS (ESI) m/z (M+H+) calcd for C19H22O: 266.1671, found:
1
746, 697cm-1; H NMR (CDCl3, 400 MHz, TMS): δ 7.99 (s, 1H), 7.83- 266.1670.
7.74 (m, 3H), 7.51-7.43 (m, 5H), 7.32-7.15 (m, 8H), 6.57 (d, J = 15.9 1,1-bis(4-fluorophenyl)-4-methylpent-3-en-1-ol (2c').
Hz, 1H), 6.08-6.04(m, 1H), 3.30-2.28 (m, 2H), 2.71 (s, 1H). 13C NMR The title compound was obtained according to the general
(100 MHz, CDCl3, TMS): δ 146.81, 144.34, 137.27, 135.94, 133.52, procedure. Yellow oil: 79 mg, 55%; IR (KBr): 3531, 3054, 2980,
132.83, 128.95, 128.77, 128.73, 128.49, 127.99, 127.96, 127.50, 1896, 1660, 1602, 1506, 1443, 1383, 1227, 1160, 1067, 912, 833,
1
126.73, 126.58, 126.56, 126.41, 125.32, 124.94, 124.68, 77.95, 734, 669cm-1; H NMR (CDCl3, 400 MHz, TMS): δ 7.41-7.36 (m, 4H),
46.32. HRMS (ESI) m/z (M+H+) calcd for C26H22O: 350.1671, found: 7.01-6.91 (m, 4H), 5.02-4.98 (m, 1H), 2.96 (d, J = 7.6 Hz, 2H), 2.56 (s,
350.1670.
1H). 1.68 (s, 3H), 1.66 (s, 3H). 13C NMR (100 MHz, CDCl3, TMS):
163.36, 160.92, 143.07, 143.04, 138.85, 128.25, 128.17, 118.39,
115.46, 115.25, 77.52, 41.47, 26.55, 18.72. HRMS (ESI) m/z (M+H+)
(E)-1,1-bis(4-fluorophenyl)-4-phenylbut-3-en-1-ol (2t).
The title compound was obtained according to the general calcd for C18H18F2O: 288.1326, found: 288.1327.
procedure. Yellow oil: 111 mg, 66%; IR (KBr): 3545, 3085, 2875, 9-allyl-9H-fluoren-9-ol (2d'). 26
1945, 1740, 1585, 1490, 1335, 1199, 978, 865, 776, 695cm-1;1H The title compound was obtained according to the general
NMR (CDCl3, 400 MHz, TMS): δ 7.33-7.30 (m, 4H), 7.18-7.11 (m, 5H), procedure. Yellow oil: 78 mg, 70%; IR (KBr): 3301, 3068, 2929,
6.94-6.89 (m, 4H), 6.46 (d, J = 15.9 Hz, 1H), 5.94-5.86 (m, 1H), 3.06 1879, 1640, 1583, 1448, 1388, 1197, 1054, 915, 761, 735, 672cm-
(d, J = 7.3 Hz, 2H), 2.51 (s, 1H). 13C NMR (100 MHz, CDCl3, TMS): δ 1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.56 (d, J = 7.6 Hz, 2H), 7.45 (d, J
163.43, 160.98, 142.66, 142.64, 137.11, 136.14, 128.24, 128.16, = 7.6 Hz, 2H), 7.33-7.22 (m, 4H), 5.57-5.46 (m, 1H), 4.92-4.88 (m,
126.7, 124.37, 115.59, 115.38, 77.81, 77.50, 77.21, 77.19, 46.62. 2H), 2.76 (d, J = 7.2 Hz, 2H), 2.31 (s, 1H). 13C NMR (100 MHz, CDCl3,
HRMS (ESI) m/z (M+H+) calcd for C22H18F2O: 336.1326, found: TMS): 148.70, 139.80, 133.10, 129.34, 128.23, 124.31, 120.33,
336.1325.
119.15, 81.95, 44.45. HRMS (ESI) m/z (M+H+) calcd for C16H14O:
222.1045, found: 222.1047.
1,1-diphenylpent-3-en-1-ol (2u) 26 (E/Z = 4:1)
1-phenyl-1-(pyridin-2-yl)but-3-en-1-ol (2e').
The title compound was obtained according to the general The title compound was obtained according to the general
procedure. Yellow oil: 92 mg, 77%; 1H NMR (CDCl3, 400 MHz, procedure. Yellow oil: 56 mg, 50%; IR (KBr): 3540, 3060, 2364,
TMS): δ 7.48-7.17 (m, 10H), 5.71-5.23 (m,2H), 3.07＆2.98 (m, J = 8 1958, 1745, 1639, 1590, 1493, 1445, 1384, 916, 752, 700cm-1;1H
Hz, 2H), 2.63-2.53 m, 1H), 1.66-1.61 (m, 3H). 13C NMR (100 MHz, NMR (CDCl3, 400 MHz, TMS): δ 8.51 (d, J = 4.4 Hz, 1H), 7.65-7.61 (m,
CDCl3, TMS): 146.70, 131.80, 129.30, 128.06, 126.74, 126.67, 125.95, 1H), 7.55-7.53 (m, 2H), 7.37-7.29 (m, 3H), 7.25-7.19 (m, 1H), 7.17-
125.46, 124.59, 77.58, 76.68, 45.52, 39.46, 18.10, 13.19. HRMS 7.13 (m, 1H), 5.78-5.68 (m, 1H), 5.57 (s, 1H), 5.12-5.02 (m, 2H),
(ESI) m/z (M+H+) calcd for C17H18O: 238.1358, found: 238.1356.
3.15-3.04 (m, 2H). 13C NMR (100 MHz, CDCl3, TMS): 163.69, 147.86,
146.38, 137.35, 134.08, 128.67, 127.42, 126.46, 122.48, 121.21,
1-phenyl-1-(p-tolyl)pent-3-en-1-ol (2v) (E/Z = 3.3:1)
The title compound was obtained according to the general 119.06, 77.33, 46.19. HRMS (ESI) m/z (M+H+) calcd for C15H15NO:
procedure. Yellow oil: 88 mg, 70%;1H NMR (CDCl3, 400 MHz, 225.1154, found: 225.1155.
TMS): δ 7.45-7.09 (m, 9H), 5.67-5.29 (m,2H), 3.05＆2.98 (m, J = 8 1-phenyl-1-(thiophen-2-yl)but-3-en-1-ol (2f').
Hz, 2H), 2.59-2.49 m, 1H), 1.66-1.61 (m, 3H). 13C NMR (100 MHz, The title compound was obtained according to the general
CDCl3, TMS): 146.91, 143. 82, 136.31, 136.22, 131.65, 129.13, procedure. Yellow oil:75 mg, 65%; IR (KBr): 3537, 3071, 2921,
128.76, 128.02, 126.64, 126.57, 125.90, 125.59, 124.73, 77.49, 2835, 1955, 1893, 1723, 1638, 1600, 1493, 1445, 1384, 1232, 1036,
76.66, 45.55, 39.50, 20.91, 18.10, 13.19. HRMS (ESI) m/z (M+H+) 986, 919, 828, 764, 699cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.51-
calcd for C18H20O: 252.1514, found: 252.1513.
7.49 (m, 2H), 7.33 (t, J = 7.2 Hz, 2H), 7.26-7.19 (m, 2H), 6.92-6.91
(m, 2H), 5.74-5.63 (m, 1H), 5.26-5.17 (m, 2H), 3.07 (d, J = 6.8 Hz,
1,1-bis(4-chlorophenyl)pent-3-en-1-ol (2w) (E/Z = 4:1)
The title compound was obtained according to the general 2H)), 2.78 (s, 1H). 13C NMR (100 MHz, CDCl3, TMS): 152.57, 146.04,
procedure. Yellow oil: 112 mg, 69%; 1H NMR (CDCl3, 400 MHz, 133.42, 128.62, 127.64, 127.01, 126.00, 125.32, 124.43, 121.24,
TMS): δ 7.46-7.23 (m, 8H), 5.74-5.18 (m,2H), 3.00＆2.915 (m, J = 8 76.38, 48.81. HRMS (ESI) m/z (M+H+) calcd for C14H14OS: 230.0765,
Hz＆J = 4 Hz, 2H), 2.64-2.53 m, 1H), 1.65-1.60 (m, 3H). 13C NMR found: 230.0763.
(100 MHz, CDCl3, TMS): 144.82, 132.85, 132.78, 132.64, 130.15, 2-phenylpent-4-en-2-ol (2g').
128.31, 127.38, 124.66, 123.73, 76.12, 45.33, 39.29, 18.13, 13.22. The title compound was obtained according to the general
HRMS (ESI) m/z (M+H+) calcd for C17H16Cl2O: 306.0578, found: procedure. Yellow oil: 45 mg, 55%; IR (KBr): 3559, 3071, 2977,
306.0579.
1947, 1635, 1487, 1445, 1383,1069, 998, 915, 862, 766, 700,
658cm-1;1H NMR (CDCl3, 400 MHz, TMS): δ 7.45-7.43 (m, 2H), 7.34
4-methyl-1-phenyl-1-(p-tolyl)pent-3-en-1-ol (2b').
The title compound was obtained according to the general (t, J = 7.6 Hz, 2H), 7.25-7.22 (m, 1H), 5.67-5.57 (m, 1H), 5.15-5.10
procedure. Yellow oil: 67 mg, 50%; IR (KBr): 3545, 3023, 2920, (m, 2H), 2.71-2.66 (m, 1H), 2.53-2.47 (m, 1H), 2.08(s, 1H)), 1.54 (s,
8 | J. Name., 2012, 00, 1-3
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3H). 13C NMR (100 MHz, CDCl3, TMS): 148.10, 134.14, 128.64,
127.08, 125.23, 119.93, 74.09, 48.93, 30.36. HRMS (ESI) m/z
(M+H+) calcd for C11H14O: 162.1045, found: 162.1046.
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Conclusions
In summary, we have documented the first Barbier-type reaction of
allyl halides with diaryl ketones mediated by neodymium. As a
complement to the traditional metal-mediated or catalyzed Barbier
reactions, this reaction was highly α-regioselective and the reaction
was conveniently carried out under mild conditions in a one-pot
fashion. In this work, a straightforward strategy to synthesize 4-
substituent homoallylic alcohols was developed. This strategy
provides a broad scope and moderate to good yields of the
products in a relatively short reaction time without use of any
additives.
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We would like to gratefully acknowledge financial support
from the A Project Funded by the Priority Academic Program
for the Development of Jiangsu Higher Education Institutions
and the National Natural Science Foundation of China (No.
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DOI: 10.1039/C6RA18378F
The first utility of neodymium as a mediatingꢀmetal in the Barbier reaction of diaryl ketones with
allyl halides was reported in this paper. Contrast to traditional metalꢀmediated or catalyzed Barbier
reactions, this reaction was highly αꢀregioselective and conveniently carried out under mild
conditions in a oneꢀpot fashion with moderate to good yields. The protocol constituted an
availability of starting materials, wide substrate scope, operational simplicity and powerful
alternative approach.