Nickel-Catalyzed Cross-Coupling of Allyl Alcohols with Aryl- or Alkenylzinc Reagents

Article abstract of DOI:10.1021/acs.joc.6b02564

Nickel-catalyzed cross-coupling of allyl alcohols with aryl- and alkenylzinc chlorides through C-O bond cleavage was performed. Reaction of (E)-3-phenylprop-2-en-1-ol and 1-aryl-prop-2-en-1-ols with aryl- or alkenylzinc chlorides gave linear cross-coupling products. Reaction of 1-phenyl- or 1-methyl-substituted (E)-3-phenylprop-2-en-1-ol with aryl- or alkenylzinc chlorides resulted in 3-aryl/alkenyl-substituted (E)-(prop-1-ene-1,3-diyl)dibenzenes or 3-aryl/alkenyl-substituted (E)-(but-1-enyl)benzene. Reaction of allyl alcohol with p-Me₂NC₆H₄ZnCl resulted in a mixture of normal coupling product 4-allyl-N,N-dimethylaniline and its isomerized product N,N-dimethyl-4-(prop-1-en-1-yl)aniline.

Full text of DOI:10.1021/acs.joc.6b02564

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Featured Article
Nickel-Catalyzed Cross-Coupling of Allyl
Alcohols with Aryl- or Alkenylzinc Reagents
Bo Yang, and Zhong-Xia Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02564 • Publication Date (Web): 15 Nov 2016
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Nickel-Catalyzed Cross-Coupling of Allyl Alcohols with Aryl- or
Alkenylzinc Reagents
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Bo Yang,† and Zhong-Xia Wang*,†,‡
† CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of
Science and Technology of China, Hefei, Anhui 230026, P. R. China
‡ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin
300072, P. R. China
E-mail: zxwang@ustc.edu.cn
ABSTRACT: Nickel-catalyzed cross-coupling of allyl alcohols with aryl- and alkenyl-zinc
chlorides through C-O bond cleavage was performed. Reaction of (E)-3-phenylprop-2-en-1-ol
and 1-aryl-prop-2-en-1-ols with aryl- or alkenylzinc chlorides gave linear cross-coupling
products. Reaction of 1-phenyl- or 1-methyl-substituted (E)-3-phenylprop-2-en-1-ol with aryl-
or alkenyl-zinc chlorides resulted in 3-aryl/alkenyl-substituted (E)-(prop-1-ene-1,3-
diyl)dibenzenes or 3-aryl/alkenyl-substituted (E)-(but-1-enyl)benzene. Reaction of allyl
alcohol with p-Me2NC6H4ZnCl resulted in a mixture of normal coupling product 4-allyl-N,N-
dimethylaniline and its isomerized product N,N-dimethyl-4-(prop-1-en-1-yl)aniline.
Introduction
Transition-metal-catalyzed allylation is a powerful tool to construct C-C bonds in organic
synthesis.1-3 Among the reactions allyl alcohol derivatives bearing a good leaving group such
as allylic carboxylates, allylic carbonates, and allylic phosphates were often employed as
electrophiles.2-6 Allyl alcohols themselves were less used due to the poor leaving ability of
hydroxide anion and the presence of acidic proton.1 However, direct catalytic transformation
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of allyl alcohols is more step and atom economical because the activated allylic substrates were
mostly prepared from allyl alcohols. Hence catalytic allylation using allyl alcohols as
electrophiles attracted considerable attention in recent years.1,7-11 For example, palladium-,
rhodium-, and iridium-catalyzed cross-coupling of allyl alcohols with organoboron reagents
have been achieved.1,11 Transition-metal-catalyzed allylic alkylation of ketones, aldehydes, and
other active methylene compounds using allyl alcohols were also carried out.1,7 However,
nucleophiles used in transformation of allyl alcohols are very limited. Among those
nucleophiles often employed in cross-coupling reactions such as organo-magnesium, -zinc, -
boron, -tin, and -silicon reagents,12 only organoboron reagents were used to react with allyl
alcohols. On the other hand, organozinc reagents show higher reactivity than organoboron, -
silicon, and -tin reagents and better functional-group compatibility than organomagnesium
reagents. Hence, it would be interesting to explore the reaction of allyl alcohols with organozinc
reagents to construct C-C bonds. In addition, most of the reported reactions with allyl alcohols
required palladium and iridium as catalysts. Inexpensive and earth-abundant nickel was rarely
used in the transformations.1 In a earlier study, we demonstrated that nickel can effectively
catalyze cross-coupling of allyl methyl ethers with arylzinc reagents.13 Here we report a nickel-
catalyzed cross-coupling of allyl alcohols with aryl- and alkenylzinc reagents.
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Results and discussion
Screening of catalyst and optimization of reaction conditions were carried out using coupling
of (E)-3-phenylprop-2-en-1-ol (1a) with p-Me2NC6H4ZnCl (2a) as a model reaction. Due to
the presence of the acidic proton in allyl alcohol, excess organozinc reagent was used or a
strong base was added to convert the allyl alcohol to its salt prior to catalytic reaction. At first
the pincer nickel complex and reaction conditions for coupling of allyl methyl ethers with aryl
zinc reagents13 were used to catalyze the coupling of 1a with excess 2a and the results showed
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that catalyst to be ineffective to current substrates. Hence we turned our attention to other nickel
compounds. In the following tests, the reaction was first run in a mixed solvent of toluene and
diisopropyl ether (3:1) at 120 °C (bath temperature) refering to reaction conditions of nickel-
catalyzed coupling of phenolic salts or benzyl alcohols with Grignard reagents.14 In the
presence of 10 mol% NiCl2(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane), reaction of 1a
with either 3.2 equiv. or 5 equiv. of 2a resulted in 4-cinnamyl-N,N-dimethylaniline (3a) in 53%
and 60% yields respectively (Table 1, entries 1 and 2). Reaction of sodium (E)-3-phenylprop-
2-en-1-olate prepared from (E)-3-phenylprop-2-en-1-ol and NaH with 2 equiv. of 2a gave a
similar yield (Table 1, entry 3). However, marked improvements were observed if 1a was pre-
treated with MeLi, MeMgBr or MeZnCl (Table 1, entries 4-6). Next we examined other pre-
catalysts including NiCl2(dppf) (dppf = 1,1'-bis(diphenylphosphino)ferrocene), NiCl2(dppp)
(dppp = 1,3-bis(diphenylphosphino)propane), NiCl2(PPh3)2 and NiCl2(PCy3)2 and
demonstrtated NiCl2(dppe) to be most effective (Table 1, entries 7-10). We also examined the
combination of simple nickel compounds and dppe and found that a combination of Ni(OTf)2
and dppe resulted in highest product yield (Table 1, entries 11-14). In the absence of dppe,
Ni(OTf)2 can catalyze the reaction in relatively low efficiency. In the absence of any nickel
catalyst the reaction also gave 28% product yield (Table 1, entries 15 and 16). In the latter case
occurrence of the reaction may result from activation of Lewis acids such as MgCl2 to the C-
O bond of allyl alcohol. We did find that reaction of 1a with 2a gave trace amounts of coupling
product in the absence of any Mg2+ ion and nickel catalyst (Table 1, entry 17). When 1.5 equiv.
of 2a were loaded or reaction time was shortened to 12 hours, the reactions gave lower yields
(Table 1, entries 18 and 19). Reaction temperature is also an important factor. Lower
temperatures than 120 °C led to lower product yields (Table 1, entries 20 and 21). Although
the mixed solvent of toluene and diisopropyl ether led to good coupling results, we still tested
other solvents including toluene, i-Pr2O, THF, n-Bu2O, dioxane, NMP, and a mixture of toluene
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and n-Bu2O (3:1). The results showed that the mixture of toluene and n-Bu2O (3:1) was as good
as the mixed solvent of toluene and i-Pr2O (3:1), and toluene alone was also a suitable solvent
for the reaction (Table 1, entries 22-28). Finally, we tested the reaction in the mixed solvent of
toluene and n-Bu2O (3:1) using 5 mol% Ni(OTf)2 and 5 mol% dppe loadings. Slightly lower
product yield was obtained (Table 1, entry 29).
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Table 1. Catalyst screening and optimization of reaction conditionsa
Entry
Amount of
zinc reagent
(equiv.)
Base
[M]
(mol%)
Ligand
(mol%)
T (°C) Solvent
Yield
(%)
1
3.2
NiCl2(dppe)
NiCl2(dppe)
NiCl2(dppe)
NiCl2(dppe)
NiCl2(dppe)
NiCl2(dppe)
NiCl2(dppf)
NiCl2(dppp)
NiCl2(PPh3)2
NiCl2(PCy3)2
Ni(COD)2
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
100
80
Tolu/i-Pr2O (3:1)
53
60
61
89
92
92
85
82
40
17
83
92
83
98
72
28
trace
65
92
95
75


2
5
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1.5
2
2
2
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)
Tolu/i-Pr2O (3:1)


3
NaH

4
MeLi

5
MeMgCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeLi

6

7

8

9

10
11
12
13
14
15
16
17b
18
19c
20
21

dppe
dppe
dppe
dppe

Ni(acac)2
NiCl2(DME)
Ni(OTf)2
Ni(OTf)2




MeZnCl
MeZnCl
MeZnCl
MeZnCl
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
dppe
dppe
dppe
dppe
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29d
2
2
2
2
2
2
2
2
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
MeZnCl
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
Ni(OTf)2
dppe
dppe
dppe
dppe
dppe
dppe
dppe
dppe
120
Tolu
96
35
8
reflux i-Pr2O
reflux THF
120
120
120
120
120
n-Bu2O
dioxane
NMP
84
23
trace
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Tolu/n-Bu2O (3:1) 98
Tolu/n-Bu2O (3:1) 92
a Unless otherwise specified, the reactions were carried out on a 0.5 mmol scale according to
the conditions indicated by the above equation; p-Me2NC6H4ZnCl was prepared from p-
b
Me2NC6H4MgBr and ZnCl2 in the presence of 2 equiv. of LiCl. p-Me2NC6H4ZnCl was
c
prepared from p-Me2NC6H4Li and ZnCl2 in the presence of 1 equiv. of LiCl. The reaction
time was 12 h. d 5 mol% Ni(OTf)2 and 5 mol% dppe were employed.
Next we examined substrate scope under the optimized conditions. Thus, allyl alcohols were
first treated with MeZnCl at room temperature and next the reaction was run in a mixed solvent
of toluene and n-Bu2O (3:1) at 120 °C for 24 h using a combination of Ni(OTf)2 (10 mol%)
and dppe (10 mol%) as pre-catalyst. To choose MeZnCl rather than MeLi or MeMgCl (cf.
Table 1, entries 4-6) as a base is to prevent undesirable side reaction when the allyl alcohols
containing reactive functional groups such as COOEt, CONEt2, and CN were employed.
Compound 1a was demonstrated to react smoothly with various arylzinc chlorides including
electron-rich and electron-poor ones (Table 2, entries 1-5). For example, the reactions with
electron-rich arylzinc reagents including (4-(dimethylamino)phenyl)zinc chloride (2a), (4-
methoxyphenyl)zinc chloride (2b) and benzo[d][1,3]dioxol-5-ylzinc chloride (2c) as well as
naphthalen-2-ylzinc chloride (2d) gave almost quantitative yields (Table 1, entry 28 and Table
2, entries 1-3). Reaction of electron-poor zinc reagent, p-CF3C6H4ZnCl (2e), resulted in lower
yield (Table 2, entry 4). This might be due to weaker nucleophilicity of 2e and existence of side
reactions as observation from TLC of the resultant reaction mixture. Reaction of o-
MeC6H4ZnCl (2f) gave excellent product yield (Table 2, entry 5). It seems that steric hindrance
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of o-tolyl group affects the reaction in a very small degree. Two heteroarylzinc reagents, furan-
2-ylzinc chloride (2g) and thiophen-2-ylzinc chloride (2h), can also react with 1a to form 2-
cinnamylfuran (3g) and 2-cinnamylthiophene (3h), respectively (Table 2, entries 6 and 7). We
noted that LiCl and MgCl2 additives can promote the coupling reaction. If furan-2-ylzinc
chloride was prepared from furan-2-yllithium and an equiv. of ZnCl2, the coupling reaction
gave 47% product yield. If the zinc reagent was prepared from furan-2-yllithium and an equiv.
of ZnCl2 in the presence of 1.0 equiv. LiCl and 1.0 equiv. MgCl2, the coupling reaction gave
62% product yield. The other reactions also required the existence of LiCl and MgCl2 to
achieve good yields. For example, catalytic reaction of 1a with 2a in the absence of any Mg2+
ion gave desired product in 72% yield which was markedly lower than that under standard
conditions (Table 1, entry 28). The acceleration effect of LiCl and MgCl2 to the reaction of
organozinc reagents has been observed previously by us and other groups.15 MgCl2 as a
stronger Lewis acid than ZnCl2 may weaken C-O bond of the allyl alcohols by coordination of
the oxygen atom to magnesium center. The role of LiCl may be to enhance reactivity of
organozinc reagents through breaking the aggregation of the organozinc reagent with MgCl2
and forming more nucleophilic lithium zincates.15c,d In addition, each of the reactions shown
in Table 2 yielded linear cross-coupling product with a trans-double bond as shown by the
CH=CH coupling constants of the 1H NMR spectra ranging from 15.6 to 16 Hz.
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Table 2. Ni-catalyzed reaction of (E)-3-phenylprop-2-en-1-ol with (hetero)arylzinc chloridesa
Entry
1
Ar
Product
Yield (%)
99
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4
5
73
88
47b
62c
6
7
86c
a
The reactions were carried out using 0.5 mmol 1a and 1.0 mmol of arylzinc chlorides
according to the conditions indicated by above equation. Unless otherwise specified, the zinc
reagents were prepared from Grignard reagents and ZnCl2 in the presence of 2 equiv. of LiCl.
b The zinc reagent was prepared from 1 equiv. of furan-2-yllithium and 1 equiv. of ZnCl2. c The
zinc reagents were prepared from 1 equiv. of furan-2-yllithium or thiophen-2-yllithium and 1
equiv. of ZnCl2 in the presence of 1 equiv. of LiCl and 1 equiv. of MgCl2.
1-Aryl-prop-2-en-1-ols reacted smoothly with arylzinc chlorides to generate exclusively
linear coupling products, (E)-1,3-diarylpropenes (Table 3, entries 1-8). The substituted phenyl
groups attached on prop-2-en-1-ols can be electron-rich and electron-deficient ones. The
reactions also tolerated functional groups on the phenyl groups including MeO, Me2N, F, CF3,
CN, and C(O)NEt2 (Table 3, entries 1, 2, and 4-8). When the substituted groups were CF3 and
CN, the reactions gave lower yields (Table 3, entries 5 and 6). It is surprising that reaction of
ethyl 4-(1-hydroxyallyl)benzoate (1h) led to very low yield of desired product (Table 3, entry
7). We inferred that a side reaction between the hydroxy group of allyl alcohol and the C(O)OEt
group may occur which complicated the catalytic process. Coupling of 1-heteroaryl-prop-2-en-
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1-ols including 1-(pyridin-2-yl)prop-2-en-1-ol (1j), 1-(furan-2-yl)prop-2-en-1-ol (1k), and 1-
(thiophen-2-yl)prop-2-en-1-ol (1l) with arylzinc chlorides also produced linear coupling
products (Table 3, entries 9-11). Reaction of 1-(pyridin-2-yl)prop-2-en-1-ol with p-tolylzinc
chloride afforded (E)-2-(3-(p-tolyl)prop-1- en-1-yl)pyridine (3p) in 77% yield. Respective
reaction of 1-(furan-2-yl)prop-2-en-1-ol and 1-(thiophen-2-yl)prop-2-en-1-ol with (4-
(dimethylamino)phenyl)zinc chloride formed mixtures of Z and E isomers of desired products
3q and 3r in excellent yields.
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Table 3. Ni-catalyzed reaction of 1-aryl-prop-2-en-1-ols with arylzinc chloridesa
Entry
1
Ar
Product
Yield (%)
96%
2
3
4
5
6
83%
99%
94%
76%
64%
20%
(25%b)
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89%
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77%
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87%c
96%d
a
The reactions were carried out on a 0.5 mmol scale and 2 equiv. of zinc reagents were
employed. The zinc reagents were prepared from corresponding Grignard reagents and ZnCl2
in the presence of 2 equiv. of LiCl. b 20 mol% Ni(OTf)2 and 20 mol% dppe were used. c Z/E =
9/91. d Z/E = 15/85.
The catalyst system also suited for the coupling of non-aryl substituted allyl alcohols. For
example, reaction of allyl alcohol with p-Me2NC6H4ZnCl under the standard conditions gave
a mixture of 4-allyl-N,N-dimethylaniline (3s) and N,N-dimethyl-4-(prop-1-en-1-yl) aniline (3t)
in 82% total yield (Scheme 1). The product 3t should be from isomerization of 3s during the
process of reaction. In addition, 3t is a mixture of Z and E isomers.
Scheme 1. Ni-catalyzed reaction of allylic alcohol with p-Me2NC6H4ZnCl
Reaction of alkenylzinc reagents with 1a and 1-aryl-prop-2-en-1-ols was carried out under
the same conditions as for reaction of arylzinc reagents. Reaction of vinylzinc chloride (4a)
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with 1a gave a mixture of (E)-penta-1,4-dien-1-ylbenzene and its isomerization species
(1E,3E)-penta-1,3-dien-1-ylbenzene in a ratio of 86 to 14 and 98% total yield. When the same
reaction was run at 80 °C, (E)-penta-1,4-dien-1-ylbenzene (5a) was obtained as sole coupling
product in 94% yield (Table 4, entry 1). Reaction of prop-1-en-2-ylzinc chloride (4b) with (E)-
3-phenylprop-2-en-1-ol (1a) under the standard conditions resulted in (E)-(4-methylpenta-1,4-
dienyl)benzene (5b) in 84% yield (Table 4, entry 2). No isomerization product was observed.
Reaction of two 1-aryl-prop-2-en-1-ols, 1-(4-methoxyphenyl)prop-2-en-1-ol (1b) and 1-(4-
(trifluoromethyl)phenyl)prop-2-en-1-ol (1f), with alkenylzinc reagents afforded desired
products 5c-5f (Table 4, entries 3-6). The former gave excellent yields, and the latter gave lower
yields. The yield difference may be due to the existence of side reactions for 1-(4-
(trifluoromethyl)phenyl)prop-2-en-1-ol rather than electron effects of aryl groups in the allyl
alcohol substrates. We did observe small amount of side products from TLC for the reaction of
1-(4-(trifluoromethyl)phenyl) prop-2-en-1-ol. Reaction of prop-1-en-2-ylzinc chloride gave
lower yields in comparison with corresponding those of vinylzinc chloride. This may result
from greater steric hindrance of prop-1-en-2-yl group than vinyl group. The above reactions
also gave linear alkenes with (E)-geometry of C-C double bonds.
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Table 4. Ni-catalyzed reaction of (E)-3-phenylprop-2-en-1-ol or 1-aryl-prop-2-en-1-ols with
alkenylzinc chloridesa
OH
MeZnCl (1.2 equiv.)
Ni(OTf)2 (10 mol%)
dppe (10 mol%)
Ar
R
R
Ar
+
or
ZnCl
Toluene/n-Bu2O (3:1)
120 °C, 24 h
Ar
Entry
OH
Alcohol
4
5a 5f
-
R
H
Product
Yield (%)
98b
94c
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Me
H
84
99
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5
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Me
H
87
79
70
Me
a
The reactions were carried out on a 0.5 mmol scale and 2 equiv. of zinc reagents were
employed. The zinc reagents were prepared from corresponding Grignard reagents and ZnCl2
in the presence of 2 equiv. of LiCl. b (E)-penta-1,4-dien-1-ylbenzene/(1E,3E)- penta-1,3-dien-
1-ylbenzene = 86/14. c The reaction temperature was 80 °C.
Both (E)-4-phenylbut-3-en-2-ol (1m) and (E)-1,3-diphenylprop-2-en-1-ol (1n) also reacted
smoothly with p-Me2NC6H4ZnCl or CH2=CHZnCl under the optimized conditions. In the
reaction of (E)-4-phenylbut-3-en-2-ol with either p-Me2NC6H4ZnCl or CH2=CHZnCl no
allylic rearrangements were observed (Table 5, entries 1 and 3). Reactions of (E)-1,3-
diphenylprop-2-en-1-ol gave lower yields of desired products (3v and 5h) than those of (E)-4-
phenylbut-3-en-2-ol (Table 5, entries 2 and 4). This is ascribed to greater steric hindrance of
(E)-1,3-diphenylprop-2-en-1-ol than (E)-4-phenylbut- 3-en-2-ol.
Table 5. Ni-catalyzed reaction of (E)-4-phenylbut-3-en-2-ol and (E)-1,3-diphenylprop-2-en-1-
ol with p-Me2NC6H4ZnCl or CH2=CHZnCla
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MeZnCl (1.2 equiv.)
Ni(OTf)2 (10 mol%)
dppe (10 mol%)
R
R
+ R1ZnCl
Ph
OH
Ph
R1
7
Toluene/n-Bu2O (3:1)
8
9
120 °C, 24 h
1m
1n
2a 4a
3
5
or
R = Me
R = Ph
or
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Entry
1
R
R1
Product
Yield (%)
94
Me
p-Me2NC6H4
p-Me2NC6H4
CH2=CH
2
3
4
Ph
Me
Ph
76
96
86
CH2=CH
a The reactions were carried out on a 0.5 mmol scale and 2 equiv. of zinc reagents were
employed. The zinc reagents were prepared from corresponding Grignard reagents and ZnCl2
in the presence of 2 equiv. of LiCl.
The reaction was not affected by 1,1-diphenylethene additive. In the presence of 1 equiv. of
1,1-diphenylethene, the catalytic reaction of 1a with 2a under standard conditions gave desired
product in 99% yield. This ruled out the possibility of a free radical process. A combination of
Ni(COD)2 (10 mol%) and dppe (10 mol%) can catalyze coupling of 1a with 2a in 83% product
yield (Table 1, entry 11). Based on these experimental results we inferred that the reaction may
proceed through a Ni(0)/Ni(II) cycle. The allylic rearrangement shown in Tables 3 and 4
supports formation of a allylnickel intermediate in the reaction process. Attempts to prepare
and isolate the intermediate through reaction of (E)-PhCH=CHCH2OZnCl or (E)-
PhCH=CHCH(Ph)OZnCl with an equiv. of Ni(COD)2/dppe were unsuccessful. The 1H NMR
spectrum of the resultant species of reaction of (E)-PhCH=CHCH(Ph)OZnCl with an equiv. of
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Ni(COD)2/dppe exhibited complicated spectral signals rather than those of simple allylnickel.
In Table 5 we showed that reaction of (E)-1,3-diphenylprop-2-en-1-ol with p-Me2NC6H4ZnCl
under standard conditions gave cross-coupling product in 76% yield. However, the same
reaction and conditions but employing an equiv. of Ni(OTf)2/dppe gave only 28% product yield.
This result made us realize that some other factors might steer the reaction process. We ran the
reaction again in the presence of 13 equiv. of ZnCl2, 25 equiv. of LiCl and 13 equiv. of MgCl2
additives and the result showed that a 84% product yield was achieved. The experimental fact
implies that a high molar ratio of Zn2+, Li+ and Mg2+ ions to nickel is necessary for a successful
catalytic process. Although we inferred that MgCl2 as a strong Lewis acid may promote
activation the C-O bond of allyl alcohols and LiCl may enhance reactivity of organozinc
reagents, the concrete mode of action was still unclear. The reaction intermediate may be a
complex cluster composed of zinc, lithium, magnesium, nickel ions and reaction substrates.
Further studies will be needed to clarify the reaction mechanism.
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Conclusions
In summary, Ni(OTf)2/dppe has been demonstrated to effectively catalyze cross-coupling of
allyl alcohols with aryl or alkenylzinc reagents through C-O bond cleavage. The reaction
exhibits high regioselectivity, both (E)-3-phenylprop-2-en-1-ol and 1-aryl-prop-2-en-1-ol
substrates resulting in linear coupling products. The reaction also shows high E/Z-selectivity
for the new C-C double bond in most cases, the alkenes with (E)-geometry being formed except
the reaction of 1-(furan-2-yl)prop-2-en-1-ol and 1-(thiophen-2-yl)prop-2-en-1-ol with arylzinc
chlorides, which afforded a mixture of (Z)- and (E)-isomers. The catalyst system also suited
for the coupling of more steric hindered secondary allyl alcohols such as (E)-4-phenylbut-3-
en-2-ol and (E)-1,3-diphenylprop-2-en-1-ol with aryl or vinylzinc reagents to afford
regioselective coupling products with (E)-C-C double bond geometry. The reaction may
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proceed through a Ni(0)/Ni(II) cycle, but lithium, magnesium and zinc ions play an important
role in the catalytic process.
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Experimental
All reactions were performed under nitrogen atmosphere using standard Schlenk and vacuum
line techniques. Toluene, THF, i-Pr2O, n-Bu2O and 1,4-dioxane were distilled under nitrogen
over sodium and degassed prior to use. NMP was dried over 4 Å molecular sieves, fractionally
distilled under reduced pressure, and stored under a nitrogen atmosphere. ZnCl2, and LiCl were
purchased from commercial vendors and dried under vacuum at 140 °C for 12 h prior to use.
MeMgCl, CH2=CHMgCl, and p-Me2NC6H4MgBr were purchased from commercial vendors
and used as received. The other Grignard reagents were prepared according to reported
procedures.16 Organozinc reagents were prepared from ZnCl2 and an equiv. of Grignard
reagents in the presence of 2 equiv. of LiCl. Various allyl alcohols including 1-phenyl-prop-2-
en-1-ol, 1-(4-methoxyphenyl)prop-2-en-1-ol, 1-(4-(dimethyl amino)phenyl)prop-2-en-1-ol, 1-
(4-fluorophenyl)prop-2-en-1-ol,
1-(4-(trifluoromethyl)
phenyl)prop-2-en-1-ol,
4-(1-
hydroxyallyl)benzonitrile, 1-(furan-2-yl)prop-2-en-1-ol, 1-(thiophen-2-yl)prop-2-en-1-ol, 1-
(pyridin-2-yl)prop-2-en-1-ol), (E)-4-phenylbut-3-en-2-ol, (E)-1,3-diphenyl-prop-2-en-1-ol,
ethyl 4-(1-hydroxyallyl)benzoate and N,N-diethyl-4-(1- hydroxyallyl)benzamide were
prepared according to reported procedures.7h,13,17 All other chemicals were obtained from
commercial vendors and used as received. NMR spectra were recorded on a 400 MHz NMR
1
spectrometer at ambient temperature. The chemical shifts of the H NMR spectra were
referenced to TMS and the chemical shifts of the C{1H} NMR spectra were referenced to
13
19
internal solvent resonances. The chemical shifts of the F NMR spectra were referenced to
external CF3COOH. High-resolution mass spectra (HR-MS) were acquired in the ESI or APCI
mode using an Orbitrap mass analyzer.
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General procedure for the catalytic coupling
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Ni(OTf)2 (17.8 mg, 10 mol%), dppe (19.9 mg, 10 mol%), and allyl alcohol (0.5 mL, 1.0 M
solution in THF, 0.5 mmol) were charged to a Schlenk tube under nitrogen. To the stirred
mixture MeZnCl (1.2 mL, 0.5 M solution in THF, 0.6 mmol) was added at room temperature.
After stirred for 5 min., a solution of aryl- or alkenylzinc reagent (2.0 mL, 0.5 M solution in
THF, 1.0 mmol) was added and the solution was stirred for additional 5 min. Solvent was
removed in vacuo. Toluene (3 mL) and n-Bu2O (1 mL) were successively added. The resultant
mixture was stirred at 120 °C for 24 h and then cooled to room temperature. A 20% aqueous
solution of NH4Cl (10 mL) was added. The mixture was extracted with ethyl acetate (3  10
mL). The combined organic phases were dried over anhydrous Na2SO4, concentrated by rotary
evaporation, and purified by column chromatography (silica gel).
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4-cinnamyl-N,N-dimethylaniline (3a).18 Elute: EtOAc/petroleum ether: 1/60 (v/v), pale yellow
oil, yield 116.3 mg (98%). 1H NMR (400 MHz, CDCl3): δ 7.35 (d, J = 7.2 Hz, 2H), 7.28 (t, J
= 7.6 Hz, 2H), 7.18 (t, J = 7.3 Hz, 1H), 7.11 (d, J = 8.7 Hz, 2H), 6.72 (d, J = 8.7 Hz, 2H), 6.43
(d, J = 15.8 Hz, 1H), 6.34 (dt, J = 15.7, 6.5 Hz, 1H), 3.46 (d, J = 6.4 Hz, 2H), 2.92 (s, 6H).
13C{1H} NMR (101 MHz, CDCl3): δ 149.5, 137.8, 130.5, 130.3, 129.4, 128.6, 128.3, 127.0,
126.2, 113.2, 41.0, 38.5.
1-cinnamyl-4-methoxybenzene (3b).18 Elute: EtOAc/petroleum ether: 1/100 (v/v), colorless oil,
yield 111.1 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.35 (d, J = 8.3 Hz, 2H), 7.28 (t, J = 6.9
Hz, 2H), 7.20 (d, J = 8.4 Hz, 1H), 7.15 (d, J = 8.8 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 6.43 (d, J
= 15.8 Hz, 1H), 6.33 (dt, J = 15.7, 6.5 Hz, 1H), 3.79 (s, 3H), 3.49 (d, J = 6.5 Hz, 2H). 13C{1H}
NMR (101 MHz, CDCl3): δ 158.2, 137.6, 132.3, 130.9, 129.8, 129.7, 128.6, 127.2, 126.2, 114.0,
55.4, 38.6.
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5-cinnamylbenzo[d][1,3]dioxole (3c).18 Elute: EtOAc/petroleum ether: 1/150 (v/v), colorless
oil, yield 118.1 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.35 (d, J = 7.2 Hz, 2H), 7.28 (t, J
= 7.5 Hz, 2H), 7.19 (t, J = 7.2 Hz, 1H), 6.77-6.66 (m, 3H), 6.43 (d, J = 15.8 Hz, 1H), 6.30 (dt,
J = 15.7, 6.7 Hz, 1H), 5.91 (s, 2H), 3.45 (d, J = 6.7 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3):
δ 147.8, 146.1, 137.5, 134.1, 131.1, 129.5, 128.6, 127.3, 126.3, 121.5, 109.3, 108.4, 101.0, 39.2.
2-cinnamylnaphthalene (3d).18 Elute: petroleum ether, white solid, yield 121.1 mg (99%). 1H
NMR (400 MHz, CDCl3): δ 7.79 (t, J = 8.7 Hz, 3H), 7.66 (s, 1H), 7.40-7.46 (m, 2H), 7.36 (d,
J = 7.6 Hz, 3H), 7.28 (t, J = 7.6 Hz, 2H), 7.23-7.16 (m, 1H), 6.50 (d, J = 16.0 Hz, 1H), 6.42
(dt, J = 15.6, 6.3 Hz, 1H), 3.69 (d, J = 6.2 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 137.8,
137.6, 133.8, 132.3, 131.5, 129.2, 128.7, 128.2, 127.8, 127.7, 127.6, 127.3, 126.9, 126.3, 126.1,
125.5, 39.6.
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1-cinnamyl-4-(trifluoromethyl)benzene (3e).11b Elute: petroleum ether, colorless oil, yield 95.7
mg (73%). 1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 8.1 Hz, 2H), 7.39-7.33 (m, 3H), 7.30 (t,
J = 7.2 Hz, 2H), 7.24-7.20 (m, 2H), 6.47 (d, J = 15.8 Hz, 1H), 6.32 (dt, J = 15.8, 6.8 Hz, 1H),
3.60 (d, J = 6.8 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 144.4, 137.3, 132.1, 129.1, 128.7
(q, J = 32.4 Hz), 128.7, 128.0, 127.5, 126.3, 125.6 (q, J = 3.7 Hz), 124.5 (q, J = 271.8 Hz),
39.2. 19F NMR (376 MHz, CDCl3): δ 62.33.
1-cinnamyl-2-methylbenzene (3f).18 Elute: petroleum ether, colorless oil, yield 92.1 mg (88%).
1H NMR (400 MHz, CDCl3): δ 7.34 (d, J = 8.4 Hz, 2H), 7.28 (t, J = 7.6 Hz, 2H), 7.22-7.13 (m,
13
5H), 6.41-6.28 (m, 2H), 3.53 (d, J = 4.8 Hz, 2H), 2.33 (s, 3H). C{1H} NMR (101 MHz,
CDCl3): δ 138.4, 137.7, 136.6, 131.0, 130.4, 129.4, 128.7, 128.6, 127.2, 126.6, 126.2, 126.2,
37.0, 19.6.
2-cinnamylfuran (3g).19 Elute: petroleum ether, colorless oil, yield 57.1g (62%). 1H NMR (400
MHz, CDCl3): δ 7.38-7.31 (m, 3H), 7.28 (t, J = 7.6 Hz, 2H), 7.23-7.17 (m, 1H), 6.48 (d, J =
15.8 Hz, 1H), 6.34-6.25 (m, 2H), 6.06 (d, J = 3.1 Hz, 1H), 3.54 (d, J = 6.8 Hz, 2H). 13C{1H}
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NMR (101 MHz, CDCl3): δ 154.0, 141.5, 137.3, 132.1, 128.6, 127.4, 126.3, 125.7, 110.4, 105.8,
5
6
31.9.
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9
1
2-cinnamylthiophene (3h).20 Elute: petroleum ether, colorless oil, yield 86.3 mg (86%). H
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NMR (400 MHz, CDCl3): δ 7.40-7.33 (m, 2H), 7.29 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 7.4 Hz,
1H), 7.14 (dd, J = 5.1, 0.9 Hz, 2H), 6.94 (dd, J = 5.1, 3.5 Hz, 1H), 6.85 (dd, J = 3.4, 0.9 Hz,
1H), 6.50 (d, J = 15.7 Hz, 1H), 6.35 (dt, J = 15.7, 6.8 Hz, 1H), 3.72 (d, J = 6.7 Hz, 2H). 13C{1H}
NMR (101 MHz, CDCl3): δ 143.2, 137.3, 131.5, 128.7, 128.3, 127.4, 127.1, 126.4, 124.8, 123.9,
33.5.
(E)-1-methoxy-4-(3-(p-tolyl)prop-1-en-1-yl)benzene (3i).21 Elute: EtOAc/petroleum ether:
1/150 (v/v), white solid, yield 114.5 mg (96%). 1H NMR (400 MHz, CDCl3): δ 7.27 (dd, J =
8.7, 2.0 Hz, 2H), 7.11 (s, 4H), 6.82 (dd, J = 8.8, 2.1 Hz, 2H), 6.38 (d, J = 15.8 Hz, 1H), 6.26-
6.12 (m, 1H), 3.78 (s, 3H), 3.48 (d, J = 6.8 Hz, 2H), 2.32 (s, 3H). 13C{1H} NMR (101 MHz,
CDCl3): δ 159.0, 137.5, 135.7, 130.6, 130.4, 129.3, 128.7, 127.5, 127.4, 114.1, 55.4, 39.1, 21.2.
(E)-4,4'-(prop-1-ene-1,3-diyl)bis(N,N-dimethylaniline) (3j).18 Elute: EtOAc/petroleum ether:
1/60 (v/v), colorless oil, yield 116.4 mg (83%). 1H NMR (400 MHz, CDCl3): δ 7.25 (d, J = 8.8
Hz, 2H), 7.12 (d, J = 8.7 Hz, 2H), 6.71 (d, J = 8.7 Hz, 2H), 6.66 (d, J = 8.8 Hz, 2H), 6.35 (d, J
= 15.7 Hz, 1H), 6.13 (dt, J = 15.6, 6.9 Hz, 1H), 3.42 (d, J = 6.9 Hz, 2H), 2.93 (s, 6H), 2.91 (s,
13
6H). C{1H} NMR (101 MHz, CDCl3): δ 149.8, 149.4, 130.3, 129.4, 129.1, 127.1, 126.6,
126.1, 113.2, 112.7, 41.1, 40.8, 38.5.
(E)-4-(3-(4-fluorophenyl)allyl)-N,N-dimethylaniline (3k).18 Elute: EtOAc/petroleum ether:
1/60 (v/v), colorless oil, yield 119.9 mg (94%). 1H NMR (400 MHz, CDCl3): δ 7.31 (dd, J =
8.6, 5.5 Hz, 2H), 7.11 (d, J = 8.6 Hz, 2H), 6.96 (t, J = 8.7 Hz, 2H), 6.72 (d, J = 8.6 Hz, 2H),
6.38 (d, J = 15.8 Hz, 1H), 6.25 (dt, J = 15.7, 6.7 Hz, 1H), 3.44 (d, J = 6.7 Hz, 2H), 2.92 (s, 6H).
13C{1H} NMR (101 MHz, CDCl3): δ 162.1 (d, J = 245.7 Hz), 149.5, 134.0 (d, J = 3.2 Hz),
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130.1 (d, J = 2.2 Hz), 129.4, 129.2, 128.1, 127.6 (d, J = 7.9 Hz), 115.4 (d, J = 21.5 Hz), 113.2,
41.0, 38.4. 19F NMR (376 MHz, CDCl3): δ 115.65.
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(E)-N,N-dimethyl-4-(3-(4-(trifluoromethyl)phenyl)allyl)aniline (3l). Elute: EtOAc/petroleum
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ether: 1/60 (v/v), white solid, yield 115.7 mg (76%), mp 106-108 °C. H NMR (400 MHz,
CDCl3): δ 7.52 (d, J = 8.2 Hz, 2H), 7.42 (d, J = 8.2 Hz, 2H), 7.10 (d, J = 8.7 Hz, 2H), 6.72 (d,
J = 8.7 Hz, 2H), 6.47-6.41 (m, 2H), 3.47 (d, J = 5.0 Hz, 2H), 2.92 (s, 6H). 13C{1H} NMR (101
MHz, CDCl3): δ 149.6, 141.3, 133.3, 129.5, 129.2, 128.8 (q, J = 32.5 Hz), 127.5, 126.3, 125.5
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(q, J = 3.8 Hz), 124.4 (d, J = 271.7 Hz), 113.2, 41.0, 38.5. F NMR (376 MHz, CDCl3): δ
62.36. IR (KBr):  3456, 2888, 2813, 1614, 1520, 1417, 1333, 1165, 1109, 1067, 856, 815
cm-1. HR-MS (ESI): m/z 306.1460 [M+H]+, calcd for C18H19NF3: 306.1464.
(E)-4-(3-(p-tolyl)prop-1-en-1-yl)benzonitrile (3m). Elute: EtOAc/petroleum ether: 1/60 (v/v),
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greenish oil, yield 74.8 mg (64%). H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 8.3 Hz, 2H),
7.41 (d, J = 8.3 Hz, 2H), 7.18-7.06 (m, 4H), 6.50 (dt, J = 15.8, 6.2 Hz, 1H), 6.42 (d, J = 16.0
Hz, 1H), 3.54 (d, J = 6.2 Hz, 2H), 2.33 (s, 3H). C{1H} NMR (101 MHz, CDCl3): δ 142.2,
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136.2, 136.18, 134.0, 132.5, 129.5, 128.7, 126.7, 119.2, 110.4, 100.1, 39.1, 21.2. IR (KBr): 
3452, 3020, 2922, 1633, 1508, 1407, 974, 808 cm-1. HR-MS (ESI): m/z 234.1271 [M+H]+,
calcd for C17H16N: 234.1277.
(E)-ethyl 4-(3-(p-tolyl)prop-1-en-1-yl)benzoate (3n). Elute: EtOAc/petroleum ether: 1/150
(v/v), colorless oil, yield 35.0 mg (25%). 1H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 8.4 Hz,
2H), 7.39 (d, J = 8.4 Hz, 2H), 7.13 (s, 4H), 6.51-6.43 (m, 2H), 4.36 (q, J = 7.1 Hz, 2H), 3.62 –
3.44 (m, 2H), 2.33 (s, 3H), 1.38 (t, J = 7.1 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 166.5,
142.0, 136.5, 135.9, 132.4, 130.0, 129.9, 129.3, 128.9, 128.6, 125.9, 60.9, 39.0, 21.1, 14.4. IR
(KBr):  2987, 2914, 1714, 1608, 1508, 1448, 1278, 1178, 1110, 1021, 964, 807, 765 cm-1.
HR-MS (APCI): m/z 281.1524 [M+H]+, calcd for C19H21O2: 281.1536.
(E)-N,N-diethyl-4-(3-(p-tolyl)prop-1-en-1-yl)benzamide (3o). Elute: EtOAc/petroleum ether:
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1/4 (v/v), colorless oil, yield 136.7 mg (89%). 1H NMR (400 MHz, CDCl3): δ 7.36 (d, J = 8.3
Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 7.12 (s, 4H), 6.44 (d, J = 15.6 Hz, 1H), 6.38 (dt, J = 15.6,
6.0 Hz, 1H), 3.64-3.40 (m, 4H), 3.26 (b, 2H), 2.33 (s, 3H), 1.23 (b, 3H), 1.11 (b, 3H). 13C{1H}
NMR (101 MHz, CDCl3): δ 171.3, 138.5, 136.8, 135.9, 135.8, 130.9, 130.2, 129.3, 128.7, 126.7,
126.1, 43.4, 39.4, 39.0, 21.1, 14.3, 13.0. IR (KBr):  2982, 2927, 1637, 1517, 1464, 1430, 1089,
964, 805 cm-1. HR-MS (ESI): m/z 308.2004 [M+H]+, calcd for C21H26ON: 308.2009.
(E)-2-(3-(p-tolyl)prop-1-en-1-yl)pyridine (3p). Elute: EtOAc/petroleum ether: 1/20 (v/v),
yellowish oil, yield 80.5 mg (77%). 1H NMR (400 MHz, CDCl3): δ 8.51 (d, J = 5.6 Hz, 1H),
7.56 (dt, J = 7.7, 1.8 Hz, 1H), 7.23 (d, J = 7.9 Hz, 1H), 7.16-7.04 (m, 5H), 6.84 (dt, J = 15.6,
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6.9 Hz, 1H), 6.50 (dt, J = 15.6, 1.4 Hz, 1H), 3.54 (d, J = 6.9 Hz, 2H), 2.31 (s, 3H). C{1H}
NMR (101 MHz, CDCl3): δ 155.9, 149.4, 136.44, 136.43, 135.8, 134.5, 130.9, 129.3, 128.7,
121.8, 121.1, 38.8, 21.1. IR (KBr):  3008, 2923, 1659, 1586, 1511, 1469, 1431, 1301, 1205,
1155, 1050, 979, 808, 762 cm-1. HR-MS (ESI): m/z 210.1274 [M+H]+, calcd for C15H16N :
210.1277.
4-(3-(furan-2-yl)allyl)-N,N-dimethylaniline (3q). Elute: EtOAc/petroleum ether: 1/60 (v/v),
yellow oil, yield 98.3 mg (87%).
NMR spectra for the E-isomer:
1H NMR (400 MHz, CDCl3): 7.29 (d, J = 1.6 Hz, 1H), 7.09 (d, J = 8.8 Hz, 2H), 6.71 (d, J =
8.8 Hz, 2H), 6.36-6.25 (m, 2H), 6.20 (d, J = 16.0 Hz, 1H), 6.13 (d, J = 3.6 Hz, 1H), 3.42 (d, J
= 6.4 Hz, 2H), 2.91 (s, 6H). 13C{1H} NMR (101 MHz, CDCl3): δ 153.4, 149.5, 141.4, 129.5,
129.2, 128.0, 119.1, 113.2, 111.2, 106.4, 41.0, 38.2. HR-MS (ESI): m/z 228.1378 [M+H]+,
calcd for C15H18ON: 228.1383.
N,N-dimethyl-4-(3-(thiophen-2-yl)allyl)aniline (3r).18 Elute: EtOAc/petroleum ether: 1/60
(v/v), yellow oil, yield 117.2 mg (96%).
NMR spectra for the E-isomer:
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1H NMR (400 MHz, CDCl3): 7.09 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 5.2 Hz, 1H), 6.91 (dd, J =
4.8, 3.6 Hz, 1H), 6.87 (d, J = 3.2 Hz, 1H), 6.71 (d, J = 8.4 Hz, 2H), 6.52 (d, J = 15.6 Hz, 1H),
6.19 (dt, J = 15.6, 6.8 Hz, 1H), 3.41 (d, J = 6.8 Hz, 2H), 2.91 (s, 6H). 13C{1H} NMR (101 MHz,
CDCl3): δ 149.5, 143.1, 130.3, 129.5, 127.9, 127.3, 124.6, 123.7, 123.4, 113.2, 41.0, 38.3. HR-
MS (ESI): m/z 244.1148 [M+H]+, calcd for C15H18NS : 244.1155.
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(E)-penta-1,4-dien-1-ylbenzene (5a).22 Elute: petroleum ether, colorless oil, yield 67.8 mg
(94%). 1H NMR (400 MHz, CDCl3): δ 7.38-7.32 (m, 2H), 7.29 (t, J = 8.0 Hz, 2H), 7.19 (t, J =
7.2 Hz, 1H), 6.41 (d, J = 15.9 Hz, 1H), 6.22 (dt, J = 15.8, 6.6 Hz, 1H), 5.97-5.84 (m, 1H), 5.15-
5.02 (m, 2H), 2.96 (dt, J = 6.5, 1.4 Hz, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 137.7, 136.6,
131.0, 128.6, 128.3, 127.2, 126.2, 115.8, 37.2.
(E)-(4-methylpenta-1,4-dien-1-yl)benzene (5b).23 Elute: petroleum ether, colorless oil, yield
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66.5 mg (84%). H NMR (400 MHz, CDCl3): δ 7.39-7.33 (m, 2H), 7.29 (t, J = 7.6 Hz, 2H),
7.23-7.17 (m, 1H), 6.42 (d, J = 15.8 Hz, 1H), 6.22 (dt, J = 15.8, 7.1 Hz, 1H), 4.81-4.75 (m, 2H),
2.90 (d, J = 7.0 Hz, 2H), 1.77 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 144.7, 137.7, 131.5,
128.6, 128.3, 127.2, 126.2, 111.2, 41.6, 22.7.
(E)-1-methoxy-4-(penta-1,4-dien-1-yl)benzene (5c).24 Elute: EtOAc/petroleum ether: 1/150
(v/v), yellowish oil, yield 86.3 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.28 (d, J = 8.7 Hz,
2H), 6.84 (d, J = 8.8 Hz, 2H), 6.35 (d, J = 15.9 Hz, 1H), 6.08 (dt, J = 15.8, 6.7 Hz, 1H), 5.97-
5.83 (m, 1H), 5.14-5.07 (m, 1H), 5.07-5.02 (m, 1H), 3.80 (s, 3H), 2.94 (td, J = 6.6, 1.4 Hz, 2H).
13C{1H} NMR (101 MHz, CDCl3): δ 158.9, 136.9, 130.6, 130.3, 127.3, 126.1, 115.6, 114.0,
55.4, 37.2.
(E)-1-methoxy-4-(4-methylpenta-1,4-dien-1-yl)benzene (5d).25 Elute: EtOAc/petroleum ether:
1/150 (v/v), colorless oil, yield 81.7 mg (87%). 1H NMR (400 MHz, CDCl3): δ 7.29 (d, J = 8.5
Hz, 2H), 6.84 (d, J = 8.8 Hz, 2H), 6.36 (d, J = 15.8 Hz, 1H), 6.08 (dt, J = 15.7, 7.1 Hz, 1H),
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4.77 (s, 2H), 3.79 (s, 3H), 2.87 (d, J = 7.0 Hz, 2H), 1.76 (s, 3H). C{1H} NMR (101 MHz,
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CDCl3): δ 158.9, 145.0, 130.8, 130.6, 127.3, 126.1, 114.0, 111.0, 55.4, 41.6, 22.6.
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(E)-1-(penta-1,4-dien-1-yl)-4-(trifluoromethyl)benzene (5e).26 Elute: petroleum ether,
colorless oil, yield 83.4 mg (79%). 1H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 8.2 Hz, 2H),
7.43 (d, J = 8.2 Hz, 2H), 6.44 (d, J = 16.0 Hz, 1H), 6.33 (dt, J = 15.9, 6.4 Hz, 1H), 5.97-5.83
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(m, 1H), 5.17-5.06 (m, 2H), 3.03-2.95 (m, 2H). C{1H} NMR (101 MHz, CDCl3): δ 141.2,
136.1, 131.2, 130.0, 129.0 (q, J = 32.4 Hz), 126.3, 125.6 (q, J = 3.8 Hz), 124.4 (q, J = 271.6
Hz), 116.3, 37.1. 19F NMR (376 MHz, CDCl3): δ 62.43.
(E)-1-(4-methylpenta-1,4-dien-1-yl)-4-(trifluoromethyl)benzene (5f).27 Elute: petroleum ether,
colorless oil, yield 79.2 mg (70%). 1H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 8.2 Hz, 2H),
7.44 (d, J = 8.4 Hz, 2H), 6.45 (d, J = 15.9 Hz, 1H), 6.33 (dt, J = 15.8, 6.9 Hz, 1H), 4.80 (d, J =
14.7 Hz, 2H), 2.92 (d, J = 6.9 Hz, 2H), 1.77 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 144.1,
141.2, 131.2, 130.3, 129.0 (q, J = 32.3 Hz), 126.3, 125.6 (q, J = 3.8 Hz, 6H), 124.4 (q, J =
271.7 Hz), 111.6, 41.6, 22.7. 19F NMR (376 MHz, CDCl3): δ 62.42.
(E)-N,N-dimethyl-4-(4-phenylbut-3-en-2-yl)aniline (3u).18 Elute: EtOAc/petroleum ether: 1/60
(v/v), colorless oil, yield 118.1 mg (94%). 1H NMR (400 MHz, CDCl3): δ 7.38-7.30 (m, 2H),
7.26 (t, J = 7.6 Hz, 2H), 7.20-7.12 (m, 3H), 6.71 (d, J = 8.8 Hz, 2H), 6.42-6.32 (m, 2H), 3.61-
3.49 (m, 1H), 2.90 (s, 6H), 1.42 (d, J = 7.0 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 149.4,
137.9, 136.2, 133.8, 128.6, 128.0, 128.0, 127.0, 126.2, 113.1, 41.7, 41.0, 21.4.
(E)-4-(1,3-diphenylallyl)-N,N-dimethylaniline (3v).28 Elute: EtOAc/petroleum ether: 1/60 (v/v),
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yellow oil, yield 119.1 mg (76%). H NMR (400 MHz, CDCl3): δ 7.37 (d, J = 7.4 Hz, 2H),
7.33-7.27 (m, 5H), 7.25-7.18 (m, 3H), 7.10 (d, J = 8.8 Hz, 2H), 6.70 (d, J = 8.8 Hz, 2H), 6.66-
6.62 (m, 1H), 6.33 (d, J = 15.8 Hz, 1H), 4.81 (d, J = 7.4 Hz, 1H), 2.92 (s, 6H). 13C{1H} NMR
(101 MHz, CDCl3): δ 149.4, 144.3, 137.6, 133.5, 131.6, 130.9, 129.4, 128.8, 128.6, 128.5,
127.2, 126.4, 126.3, 112.9, 53.4, 40.9.
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(E)-(3-methylpenta-1,4-dien-1-yl)benzene (5g).29 Elute: petroleum ether, colorless oil, yield
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76.0 mg (96%). H NMR (400 MHz, CDCl3): δ 7.40-7.32 (m, 2H), 7.29 (t, J = 7.6 Hz, 2H),
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7.19 (t, J = 7.2 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 6.17 (dd, J = 15.9, 7.0 Hz, 1H), 5.93-5.80
(m, 1H), 5.11-4.97 (m, 2H), 3.09-2.96 (m, 1H), 1.20 (d, J = 6.9 Hz, 3H). 13C{1H} NMR (101
MHz, CDCl3): δ 142.6, 137.8, 134.4, 128.8, 128.6, 127.1, 126.2, 113.5, 40. 8, 19.9.
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(E)-penta-1,4-diene-1,3-diyldibenzene (5h).30 Elute: petroleum ether, colorless oil, yield 94.9
mg (86%). 1H NMR (400 MHz, CDCl3): δ 7.42-7.17 (m, 10H), 6.50-6.33 (m, 2H), 6.19-6.03
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(m, 1H), 5.25-5.07 (m, 2H), 4.22 (t, J = 5.5 Hz, 1H). C{1H} NMR (101 MHz, CDCl3): δ
142.8, 140.2, 137.5, 131.9, 130.8, 128.7, 128.7, 128.2, 127.4, 126.7, 126.4, 115.8, 52.5.
Acknowledgments
Financial support from the National Natural Science Foundation of China (grant no. 21172208)
and the National Basic Research Program of China (grant no. 2015CB856600) is greatly
acknowledged.
Supporting Information
1
13
Copies of H and C{1H} NMR spectra of the cross-coupling products. This material is
available free of charge via the Internet at http://pubs.acs.org.
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