α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium

Article abstract of DOI:10.1021/acs.joc.6b01466

The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obta

Full text of DOI:10.1021/acs.joc.6b01466

Note
pubs.acs.org/joc
α‑Regioselective Barbier Reaction of Carbonyl Compounds and Allyl
Halides Mediated by Praseodymium
San Wu, Ying Li, and Songlin Zhang*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu
Lake Campus, Soochow University, Suzhou, 215123, People’s Republic of China
S
* Supporting Information
ABSTRACT: The first utility of praseodymium as a mediating
metal in the Barbier reaction of carbonyl compounds with allyl
halides was reported in this paper. In contrast to the traditional
metal-mediated or catalyzed Barbier reactions, exclusive α-
adducts were obtained in this one-pot reaction with a broad
scope of substrates and feasible reaction conditions.
he homoallylic alcohols are important building blocks to
be applied in the synthesis of many biologically active
addition products, high boiling solvents were essential in their
research. Thus, a more energy efficient and feasible method for
α-selective allylation is still in demand.
T
molecules.1 And the metal mediated or catalyzed addition of
allylic agents to carbonyl compounds is the most efficient
method to obtain such valuable compounds. Conventionally
these metal-mediated Barbier reactions are highly γ-selective to
give γ-adducts2 (Scheme 1, reaction a), despite the fact that the
The utilization of samarium diiodide in synthetic chemistry
as an effective one-electron transfer reducing agent8 has been
extensively reported since the pioneering discovery study by
Kagan et al.9 Then, some other divalent lanthanide reagents
with better solubility, LnX2 (Ln = Nd,10 Dy,11 Tm,12 X = I, Br,
Cl), whose reduction potentials were similar to that of SmI2
have been reported. In the meantime, the Barbier-type
reactions of halides and carbonyl compounds mediated by
these divalent lanthanide reagents were developed.13 Due to the
fact that these reagents are expensive and both moisture and
oxygen sensitive unfortunately, the direct use of zerovalent
lanthaniod metals was determined to be an alternative method
in organic chemistry. However, the use of zerovalent lanthaniod
metals in Barbier reaction was still limited to Sm.14 To the best
of our knowledge, only a few cases using praseodymium metal
directly in organic synthesis have been reported.15 Very
recently, our group became deeply interested in the application
of lanthanide metals in organic synthesis.16 Herein, based on
our recent work, we would like to report the utility of
praseodymium as a mediating metal in the Barbier reaction of
carbonyl compounds with allyl halides (Scheme 1, reaction b).
And more importantly, the α-adducts can be obtained
exclusively in this one-pot reaction.
Scheme 1. Regioselective Barbier Reaction of Carbonyl
Compounds and Allyl Halides
α-adduct 4-substituted homoallylic alcohols also play an
important role in organic synthesis.3 By far, the most
straightforward approach to obtain 4-substituted homoallylic
alcohols is metal-mediated α-selective allylation of carbonyl
compounds. And many an endeavor has been made to realize
α-selective allylation of aldehydes and ketones. The Yamamoto
group reported the first direct preparation of allylbarium
reagents in situ and their unexpected α-selective allylation
reactions with carbonyl compounds.4 And they explored metal
effects on the α/γ selectivity in the reaction of various
organometallic reagents with benzaldehyde. The first α-
selective crotylation of aldehyde mediated by indium, zinc,
and tin was reported by Loh’s group.5 However, the reaction
appeared to be slow and lengthy. Wang’s group6 reported two
examples of the regioselective allylation of benzaldehyde
mediated by Sn in water in the presence of NaBF4. And the
α-selective allylation of ketone was first reported by Zhao and
co-workers.7 Since a high temperature leads to an increase of α-
The reaction between the benzophenone 1a and allyl iodide
was selected as a model reaction to optimize reaction
conditions (Table 1, entries 1−10). First, the ratio of Pr and
allyl iodide and temperature were examined, and the results
were summarized in Table 1. To our delight, the yield could be
improved to 82% by optimizing the molar ratio of 1a/Pr/2
Received: June 20, 2016
© XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.6b01466
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
a
Finally, crotyl bromide was employed to investigate whether
the steric hindrance affects the regioselectivity (Table 3, entries
16−17). A mixture of E and Z α-addition products was
obtained in moderate yields which indicated the hindrance had
no effect on regioselectivity.
Table 1. Optimization of Reaction Conditions
In summary, we have documented the first Barbier-type
reaction of allyl halides with carbonyl compounds mediated by
praseodymium. 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.
b
entry
1a:Pr:2
time (h)
temp (°C)
yield (%)
1
1:2:6
2
2
2
2
2
2
2
2
4
1
2
2
2
rt
74
79
75
81
82
82
45
23
84
70
74
79
75
2
1:2:4
rt
3
1:2:2.4
1:1.6:1.6
1:1.6:2
1:2.0:2
1:1.6:2
1:1.6:2
1:1.6:2
1:1.6:2
1:2:6
rt
4
rt
5
rt
6
rt
7
0
8
−20
rt
9
EXPERIMENTAL SECTION
10
11
12
13
rt
■
rt
General Details. All of the reagents and solvents were used
directly as obtained commercially unless otherwise noted. The
petroleum ether (PE) used refers to the 60−90 °C boiling point
fraction of petroleum. Column chromatography was performed with
1:2:4
rt
1:2:2.4
rt
a
Unless noted, to a solution of 1a (0.5 mmol), Pr (X mmol), and 2 (Y
mmol) in THF (3 mL) under a nitrogen atmosphere, and the mixture
was stirred. Isolated yield based on 3a after silica gel chromatography.
200−300 mesh silica gel using flash column techniques. H and 13C
1
b
NMR spectra were determined in CDCl3 or DMSO-d6 on a 400 MHz
spectrometer. Chemical shifts in 1H NMR spectra are reported in parts
per million (ppm, δ) downfield from the internal standard Me4Si
(TMS, δ = 0.00 ppm) or DMSO (2.50 ppm). Chemical shifts in 13C
NMR spectra are reported relative to the central line of the chloroform
signal (δ = 77.00 ppm) or DMSO signal (δ = 40.00 ppm). High-
resolution mass spectra were obtained with a GCT-TOF instrument.
General Procedure for Synthesis of Alcohol. Allyl halides (1.0
mmol), ketones (0.5 mmol), and Pr powder (0.8 mmol) were mixed
in dry THF (3 mL) under a nitrogen atmosphere at room
temperature. The mixture was stirred for about 2 h (the reaction
was monitored by TLC). The reaction mixture was then quenched
with dilute hydrochloric acid. The resulting mixture was extracted with
diethyl ether (3 × 10 mL) and dried over anhydrous Na2SO4. The
solvent was removed by evaporation under reduced pressure.
Purification by column chromatography on silica gel (eluent:
EtOAc/Pet ether = 1/20) afforded alcohols.
(Table 1, entries 5 vs 1−4 and 6). When the reaction was
carried out at a lower temperature, the yield decreased
significantly (Table 1, entries 7−8). Thus, a 1.0/1.6/2.0
molar ratio of 1a/Pr/2 at room temperature proved to be the
optimal reaction conditions. And the reaction time was able to
be shortened to 2 h.
With the optimized reaction conditions in hand, the substrate
scope of the reaction of various benzophenones with allyl
iodide was subsequently explored and the results were
summarized in Table 2. As shown in Table 2, we found
ketones bearing an electron-donating substituent gave high
yields, such as 4,4′-dimethoxy, 4-methyl-, and 4-phenyl-
benzophenone (Table 2, entries 2−4). For ketones bearing
electron-withdrawing groups on aryl rings, such as 4,4′-
dichloro-, 4,4′-difluoro-, and 3,4-dichlorobenzaldehyde, the
products were obtained in moderate yields (Table 2, entries
5−7). The above-mentioned results indicated that electron-
donating groups on the aryl ring were favored in the reaction
rather than electron-withdrawing groups. Ethyl benzoate also
gave the product 3h in 56% yield (Table 2, entry 8). To
broaden the scope of this reaction, allyl bromides were also
examined (Table 2, entries 9−10). To our delight, the
corresponding homoallylic alcohols were obtained in high
yields as well.
1,1-Diphenylbut-3-en-1-ol (3a).17 The title compound was
obtained according to the general procedure. Pale yellow oil; yield
82% (91.9 mg); IR (KBr): 3556, 3047, 2910, 2840, 1944, 1769, 1640,
1
1550, 1470, 1386, 1160, 992, 812, 769, 690 cm−1; H NMR (CDCl3,
400 MHz, TMS): δ 7.40−7.20 (m, 10H), 5.60−5.47 (m, 1H), 5.15−
5.06 (m, 2H), 2.96 (d, J = 7.10 Hz, 2H), 2.49 (s, 1H); 13C NMR (100
MHz, CDCl3, TMS): δ 146.9, 133.9, 128.6, 127.3, 126.4, 121.0, 77.3,
47.1; HRMS (EI+) calcd for C16H16O (M+): 224.1202; found
224.1203.
1,1-Bis(4-methoxyphenyl)but-3-en-1-ol (3b).18 The title com-
pound was obtained according to the general procedure. Pale yellow
oil; yield 89% (126.4 mg); IR (KBr): 3490, 3074, 2930, 2830, 2545,
1
2048, 1890, 1610, 1510, 1465, 1380, 990, 829, 735 cm−1; H NMR
Next, we turned our attention to the regioselectivity of this
Barbier-type reaction. First, 3,3-dimethylallyl chloride was
employed to investigate the regioselectivity (Table 3, entries
1−2). To our surprise, no γ-adducts, which are the dominant
products in conventional Barbier reactions, were observed. 4,4-
Dimethylallyl homoallylic alcohols were obtained in moderate
to good yields. Then, to broaden the reaction scope, 3,3-
dimethylallyl bromide was employed to react with a series of
benzophenones (Table 3, entries 3−8). And the α-adducts
were obtained exclusively in moderate to good yields. When
cinnamon bromide reacted with benzophenones, trans-4-phenyl
homoallylic alcohols could be gained in moderate yields (Table
3, entries 9−15). The results indicated that the Praseodymium-
mediated Barbier-type reaction was highly α-regioselective.
(CDCl3, 400 MHz, TMS): δ 7.26 (d, J = 8.4 Hz, 2H), 6.75 (d, J = 8.4
Hz, 2H), 5.62−5.52 (m, 1H), 5.15−5.04 (m, 2H), 3.67(s, 6H), 2.92
(d, J = 6.9 Hz, 2H), 2.44 (s, 1H); 13C NMR (100 MHz, CDCl3,
TMS): δ 158.3, 139.0, 133.7, 133.6, 127.4, 126.9, 120.1, 113.6, 113.2,
76.4, 55.3, 55.0, 46.9; HRMS (EI+) calcd for C18H20O3 (M+):
284.1412; found 284.1410.
1-Phenyl-1-p-tolylbut-3-en-1-ol (3c).19 The title compound was
obtained according to the general procedure. Pale yellow oil; yield 74%
(88.1 mg); IR (KBr): 3555, 3060, 3025, 2975, 2920, 1955, 1639, 1510,
1
1445, 1383, 998, 810, 765, 699 cm−1; H NMR (CDCl3, 400 MHz,
TMS): δ 7.34−7.03 (m, 9H), 5.61−5.51 (m, 1H), 5.14−5.03 (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 147.1, 144.0, 136.8, 134.0, 129.3, 128.5, 127.2,
126.5, 126.3, 120.7, 77.1, 47.1, 21.4; HRMS (EI+) calcd for C17H18O
(M+): 238.1358; found: 238.1354.
B
DOI: 10.1021/acs.joc.6b01466
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
a
Table 2. Reactions of Ketone Compounds with Allyl Iodide Promoted by Praseodymium Metal
a
Unless noted, to a solution of 1a (0.5 mmol), Pr (0.8 mmol), and allyl iodide (1.0 mmol) in THF (3 mL) were added under a nitrogen atmosphere,
b
c
and the mixture was stirred for 2 h. Isolated yield based on 1a after silica gel chromatography. To a solution of 1a (0.5 mmol), Pr (3.0 mmol), and
2 (3.5 mmol)in THF (6 mL) were added under a nitrogen atmosphere, and the mixture was stirred for 2 h. Allyl bromide was used instead of allyl
d
iodide.
1-Phenyl-1-(4′-phenyl)phenylbut-3-en-1-ol (3d). The title com-
pound was obtained according to the general procedure. Pale yellow
oil; yield 88% (132.1 mg); IR (KBr): 3555, 3071, 2920, 2835, 1951,
(m, 1H), 5.15−5.03 (m, 2H), 2.97 (d, J = 7.1 Hz, 2H), 2.50 (s, 1H);
13C NMR (100 MHz, CDCl3, TMS): δ 146.5, 145.7, 140.7, 139.7,
133.5, 128.8, 128.3, 127.3, 127.1, 127.0, 127.0, 126.5, 126.1, 120.7,
76.8, 46.8; HRMS (EI+) calcd for C22H20O (M+): 300.1514; found:
300.1510.
1
1770, 1625, 1510, 1460, 1385, 1175, 930, 815, 769, 689 cm−1; H
NMR (CDCl3, 400 MHz, TMS): δ 7.46−7.11 (m, 14H), 5.61−5.55
C
DOI: 10.1021/acs.joc.6b01466
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
a
Table 3. Reactions of Ketone Compounds with Allyl Iodide Promoted by Praseodymium Metal
a
Unless noted, to a solution of 1a (0.5 mmol), Pr (0.8 mmol), and 2 (1.0 mmol) in THF (3 mL) were added under a nitrogen atmosphere, and the
b
mixture was stirred for 2 h. Isolated yield based on 1a after silica gel chromatography.
1,1-Bis(4-chlorophenyl)but-3-en-1-ol (3e).20 The title compound
74% (108.1 mg); IR (KBr): 3555, 3085, 2979, 2855, 1910, 1777, 1640,
1
was obtained according to the general procedure. Pale yellow oil; yield
1595, 1495, 1410, 1095, 930, 825, 759, 670 cm−1; H NMR (CDCl3,
D
DOI: 10.1021/acs.joc.6b01466
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
400 MHz, TMS): δ 7.24 (d, J = 8.4 Hz, 4H), 7.15 (d, J = 8.4 Hz, 4H),
5.52−5.50 (m, 1H), 5.15−5.06 (m, 2H), 2.89 (d, J = 7.2 Hz 2H), 2.51
(s, 1H); 13C NMR (100 MHz, CDCl3, TMS): δ 144.6, 133.0, 132.6,
128.4, 127.4, 121.3, 76.3, 46.5; HRMS (EI+) calcd for C16H14Cl2O
(M+): 292.0422 and 294.0392; found: 292.0422 and 294.0393.
1,1-Bis(4-fluorophenyl)but-3-en-1-ol (3f).18 The title compound
was obtained according to the general procedure. Pale yellow oil; yield
85% (110.6 mg); IR (KBr): 3555, 3080, 2910, 2845, 1955, 1730, 1640,
129.1, 128.6, 127.6, 127.4, 127.2, 127.2, 126.9, 126.4, 118.8, 78.0, 41.2,
26.5, 18.7; HRMS (EI+) calcd for C24H24O (M+): 328.1827; found
328.1821.
1,1-Bis(4-chlorophenyl)-4-methylpent-3-en-1-ol (4e). The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 63% (101.2 mg); IR (KBr): 3545, 3025, 1890, 1765,
1
1605, 1450, 1406, 1380, 1155, 971, 835, 748, 699 cm−1; H NMR
(CDCl3, 300 MHz, TMS): δ 7.28−7.23 (m, 4H), 7.20−7.15 (m, 4H),
4.90 (t, J = 6.8 Hz, 1H), 2.85 (d, J = 7.2 Hz, 2H), 2.48 (s, 1H), 1.60−
1.54 (m, 6H); 13C NMR (100 MHz, CDCl3, TMS): δ 145.1, 138.8,
132.8, 128.4, 127.5, 127.5, 117.7, 77.0, 40.7, 26.2, 18.3; HRMS (EI+)
calcd for C18H18Cl2O (M+): 320.0735; found 320.0733.
1
1560, 1490, 1360, 1110, 989, 821, 769, 689 cm−1; H NMR (CDCl3,
400 MHz, TMS): δ 7.29 (dd, J = 14.0 Hz, J = 3.06 Hz, 4H), 6.90 (t, J
= 8.6 Hz, 4H), 5.57−5.50 (m, 1H), 5.17−5.09 (m, 2H), 2.93 (d, J =
7.18 Hz, 2H), 2.50 (s, 1H); 13C NMR (100 MHz, CDCl3, TMS): δ
1
3
160.20 (d, JC−F = 244.0 Hz), 142.6 (d, JC−F = 3.0 Hz), 133.3, 128.1,
1-(4-Methoxyphenyl)-4-methyl-1-phenylpent-3-en-1-ol (4i). The
title compound was obtained according to the general procedure. Pale
yellow oil; yield 72% (101.6 mg); IR (KBr): 3515, 3030, 2910, 2835,
2045, 1880, 1769, 1610, 1515, 1440, 1383, 1250, 1178, 905, 828, 769,
709 cm−1; 1H NMR (CDCl3, 400 MHz, TMS): δ 7.37−7.27 (m, 7H),
6.75−6.70 (m, 2H), 4.96 (s, 1H), 3.68 (s, 3H), 2.90 (d, J = 7.2 Hz,
2H), 2.45 (s, 1H), 1.59 (s, 6H); 13C NMR (100 MHz, CDCl3, TMS):
δ 158.4, 147.3, 139.3, 137.6, 128.1, 127.4, 126.7, 126.1, 118.7, 113.5,
77.5, 55.2, 41.0, 26.2, 18.4; HRMS (EI+) calcd for C19H22O2 (M+):
282.1620; found 282.1618.
121.4, 115.4 (d, JC−F = 21 Hz), 76.7, 47.3; HRMS (EI+) calcdfor C
2
16H14F2O (M+): 260.1013; found 260.1010.
1-(3,4-Dichlorophenyl)-1-phenylbut-3-en-1-ol (3g).21 The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 72% (105.5 mg); IR (KBr): 3540, 3065, 2920, 2845,
1955, 1760, 1640, 1560, 1468, 1382, 1175, 992, 820, 765, 699 cm−1;
1H NMR (CDCl3, 400 MHz, TMS): δ 7.48−7.13 (m, 8H), 5.53−5.49
(m, 1H), 5.17−5.12 (m, 2H), 297−2.84 (m, 2H), 2.52 (s, 1H); 13C
NMR (100 MHz, CDCl3, TMS): δ 147.1, 145.6, 132.7, 132.5, 131.0,
130.3, 130.2, 128.6, 128.3, 127.5, 126.0, 121.4, 76.4, 46.6; HRMS(EI+)
calcd for C16H14Cl2O (M+): 292.0422 and 294.0392; found: 292.0420
and 294.0393.
(E)-1,1,4-Triphenylbut-3-en-1-ol (5a).23 The title compound was
obtained according to the general procedure. Pale yellow oil; yield 68%
(102.1 mg); IR (KBr): 3538, 3085, 2887, 1958, 1755, 1590, 1491,
1
1353, 1120, 968, 869, 776, 699 cm−1; H NMR (CDCl3, 400 MHz,
4-Phenylhepta-1,6-dien-4-ol (3h).22 The title compound was
obtained according to the general procedure. Pale yellow oil; yield
56% (52.7 mg); IR (KBr): 3555, 3070, 2979, 1945, 1630, 1490, 1440,
TMS): δ 7.51−7.45 (m, 4H), 7.39−7.35 (m, 3H), 7.30−7.24 (m, 7H),
6.61 (d, J = 15.8 Hz, 1H), 6.10−6.04 (m, 1H), 3.26 (d, J = 7.3 Hz,
2H), 2.64 (s, 1H); 13C NMR (100 MHz, CDCl3, TMS): δ 146.8,
137.2, 135.6, 130.51, 128.8, 128.5, 127.8, 127.2, 126.8, 126.5, 126.3,
124.9, 119.4, 77.7, 46.3; HRMS (EI+) calcd for C22H20O (M+):
300.1514; found 300.1516.
1
1383, 998, 915, 865, 766, 659 cm−1; H NMR (CDCl3, 400 MHz,
TMS): δ 7.44−7.38 (m, 2H), 7.36−7.23 (m, 2H), 7.25−7.20 (m,
2H),5.67−5.53 (m, 2H), 5.14−5.05 (m, 2H), 2.69 (q, d, J = 8.0 Hz,
2H), 2.52 (q, d, J = 4.0 Hz, 2H), 2.19 (s, 1H); 13C NMR (100 MHz,
CDCl3, TMS): 135.8, 133.5, 128.1, 126.6, 125.3, 119.2, 75.1, 46.9;
HRMS(EI+) calcd for C13H16O (M+): 188.1201; found: 188.1200.
4-Methyl-1,1-diphenylpent-3-en-1-ol (4a).18 The title compound
was obtained according to the general procedure. Pale yellow oil; yield
67% (84.5 mg); IR (KBr): 3550, 3080, 3030, 2925, 1950, 1665, 1600,
1445, 1380, 1265, 1169, 1055, 905, 754, 642 cm−1; 1H NMR (CDCl3,
400 MHz, TMS): δ 7.38−7.08 (m, 10H), 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 (100 MHz,
CDCl3, TMS): δ 147.3, 146.7, 138.2, 128.8, 128.4, 127.6, 127.0, 127.0,
126.4, 118.8, 78.0, 41.2, 26.5, 18.7; HRMS (EI+) calcd for C24H24O
(M+): 328.1827; found 328.1829.
(E)-1,1-Bis(4-methoxyphenyl)-4-phenylbut-3-en-1-ol (5b). The
title compound was obtained according to the general procedure.
Pale yellow oil; yield 57% (102.7 mg); IR (KBr): 3550, 3083, 2885,
1
1955, 1751, 1599, 1485, 1383, 1190, 968, 867, 779, 699 cm−1; H
NMR (CDCl3, 400 MHz, TMS): δ 7.34 (d, J = 8.0 Hz, 4H), 7.27−
7.13 (m, 5H), 6.83 (d, J = 8.0 Hz, 4H), 6.52 (d, J = 16.0 Hz, 1H),
6.10−6.00 (m, 1H), 3.74 (s, 6H), 3.14 (d, J = 8.0 Hz, 2H), 2.56 (s,
1H); 13C NMR (100 MHz, CDCl3, TMS): δ 158.4, 139.2, 137.1,
135.0, 128.6, 127.5, 127.4, 126.3, 125.1, 113.5, 77.0, 55.3, 46.4; HRMS
(EI+) calcd for C24H24O3 (M+): 360.1725; found 360.1726.
(E)-1,4-DFiphenyl-1-p-tolylbut-3-en-1-ol (5c). The title compound
was obtained according to the general procedure. Pale yellow oil; yield
70% (110.0 mg); IR (KBr): 3545, 3085, 2883, 1956, 1750, 1590, 1485,
1,1-Bis(4-methoxyphenyl)-4-methylpent-3-en-1-ol (4b). The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 77% (120.3 mg); IR (KBr): 3545, 3030, 1899, 1765,
1
1383, 1195, 978, 877, 789, 698 cm−1; H NMR (CDCl3, 400 MHz,
1
1605, 1449, 1405, 1380, 1155, 975, 835, 745, 699 cm−1; H NMR
TMS): δ 7.51−7.05 (m, 14H), 6.54 (d, J = 16.0 Hz, 1H), 6.11−6.00
(m, 1H), 3.18 (d, J = 8.0 Hz, 2H), 2.54 (s, 1H), 2,30 (s, 6H); 13C
NMR (100 MHz, CDCl3, TMS): δ 146.9, 143.8, 137.0, 136.6, 135.3,
129.0, 128.6, 128.3, 127.6, 127.0, 126.4, 126.1, 124.9, 77.4, 46.2, 21.1;
HRMS (EI+) calcd for C23H22O (M+): 314.1671; found 314.1672.
(E)-1-([1,1′-Biphenyl]-4-yl)-1,4-diphenylbut-3-en-1-ol (5d). The
title compound was obtained according to the general procedure.
Pale yellow oil; yield 67% (126.1 mg); IR (KBr): 3545, 3030, 2835,
(CDCl3, 400 MHz, TMS): δ 7.33 (d, J = 8.0 Hz, 4H), 6.83 (d, J = 8.0
Hz, 4H), 5.04 (t, J = 8.0 Hz, 1H), 3.78(s, 6H), 2.95(d, J = 8.0 Hz, 2H),
2.45(s, 1H), 1.68(d, J = 4.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ
158.3, 139.6, 129.7, 127.3, 118.8, 113.4, 112.5, 77.2, 55.2, 41.1, 26.2,
18.3; HRMS (EI+) calcd for C20H24O3 (M+): 312.1725; found
312.1723.
4-Methyl-1-phenyl-1-m-tolylpent-3-en-1-ol (4c). The title com-
pound was obtained according to the general procedure. Pale yellow
oil; yield 76% (101.2 mg); IR (KBr): 3550, 3020, 2925, 1945, 1805,
1678, 1605, 1510, 1446, 1383, 1169, 1058, 1009, 879, 815, 761, 646
cm−1; 1H NMR (CDCl3, 400 MHz, TMS): δ 7.43 (d, J = 8.0 Hz, 2H),
7.34−7.17 (m, 5H), 7.10 (d, J = 8.0 Hz, 2H), 5.04 (t, J = 8.0 Hz, 1H),
2.99 (d, J = 8.0 Hz, 2H),2.56 (s, 1H), 2.30 (s, 3H), 1.66 (s, 6H); 13C
NMR (100 MHz, CDCl3): δ 147.65, 143.90, 138.20, 136.79, 129.72,
128.52, 127.06, 126.44, 119.02, 78.00, 41.30, 26.56, 21.44, 18.76;
HRMS (EI+) calcd for C14H12O (M+): 196.0888; found 196.0889.
4-Methyl-1-phenyl-1-(4′-phenyl)phenylpent-3-en-1-ol (4d). The
title compound was obtained according to the general procedure. Pale
yellow oil; yield 66% (108.4 mg); IR (KBr): 3555, 3055, 3040, 2910,
1950, 1670, 1600, 1465, 1380, 1259, 1168, 1055, 905, 750, 709, 649
1
1945, 1799, 1605, 1486, 1345, 1074, 988, 856, 699 cm−1; H NMR
(CDCl3, 400 MHz, TMS): δ 7.67−7.23 (m, 19H), 6.67 (d, J = 15.9
Hz, 1H), 6.19−6.14 (m, 1H), 3.33 (d, J = 7.2 Hz, 2H), 2.75 (s, 1H);
13C NMR (100 MHz, CDCl3, TMS): 146.8, 146.0, 141.0, 140.0, 137.2,
135.8, 129.1, 128.9, 128.6, 127.9, 127.6, 127.4, 127.3, 127.2, 126.8,
126.6, 126.4, 124.9, 77.7, 46.4; HRMS (EI+) calcd for C28H24O (M+):
376.1827; found 376.1828.
(E)-1,1-Bis(4-chlorophenyl)-4-phenylbut-3-en-1-ol (5e). The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 54% (99.7 mg); IR (KBr): 3555, 3083, 2885, 1959,
1
1751, 1599, 1485, 1386, 1195, 968, 877, 779, 698 cm−1; H NMR
(CDCl3, 400 MHz, TMS): δ 7.37 (d, J = 8.0 Hz, 4H), 7.34−7.15 (m,
9H), 6.56 (d, J = 16.0 Hz, 1H), 6.03−5.90 (m, 1H), 3.14 (d, J = 8.0
Hz, 2H), 2.60 (s, 1H); 13C NMR (100 MHz, CDCl3, TMS): δ 144.7,
136.6, 136.1, 133.1, 128.6, 128.5, 127.9, 127.5, 126.3, 123.6, 76.8, 45.9;
HRMS (EI+) calcd for C22H18Cl2O (M+): 368.0735; found 368.0737.
1
cm−1; H NMR (CDCl3, 400 MHz, TMS): δ 7.48−7.11 (m, 14H),
4.98 (s, 1H), 2.95 (d, J = 7.1 Hz, 2H), 2.51 (s, 1H), 1.59(s, 6H); 13C
NMR (100 MHz, CDCl3, TMS): δ 147.3, 146.4, 141.2, 139.9, 138.4,
E
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The Journal of Organic Chemistry
Note
(E)-1,1-Bis(4-fluorophenyl)-4-phenylbut-3-en-1-ol (5f). The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 37% (62.2 mg); IR (KBr): 3550, 3088, 2879, 1955,
(2) (a) Denmark, S. E.; Fu, J. Chem. Rev. 2003, 103, 2763. (b) Loh,
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Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 6130.
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Lett. 2001, 42, 8701. (b) Tan, K. T.; Chng, S. S.; Cheng, H. S.; Loh, T.
P. J. Am. Chem. Soc. 2003, 125, 2958.
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Chem. 2003, 27, 1297.
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1
1730, 1595, 1490, 1338, 1189, 978, 865, 786, 697 cm−1; H NMR
(CDCl3, 400 MHz, TMS): δ 7.46−7.40 (m, 4H), 7.28−7.20 (m, 5H),
7.04−7.00 (m, 4H), 6.58 (d, J = 15.9 Hz, 1H), 6.03−5.99 (m, 1H),
3.18 (d, J = 7.3 Hz, 2H), 2.62 (s, 1H); 13C NMR (100 MHz, CDCl3,
TMS): δ162.1 (d, 1JC−F = 244.0 Hz), 142.5 (d, 3JC−F = 3.0 Hz), 137.0,
136.0, 128.9, 128.1, 128.0, 126.6, 124.2, 115.3 (d, 2JC−F = 21 Hz), 77.1,
77.0, 46.5; HRMS (EI+) calcd for C22H18F2O (M+): 336.1326; found
336.1328.
(E)-1-(4-Methoxyphenyl)-1,4-diphenylbut-3-en-1-ol (5i). The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 61% (100.7 mg); IR (KBr): 3555, 3083, 2880, 1955,
1
1755, 1599, 1485, 1383, 1195, 968, 870, 779, 699 cm−1; H NMR
(CDCl3, 400 MHz, TMS): δ 7.44 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0
Hz, 2H), 7.34−7.10 (m, 8H), 6.83 (d, J = 8.0 Hz, 2H), 6.53 (d, J =
16.0 Hz, 1H), 6.10−5.90 (m, 1H), 3.73 (s, 3H), 3.17 (d, J = 8.0 Hz,
2H), 2.58 (s, 1H); 13C NMR (100 MHz, CDCl3, TMS): δ 158.5,
135.2, 128.6, 128.3, 127.6, 127.4, 126.9, 126.4, 126.1, 124.9, 113.6,
77.3, 55.3, 46.3. HRMS (EI+) calcd for C23H22O2 (M+): 330.1620;
found 330.1621.
1,1-Diphenylpent-3-en-1-ol (6a)24 (E/Z = 4:1). The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 70% (83.3 mg); 1H NMR (CDCl3, 400 MHz, TMS):
δ 7.46−7.17 (m, 10H), 5.70−5.64 (m, 1H), 5.31−5.25 (m, 1H), 3.08−
2.97 (m, 2H), 2.63 and 2.53 (s, 1H), 1.66−1.61 (m, 3H); 13C NMR
(100 MHz, CDCl3, TMS): 146.7, 131.8, 129.3, 128.1, 126.7, 126.7,
125.9, 125.5, 124.6, 77.6, 76.8, 45.5, 39.5, 18.1, 13.2; HRMS (EI+)
calcd for C17H18O (M+): 238.1358; found 238.1360.
1-Phenyl-1-(p-tolyl)pent-3-en-1-ol (6c) (E/Z = 3.3:1). The title
compound was obtained according to the general procedure. Pale
yellow oil; yield 65% (81.9 mg); 1H NMR (CDCl3, 400 MHz, TMS):
δ 7.45−7.09 (m, 9H), 5.71−5.62 (m, 1H), 5.33−5.23 (m, 1H), 3.05
and 2.96 (d, J = 7.6 and 7.2 Hz, 2H), 2.59 and 2.49 (s, 1H), 2.29 (s,
3H), 1.66−1.61 (m, 3H); 13C NMR (100 MHz, CDCl3, TMS): 146.9,
143.8, 136.3, 136.2, 131.6, 129.1, 128.8, 128.8, 128.0, 128.0, 126.6,
126.6, 125.9, 125.6, 124.7, 77.5, 76.7, 45.6, 39.5, 20.9, 18.1, 13.2.;
HRMS (EI+) calcd for C18H20O (M+): 252.1514; found 252.1510.
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ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.6b01466.
1H and 13C NMR spectra for all compounds (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: zhangsl@suda.edu.cn.
■
Notes
The authors declare no competing financial interest.
(13) (a) Evans, W. J.; Workman, P. S.; Allen, N. T. Org. Lett. 2003, 5,
2041. (b) Evans, W. J.; Allen, N. T.; Ziller, J. W. J. Am. Chem. Soc.
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2000, 122, 2118.
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44, 1007. (c) Goryunkov, A. A.; Mazej, Z.; Zemva, B.; Strauss, S. H.;
Boltalina, O. V. Mendeleev Commun. 2006, 16, 159. (d) Drapo, J. R.;
Priefer, R. Synth. Commun. 2008, 39, 85.
ACKNOWLEDGMENTS
■
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, The
Project of Scientific and Technologic Infrastructure of Suzhou
(No. SZS201207), and the National Natural Science
Foundation of China (No. 21072143).
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