Nickel-Catalyzed Alkylation or Reduction of Allylic Alcohols with Alkyl Grignard Reagents

Article abstract of DOI:10.1021/acs.joc.0c00008

By choosing different phosphine ligands, nickel-catalyzed selective alkylation and reduction of allylic alcohols with alkyl Grignard reagents were performed. The reaction using Ni(dppe)Cl₂ as the catalyst resulted in the cross-coupling of allylic alcohols with primary alkyl Grignard reagents and cyclopropylmagnesium bromide. The reaction catalyzed by the combination of Ni(PCy₃)₂Cl₂ and dcype led to the reduction of allylic alcohols. Secondary alkyl Grignard reagents except cyclopropylmagnesium bromide always led to reduction of allylic alcohols using either Ni(dppe)Cl₂ or Ni(PCy₃)₂Cl₂/dcype as the catalyst. In the reductive reaction β-H-containing alkyl Grignard reagents were required.

Full text of DOI:10.1021/acs.joc.0c00008

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Article
Nickel-Catalyzed Alkylation or Reduction of
Allylic Alcohols with Alkyl Grignard Reagents
Bo Yang, and Zhong-Xia Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c00008 • Publication Date (Web): 09 Mar 2020
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Nickel-Catalyzed Alkylation or Reduction of Allylic Alcohols
with Alkyl Grignard 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 300072, P. R.
China.
Abstract: By choosing different phosphine ligands nickel-catalyzed selective alkylation and
reduction of allylic alcohols with alkyl Grignard reagents were performed. The reaction using
Ni(dppe)Cl2 as the catalyst resulted in the cross coupling of allylic alcohols with primary alkyl
Grignard reagents and cyclopropylmagnesium bromide. The reaction catalyzed by the
combination of Ni(PCy3)2Cl2 and dcype led to the reduction of allylic alcohols. Secondary alkyl
Grignard reagents except cyclopropylmagnesium bromide always led to reduction of allylic
alcohols using either Ni(dppe)Cl2 or Ni(PCy3)2Cl2/dcype as the catalyst. In the reductive reaction
-H-containing alkyl Grignard reagents were required.
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Introduction
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Compounds containing allyl moiety are widely existent in natural products and bioactive
molecules and often used as versatile building blocks in organic synthesis.1 Hence synthesis and
transformation of allyl compounds have attracted much attention. Transition-metal-catalyzed
transformation of allyl compounds such as cross-coupling and hydrogenation is among the most
widely investigated reactions. The allyl substrates employed in the transformations were often
allylic halides and allylic alcohol derivatives.2,3 However, direct use of allylic alcohols is more
step- and atom-economical because the allylic substrates such as allylic halides, allylic
carboxylates, allylic tosylates and allylic phosphates were mostly prepared from allylic alcohols.
Hence catalytic transformation of allylic alcohols via C-O bond cleavage attracts considerable
attention although the reaction is often more difficult due to the poor leaving ability of the
hydroxy group.4,5
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Kumada reaction has been extensively explored over the years.6 Compared with aryl and
alkenyl substrates, alkyl substrates involving electrophilic and nucleophilic substrates are less to
use because alkyl metal intermediates are prone to unproductive -H elimination although some
examples have been reported.6,7 Electrophilic substrates used in the successful examples are also
limited, being mainly alkyl halides. The Kumada coupling employing an alcohol as the
electrophile was rare as the reasons mentioned above.8 On the other hand, the -H elimination
side reaction in the reaction of alkyl Grignard reagents with electrophiles might become a main
reaction through choice of catalysts and conditions. Thus, reaction of alkyl Grignard reagents
with electrophilic species can be utilized to perform reduction of the organic molecules. Several
examples of transition-metal-catalyzed reduction reactions using alkyl Grignard reagents have
been reported.9 We describe here ligand-controlled nickel-catalyzed selective alkylation and
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reduction of allylic alcohols with alkyl Grignard reagents.
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Results and Discussion
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We chose reaction of (E)-3-(3-methoxyphenyl)prop-2-en-1-ol (1a) with hexylmagnesium
bromide to screen catalysts and conditions (Table 1). In the absence of a transition metal catalyst,
the reaction cannot occur at all (entry 1). In the presence of 10 mol% Fe(acac)3 and 20 mol%
PCy3, the reaction gave a reductive product 4a in 13% yield. No cross-coupling product was
obtained. A combination of CoCl2 or CoBr2 (10 mol%) and PCy3 (20 mol%) as well as
Co(PPh3)2Cl2 (10 mol%) showed higher catalytic activity than the combination of Fe(acac)3 and
PCy3 and each of the cobalt catalysts led to formation of 4a in 47% yield (entries 2-4). Both
PdCl2(dppf) and PdCl2(PPh3)2 cannot catalyze the reaction (entries 5 and 6). Several nickel
complexes including NiCl2(PPh3)2, NiCl2(PCy3)2 and NiCl2(PMe3)2 were demonstrated to be
more active catalysts than the iron and cobalt catalysts. They catalyzed the reaction to yield
reductive product 4a without exception (entries 7-9). However, bidentate phosphine ligand
coordinated nickel complexes such as NiCl2(dppe) and NiCl2(dppp) led to formation of cross-
coupling product 3a, along with a small amount of reductive product 4a (entries 10 and 11).
NiCl2(dppf) and the combination of NiCl2(DME), Ni(OTf)2 or Ni(acac)2 and dcype behaved
different from NiCl2(dppe) and NiCl2(dppp). They drove the reaction to form reductive product
4a (entries 12-15). Further tests showed that the combination of NiCl2(PCy3)2 (10 mol%) and
dcype (10 mol%) led to formation of 4a in the highest yield (entry 16). Higher loading of dcype
was unfavorable (entry 17). Next, we optimized other conditions including reaction temperature,
solvent, loading amount of the catalysts, loading amount of n-HexMgBr, and reaction time
employing NiCl2(dppe) as the coupling catalyst and NiCl2(PCy3)2/dcype as the reduction catalyst,
respectively (Tables S1-S5 in the Supporting Information). The results showed that reaction of
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1a with 3.0 equiv of n-HexMgBr in the presence of 10 mol% NiCl2(dppe) in toluene at 50 °C for
5 h gave the optimal yield of the cross-coupling product. The reductive reaction required 3.5
equiv of n-HexMgBr and 10 mol% of NiCl2(PCy3)2/dcype loadings to achieve the optimal results.
Higher reaction temperature (100 °C) and longer reaction time (12 h) were necessary. Toluene
was also suitable solvent for this transformation.
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Table 1. Screening of transition-metal catalystsa
Entry
Cat. (mol%)
Yield (%)b (3a:4a)
0
1
2
3

Fe(acac)3 (10) + PCy3 (20)
CoX2 (10) + PCy3 (20)
(X = Cl or Br)
13 (0:100)
47 (0:100)
4
Co(PPh3)2Cl2 (10)
PdCl2(dppf)
47 (0:100)

5c
6
PdCl2(PPh3)2

7
NiCl2(PPh3)2 (10)
NiCl2(PCy3)2 (10)
NiCl2(PMe3)2 (10)
NiCl2(dppe) (10)
NiCl2(dppp) (10)
NiCl2(dppf) (10)
NiCl2(DME) (10) + dcype (10)
Ni(OTf)2 (10) + dcype (10)
57 (0:100)
60 (0:100)
50 (0:100)
96 (95:5)
96 (89:11)
60 (0:100)
16 (0:100)
13 (0:100)
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Ni(acac)2 (10) + dcype (10)
60 (0:100)
91 (0:100)
39 (0:100)
NiCl2(PCy3)2 (10) + dcype (10)
NiCl2(PCy3)2 (10) + dcype (20)
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a
The reactions were carried out on a 0.2 mmol scale according to the conditions indicated by
b
1
the above equation. Yields were determined by H NMR spectra using CHCl2CHCl2 as an
internal standard. The reaction was carried out in toluene (120 °C), THF (80 °C) and Et2O
(50 °C), respectively.
c
With the optimized conditions in hand, we first examined the scope of substrates of the cross-
coupling reaction. Reaction of various allylic alcohols with n-HexMgCl was tested (Table 2). A
series of 3-(substituted phenyl)prop-2-en-1-ols, RC6H4CH=CHCH2OH (R = m-OMe, m-CF3, p-t-
Bu, p-OMe, p-NMe2, p-OCF3 and p-CF3), were demonstrated to react smoothly with n-
HexMgCl, affording the cross-coupling products along with a small amount of reductive side
products (entries 1-7). Reaction of the above subtrates with m-CF3 and p-CF3 groups on the
phenyl rings gave relatively low product yields because of the existence of side reactions (entries
2 and 7). Reaction of the other substrates resulted in the desired products in excellent yields. The
allylic alcohols with electron-poor phenyl substituents gave higher ratio of cross-coupling
products (entries 2, 6 and 7). Reaction of (E)-3-(4-fluorophenyl)prop-2-en-1-ol with n-HexMgCl
generated a mixture of (E)-1-fluoro-4-(non-1-en-1-yl)benzene (3h) and (E)-non-1-en-1-
ylbenzene (3h') in a ratio of 58 to 42 (entry 8). The latter was formed via catalytic reduction of
the aromatic C-F bond by n-HexMgCl.10 Reaction of both (E)-3-(4-chlorophenyl)prop-2-en-1-ol
and (E)-3-(4-(methylthio)phenyl) prop-2-en-1-ol with n-HexMgCl gave (E)-1-hexyl-4-(non-1-
en-1-yl)benzene (entries 9 and 10). This resulted from further alkylation of the aromatic C-Cl
and C-SMe bonds under the current conditions.11 Reaction of other 3-arylprop-2-en-1-ols
including
(E)-3-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)prop-2-en-1-ol,
(E)-3-(benzo[d][1,3]
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dioxol-5-yl)prop-2-en-1-ol, and (E)-3-(naphthalen-2-yl)prop-2-en-1-ol with n-HexMgCl resulted
in the corresponding cross-coupling products along with a small amount of reductive products
(entries 11-13). (E)-4-Phenylbut-3-en-2-ol exhibited lower reactivity than the (E)-3-arylprop-2-
en-1-ols shown in entries 1-7. Its reaction with n-HexMgCl required higher temperature and
longer time to reach completion and gave relatively low product yield (entry 14). Several (E)-3-
alkylprop-2-en-1-ols were also tested (entries 15-18). They reacted smoothly with n-HexMgCl
under the optimized conditions. Reaction of 1-arylprop-2-en-1-ols including 1-(4-
methoxyphenyl)prop-2-en-1-ol and 1-(4-(dimethylamino)phenyl) prop-2-en-1-ol resulted in
linear coupling products 3d and 3e, respectively. Small amount of reductive product was also
observed in each case (entries 19 and 20).
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Table 2. Cross-coupling of allylic alcohols with n-HexMgCla
Entry
1
Allylic alcohol
Product (major)
Yield [%]b (3:4)
97 (95:5)
2
79 (>99:1)
OH
R
3
4
R = t-Bu 3c
96 (96:4)
99 (97:3)
R = OMe 3d
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R = NMe2 3e
R = OCF3 3f
R = CF3 3g
91 (94:6)
98 (>99:1)
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79 (>99:1)
99 (3h:3h' = 58:42)c
OH
R
9
R = Cl
99 (98:2)c
92 (97:3)c
85 (95:5)
10
11
R = SMe
12
13
69 (95:5)d
99 (96:4)
14
53e
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X= CH2 3n
X = O 3o
72 (/ = 95:5)
76 (/ = 98:2)
97 (/ = 86:14)
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99 (/ = 85:15)
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R = OMe 3d
R = NMe2 3e
92 (95:5)
94 (89:11)
a
Unless otherwise specified, the reactions were carried out on a 0.2 mmol scale according to
b
the conditions indicated by the above equation. Isolated yield. The product ratio was obtained
by the 1H NMR integration. c 3.5 equiv of n-HexMgCl were used. d 100 °C, 12 h. e 120 °C, 12 h.
Next, various alkyl Grignard reagents were tested by reaction with 1a (Table 3). Each of
EtMgCl, n-PrMgBr, n-BuMgCl, and n-C8H17MgBr exhibited similar reactivity to n-HexMgCl.
Their reaction with 1a resulted in the desired cross-coupling products in very good yields along
with a small amount of reductive species (entries 1-4). Reaction of both EtMgCl and n-PrMgBr
gave the reductive species in a higher ratio than those of n-BuMgCl, n-C6H13MgCl and n-
C8H17MgBr. Reaction of Ph(CH2)2MgBr with 1a gave a mixture of coupling product and
reductive product in 74 to 26 ratio (entry 5). Relatively high ratio of reductive product is ascribed
to the formation of stable styrene via -H elimination of the alkylnickel intermediate. This is
supported by reaction of Ph(CH2)3MgBr with 1a, which resulted in a mixture of coupling
product and reductive product in 93 to 7 ratio (entry 6). Several -H-free alkyl Grignard reagents
including MeMgCl, PhCH2MgCl, t-BuCH2MgBr, and Me3SiCH2MgCl were also employed in
the transformation (entries 7-10). Except t-BuCH2MgBr each of the Grignard reagents resulted in
the desired cross-coupling product in excellent yield. Reaction of t-BuCH2MgBr with 1a under
catalysis of NiCl2(dppe) gave the cross-coupling product (3ai) in 50% yield. However, the
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reaction under catalysis of NiCl2(PCy3)/dcype at 120 °C resulted in 3ai in 85% yield (entry 9).
Reaction of secondary alkyl Grignard reagent, cyclopropylmagnesium bromide, with 1a required
higher temperature and longer time, and gave the cross-coupling product in relatively low yield,
along with a small amount of reductive species (entry 11). Other secondary alkyl Grignard
reagents including cyclobutylmagnesium bromide, cyclopentylmagnesium bromide,
cyclohexylmagnesium bromide, and isopropylmagnesium bromide were also examined. No
cross-coupling reaction occurred under the standard conditions. When the reactions were
performed at 120 °C, the reductive product 4a was obtained in moderate yields (Scheme 1).
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Table 3. Cross-coupling of (E)-3-(3-methoxyphenyl)prop-2-en-1-ol with RMgXa
Entry
1
RMgX
Product (major)
3aa
3ab
3ac
3ad
3ae
3af
Yield (%)b (3:4a)
EtMgCl
95 (85:15)
2
3
4
5
6
7
8
n-PrMgBr
93 (82:18)
99 (95:5)
99 (95:5)
99 (74:26)c
99 (93:7)d
91e
n-BuMgCl
n-C8H17MgBr
Ph(CH2)2MgBr
Ph(CH2)3MgBr
MeMgCl
3ag
3ah
PhCH2MgCl
94e
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t-BuCH2MgBr
50e (85f,g)
99e
3ai
3aj
10
11
Me3SiCH2MgCl
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42 (92:8)e
3ak
a
Unless otherwise specified, the reactions were carried out on a 0.2 mmol scale according to
b
the conditions indicated by the above equation. Isolated yield. The product ratio was obtained
by the 1H NMR integration. c Yield of pure 3ae was 73%. d Yield of pure 3af was 92%. e 80 °C. f
A combination of NiCl2(PCy3)2 (10 mol%) and dcype (10 mol%) as catalyst. g 120 °C, 12 h.
Scheme 1. Reaction of allylic alcohol 1a with secondary alkyl Grignard reagents.
R-MgX (3 equiv)
MeO
MeO
NiCl2(dppe) (10 mol%)
OH
H
toluene, 120 °C, 12 h
1a
4a
MgBr
MgBr
62%
RMgX
MgCl
59%
MgBr
4a
Yield of
63%
64%
Reduction of various allylic alcohols was examined by reaction with n-HexMgCl under the
optimized conditions (Table 4). 3-(meta-, ortho- and para-substituted phenyl)prop-2-en-1-ols
showed good reactivity. Their reactions with n-HexMgCl gave the reductive products in very
good yields (entries 1-6). Reaction of (E)-3-(3-phenoxyphenyl)prop-2-en-1-ol and (E)-3-
(biphenyl-2-yl)prop-2-en-1-ol also gave small amount of -hydrogenated isomers besides the
corresponding main products (entries 2 and 3). Several 3-(para-substituted phenyl)prop-2-en-1-
ols including (E)-3-(4-(methylthio)phenyl)prop-2-en-1-ol, (E)-3-(4-fluorophenyl)prop-2-en-1-ol
and (E)-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-ol showed different reactivity from the
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compounds mentioned above. Reaction of each of them with n-HexMgCl resulted in (E)-1-
hexyl-4-(prop-1-en-1-yl)benzene, along with a small amount of 1-allyl-4-hexylbenzene. In these
reactions, the SMe, F and OCF3 groups on the aromatic rings were converted to n-C6H13 group
via nickel-catalyzed cross-coupling with n-HexMgCl. Meanwhile, the OH group in each
molecule was catalytically reduced by n-HexMgCl (entries 7-9). Other aryl-substituted allylic
alcohols such as (E)-3-(benzo[d][1,3]dioxol-5-yl)prop-2-en-1-ol, (E)-3-(naphthalen-1-yl)prop-2-
en-1-ol and (E)-3-(1-methyl-1H-indol-5-yl)prop-2-en-1-ol resulted in normal reductive products
when reaction with n-HexMgCl (entries 10-12). Reaction of (E)-3-(naphthalen-1-yl)prop-2-en-1-
ol also formed a small amount of 1-allylnaphthalene as the side product (entry 11). Alkyl-
substituted allylic alcohol, (E)-5-(4-methoxy phenyl)pent-2-en-1-ol, reacted with n-HexMgCl
under the standard conditions to give a mixture of regio isomers (/ = 82:18) in 91% total yield
(entry 13). 1,3-Disubstituted allylic alcohol, (E)-1,3-diphenylprop-2-en-1-ol, also reacted
smoothly with n-HexMgCl to afford (E)-prop-1-ene-1,3-diyldibenzene in 64% yield (entry 14).
Finally, we examined reaction of two 1-arylprop-2-en-1-ols, 1-(4-methoxyphenyl)prop-2-en-1-ol
and 1-(4-(dimethylamino)phenyl)prop-2-en-1-ol. Reaction of each of them with n-HexMgCl
gave terminal hydrogenation species in good yield (entries 15 and 16).
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Table 4. Reduction of Allylic Alcohols with n-HexMgCla
Entry
Allylic alcohol
Product
Yield (%)b
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81
(/ = 94:6)c
89
(/ = 94:6)c
4
5
6
R = t-Bu 4d
R = OMe 4e
R = NMe2 4f
86
86
89
7
R = SMe
R = F
44d
86d
50d
62
8
9
R = OCF3
10
11
78
OH
(/ = 94:6)c
12
13
50
91
(/ = 82:18)c
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15
16
R = OMe 4e
R = NMe2 4f
75%
76%
a
The reactions were carried out on a 0.2 mmol scale according to the conditions indicated by
the above equation. b Isolated yield. c The isomer ratio was obtained by the 1H NMR integration.
d The products were a mixture of regio isomers (/ = 88:12).
We also examined the reductive reaction using other alkyl Grignard reagents under the
optimized conditions (Table 5). Thus, reaction of (E)-3-(3-methoxyphenyl) prop-2-en-1-ol with
3.5 equiv of Grignard reagents was performed in the presence of NiCl2(PCy3)2 (10 mol%)/dcype
(10 mol%) in toluene at 100 °C for 12 h. The reductive product 4a was obtained in 56% to 91%
yields. Among the primary alkyl Grignard reagents EtMgCl led to relatively low yield of 4a, and
n-PrMgBr and n-BuMgCl led to excellent yields of 4a (entries 1-3). Among the secondary alkyl
Grignard reagents tested, i-PrMgCl exhibited good reactivity and led to formation of 4a in very
good yield; whereas cyclobutylmagnesium bromide, cyclopentyl magnesium bromide and
cyclohexylmagnesium bromide led to the desired procucts in 72-74% yields (entries 4-7).
Tertiary alkyl Grignard reagent, t-BuMgCl, showed very similar reactivity to i-PrMgCl. Its
reaction under the standard conditions gave the reductive product in 83% yield (entry 8).
Table 5 Reduction of (E)-3-(3-methoxyphenyl)prop-2-en-1-ol with various Grignard reagentsa
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Entry
RMgX
Yield (%)b
1
2
3
4
5
EtMgCl
56
91
90
83
73
n-PrMgBr
n-BuMgCl
i-PrMgCl
6
7
72
74
8
t-BuMgCl
83
a The reactions were carried out on a 0.2 mmol scale according to the conditions indicated by
the above equation. b Yields were determined by H NMR spectra using CHCl2CHCl2 as an
1
internal standard.
The optimized conditions for coupling and reduction also suited for a larger scale of
preparation. 2 mmol of (E)-3-(3-methoxyphenyl)prop-2-en-1-ol was treated with an equiv of
MeMgCl and then coupled with n-HexMgCl under the standard coupling conditions to afford
cross-coupling product 3 in excellent yield, along with a small amount of reductive product 4a
(Scheme 2a). Similarly, 2 mmol of (E)-3-(3-methoxyphenyl) prop-2-en-1-ol was treated with an
equiv of MeMgCl and then n-HexMgCl under the standard reduction conditions to give
reductive species 4a in 83% yield (Scheme 2b). These experimental results attested to the
synthetic utility of the methods.
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Scheme 2. Scale-up experiments.
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Preliminary mechanistic studies were performed. Reaction of (E)-3-cyclopropylprop-2-en-1-ol
with 3 equiv of Ph(CH2)3MgBr in the presence of NiCl2(dppe) (10 mol%) afforded the cross-
coupling product (E)-(6-cyclopropylhex-5-en-1-yl)benzene in 59% yield, along with
homocoupling species of Ph(CH2)3MgBr. No products formed via ring-opening of cyclopropyl
group were observed. This rules out the possibility of a free radical process (Scheme 3a). The
homocoupling species of Ph(CH2)3MgBr might be generated via reaction of the Grignard reagent
with NiCl2(dppe) which results in formation of a Ni(0) species. The catalytic activity of the
combination of Ni(COD)2 (10 mol%), PCy3 (20 mol%) and dcype (10 mol%) towards the
reaction of (E)-3-(3-methoxyphenyl)prop-2-en-1-ol with n-HexMgCl is comparable to that of the
combination of NiCl2(PCy3)2 (10 mol%) and dcype (10 mol%). This implies that the reductive
reaction might be through a Ni(0)/Ni(II) catalytic cycle (Scheme 3b). Under the optimized
reductive conditions reaction of (E)-3-(3-methoxyphenyl)prop-2-en-1-ol with MeMgCl
generated a cross-coupling product (Scheme 3c). No reductive product was observed. This
experimental fact shows that the reductive reaction cannot occur between a allylic alcohol and a
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-H-free alkyl Grignard reagent. When a -deuterated alkyl Grignard reagent, 2-
NapCD2CH2MgCl (2-Nap = 2-naphthyl), was reacted with (E)-3-cyclopropylprop-2-en-1-ol
under the standard reductive conditions, m-MeOC6H4CH=CHCH2D and 2-NapC(D)=CH2 were
obtained in 50% and 83% yields, respectively (Scheme 3d). Under the coupling conditions
reaction of 2-NapCD2CH2MgCl with (E)-3-cyclopropylprop-2-en-1-ol afforded the cross-
coupling product in 75% yield (Scheme 3e). Formation of - and -isomers in the coupling
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reaction and reductive reaction of 3-alkyl allylic alcohols implies the existence of an 3-
allylnickel intermadiate in the catalytic process (Table 2, entries 15-18 and Table 4, entry 13).
On the basis of above experimental facts, a Ni(0)/Ni(II) process might operate in the catalytic
cycle. But a Ni(I)/Ni(III) mechanism cannot be ruled out. The possible mechanism via
Ni(0)/Ni(II) process is proposed in Scheme 4. Thus, in the catalytic cycle a Ni(0) species A is
first formed through reduction of Ni(II) with the Grignard reagent. Oxidative addition of the Ni(0)
with allyloxomagnesium B produces allylnickel intermediates which involve C (3-allyl) and D
(1-allyl) as an equilibrium mixture.8a,12a-b Subsequently, transmetalation of C and D with
Grignard reagent forms allylnickel complexes E (3-allyl) and F (1-allyl) as another
equilibrium mixture. If the ligand is not bulky enough (e.g. dppe), 3-allylnickel C and E might
be the major constituent in the respective equilibrium. Reductive elimination of E results in - or
-alkylated product of the allyl alcohol. When one of the R’ and R” groups is an aryl group, the
more stable aryl-alkenyl - conjugated product is preferred. If the ligand is bulky enough (e.g.
dcype), 1-allylnickel D and F might be the major constituent in the equilibriums. In addition,
stronger electron-donation of ligand is better for the -H elimination.12c Both steric and
electronic factors promote -H elimination of F which gives 3-allylnickel hydride intermediate
G. Reductive elimination of G results in - or - hydrogenated product of the allyl alcohol, and
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regenerates catalytically active Ni(0) species.
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Scheme 3. Mechanistic studies.
a)
Ph(CH2)3MgBr (3 equiv)
Ph
NiCl2(dppe) (10 mol%)
3r
, 0.118 mmol (59%)
HO
1r
+
toluene, 50 °C, 5 h
Ph
Ph
(0.2 mmol)
5a
, 0.07 mmol
n-HexMgCl (3.5 equiv)
Ni(COD)2 (10 mol%)
PCy3 (20 mol%), dcype (10 mol%)
b)
c)
Ar
H
Ar
Ar
OH
toluene, 100 °C, 12 h
4a
, 85%
1a
CH3MgCl (3.5 equiv)
NiCl2(PCy3)2 (10 mol%)
dcype (10 mol%)
Ar
OH
CH3
, 78%
toluene, 100 °C, 12 h
1a
3ag
D
d)
+
Ar
D
2-Nap
, 83%
D D
2-NapCD2CH2MgCl
(3.5 equiv)
4m
6
, 50%
Ar
OH
H2
C
NiCl2(PCy3)2 (10 mol%)
dcype (10 mol%)
2-Nap
+
+
1a
(0.2 mmol)
2-Nap
D D
, 0.04 mmol
toluene, 100 °C, 12 h
2
5b
7
, 0.37 mmol
2-NapCD2CH2MgCl (3 equiv)
NiCl2(dppe) (10 mol%)
D D
e)
Ar
OH
Ar
2-Nap
toluene, 50 °C, 5 h
1a
3s
, 75%
Ar = m-MeOC6H4 in entries b)-e)
Scheme 4. Proposed catalytic cycle for the cross-coupling.
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Conclusion
In summary, nickel-catalyzed reaction of allylic alcohols with alkyl Grignard reagents was
performed, affording alkylation or reductive products of allylic alcohols depending on ligands.
Ni(dppe)Cl2 catalyst resulted in the cross coupling of allylic alcohols with alkyl Grignard
reagents. The combination of Ni(PCy3)2Cl2 and dcype led to the reduction of allylic alcohols by
alkyl Grignard reagents. Under the alkylation conditions primary alkyl Grignard reagents
including -H-containing and -H-free ones as well as secondary alkyl Grignard reagent,
cyclopropylmagnesium bromide, were demonstrated to be practicable nucleophiles. Secondary
alkyl Grignard reagents except cyclopropylmagnesium bromide made the reaction to form
reductive products of allylic alcohols in fair yields even in the presence of Ni(dppe)Cl2 catalyst.
Primary, secondary and tertiary alkyl Grignard reagents can be used as the reducing agents in the
presence of Ni(PCy3)2Cl2/dcype. The presence of -H was indispensable and primary alkyl
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Grignard reagents such as n-PrMgBr, n-BuMgCl and n-HexMgCl were superior to the secondary
and tertiary alkyl Grignard reagents. A range of allylic alcohols including 3-aryl and 3-alkyl
allylic alcohols, 1,3-disubstituted allylic alcohols, and 1-aryl allylic alcohols can be used in the
coupling or reductive reactions. No matter coupling or reductive reaction, 3-aryl allylic alcohols
and 1-aryl allylic alcohols resulted in linear products, whereas 3-alkyl allylic alcohols led to a
mixture of - and -alkylation/hydrogenation isomers.
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Experimental section
All reactions were performed under a nitrogen atmosphere using standard Schlenk and vacuum
line techniques. All chemicals were purchased as reagent grade and used without further
purification unless otherwise noted. Toluene, tetrahydrofuran (THF) and diethyl ether (Et2O)
were purified by JC Meyer Phoenix Solvent Systems. Butyl ether (n-Bu2O) was distilled under
nitrogen over sodium and degassed prior to use. MeMgCl, EtMgCl, n-PrMgBr, i-PrMgCl, n-
BuMgCl, t-BuMgCl, cyclopropylmagnesium bromide, cyclohexylmagnesium bromide and
benzylmagnesium chloride were purchased from commercial vendors and used as received.
Octylmagnesium bromide, phenethylmagnesium bromide, (3-phenylpropyl)magnesium bromide,
neopentylmagnesium
bromide,
((trimethylsilyl)methyl)magnesium
chloride,
cyclobutylmagnesium bromide and cyclopentylmagnesium bromide were prepared according to
the general procedure reported by Watson.13a Each of these Grignard reagents are known.13a-f
Their concentrations were titrated using Knochel’s method.14 Allylic alcohols were prepared
according to reported procedure.15 NMR spectra were recorded on a Bruker AV400 or Bruker
1
AV300 spectrometer at 25 °C. The chemical shifts of the H NMR spectra were referenced to
TMS or internal solvent resonances and the chemical shifts of the 13C NMR spectra were
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referenced to internal solvent resonances. The chemical shifts of the 19F NMR spectra were
referenced to external CF3COOH. High-resolution mass spectra (HR-MS) were acquired in the
EI mode using an Orbitrap mass analyzer.
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General procedure for the catalytic coupling of allylic alcohols with alkyl Grignard
reagents. Allylic alcohol (1.0 mL, 0.2 M solution in THF, 0.2 mmol) and Ni(dppe)Cl2 (10.6 mg,
10 mol %) were charged to a Schlenk tube under nitrogen. To the mixture was added alkyl
Grignard reagent (0.6 mmol, THF solution) at room temperature. The mixture was stirred for 5
min. and then solvent was removed in vacuo. Toluene (2 mL) was added and the resultant
mixture was stirred at 50 °C (oil bath) for 5 h. The mixture was cooled to room temperature,
diluted with EtOAc (5 mL) and filtered through a plug of silica gel which was rinsed with EtOAc
(20 mL). The filtrate was concentrated and the residue was purified by silica gel chromatography
to give the desired product.
(E)-1-methoxy-3-(non-1-en-1-yl)benzene (3a). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 44.3 mg (97%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H), 6.94 (d, J
= 7.6 Hz, 1H), 6.88 (t, J = 1.9 Hz, 1H), 6.75 (dd, J = 8.2, 2.6 Hz, 1H), 6.35 (d, J = 15.8 Hz, 1H),
6.23 (dt, J = 15.7, 6.8 Hz, 1H), 3.81 (s, 3H), 2.24–2.15 (m, 2H), 1.51–1.42 (m, 2H), 1.38–1.23
(m, 8H), 0.92–0.85 (m, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.6, 131.8, 129.7,
129.6, 118.7, 112.5, 111.4, 55.3, 33.2, 32.0, 29.5, 29.4, 22.8, 14.3. HRMS (EI-TOF) m/z: [M]+
Calcd for C16H24O 232.1822; Found 232.1822.
(E)-1-(non-1-en-1-yl)-3-(trifluoromethyl)benzene (3b). Eluent: petroleum ether. Colorless oil,
42.7 mg (79%). 1H NMR (400 MHz, CDCl3): δ 7.57 (s, 1H), 7.49 (d, J = 7.4 Hz, 1H), 7.46–7.34
(m, 2H), 6.41 (d, J = 15.9 Hz, 1H), 6.31 (dt, J = 15.8, 6.6 Hz, 1H), 2.27–2.17 (m, 2H), 1.53–1.43
(m, 2H), 1.38–1.23 (m, 8H), 0.90 (t, J = 6.9 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 138.9,
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133.5, 131.0 (q, J = 32.0 Hz), 129.2, 129.0, 128.6, 124.4 (q, J = 272.3 Hz), 123.4 (q, J = 3.8 Hz),
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122.7 (q, J = 3.8 Hz), 33.2, 32.0, 29.4, 29.3, 22.8, 14.2. F{1H} NMR (376 MHz, CDCl3): δ –
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62.76. HRMS (EI-TOF) m/z: [M]+ calcd for C16H21F3 270.1590; Found 270.1589.
(E)-1-(tert-butyl)-4-(non-1-en-1-yl)benzene (3c). Eluent: petroleum ether. Colorless oil, 48.9 mg
1
(96%). H NMR (400 MHz, CDCl3): δ 7.31 (d, J = 8.5, 2H), 7.27 (d, J = 8.5, 2H), 6.35 (d, J =
15.8 Hz, 1H), 6.18 (dt, J = 15.8, 6.9 Hz, 1H), 2.25–2.13 (m, 2H), 1.49–1.40 (m, 2H), 1.34–1.25
(m, 17H), 0.88 (t, J = 6.8 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 149.9, 135.4, 130.6,
129.5, 125.7, 125.5, 34.6, 33.2, 32.0, 31.5, 29.6, 29.4, 29.3, 22.8, 14.3. HRMS (EI-TOF) m/z:
[M]+ Calcd for C19H30 258.2342; Found 258.2343.
(E)-1-methoxy-4-(non-1-en-1-yl)benzene (3d).16 Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 45.5 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.26 (d, J = 8.5 Hz, 2H), 6.82 (d, J
= 8.5 Hz, 2H), 6.31 (d, J = 15.8 Hz, 1H), 6.07 (dt, J = 15.8, 6.8 Hz, 1H), 3.78 (s, 3H), 2.23–2.10
13
(m, 2H), 1.49–1.38 (m, 2H), 1.37–1.20 (m, 8H), 0.94–0.81 (m, 3H). C{1H} NMR (101 MHz,
CDCl3): δ 158.7, 131.0, 129.2, 129.1, 127.1, 114.0, 55.4, 33.2, 32.0, 29.7, 29.4, 22.8, 14.2.
(E)-N,N-dimethyl-4-(non-1-en-1-yl)aniline (3e). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 43.7 mg (91%). 1H NMR (400 MHz, CDCl3): δ 7.23 (d, J = 8.7 Hz, 2H), 6.67 (d, J
= 8.8 Hz, 2H), 6.28 (d, J = 15.8 Hz, 1H), 6.01 (dt, J = 15.7, 6.9 Hz, 1H), 2.92 (s, 6H), 2.21–2.12
(m, 2H), 1.49–1.38 (m, 2H), 1.36–1.22 (m, 8H), 0.88 (t, J = 6.8 Hz, 3H). 13C{1H} NMR (101
MHz, CDCl3): δ 149.8, 129.5, 127.2, 127.0, 126.8, 112.8, 40.8, 33.2, 32.0, 29.9, 29.4, 29.3, 22.8,
14.3. HRMS (EI-TOF) m/z: [M]+ Calcd for C17H27N 245.2138; Found 245.2140.
(E)-1-(non-1-en-1-yl)-4-(trifluoromethoxy)benzene (3f). Eluent: petroleum ether. Colorless oil,
56.1 mg (98%). 1H NMR (400 MHz, CDCl3): δ 7.34 (d, J = 8.7 Hz, 2H), 7.13 (d, J = 8.2 Hz, 2H),
6.35 (d, J = 15.9 Hz, 1H), 6.20 (dt, J = 15.8, 6.8 Hz, 1H), 2.26–2.14 (m, 2H), 1.51–1.41 (m, 2H),
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1.35–1.25 (m, 8H), 0.89 (t, J = 7.0 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 148.1 (m),
136.9, 132.6, 128.4, 127.2, 121.2, 120.7 (q, J = 256.6 Hz), 33.2, 32.0, 29.4, 29.1, 22.8, 14.3.
19F{1H} NMR (376 MHz, CDCl3): δ –57.91. HRMS (EI-TOF) m/z: [M]+ Calcd for C16H21OF3
286.1539; Found 286.1541.
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(E)-1-(non-1-en-1-yl)-4-(trifluoromethyl)benzene (3g). Eluent: petroleum ether. Colorless oil,
42.7 mg (79%). 1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.2 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H),
6.40 (d, J = 16.0 Hz, 1H), 6.33 (dt, J = 15.8, 6.3 Hz, 1H), 2.28–2.18 (m, 2H), 1.52–1.43 (m, 2H),
1.38–1.22 (m, 8H), 0.89 (t, J = 6.7 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 141.6 (m),
134.3, 128.71 (q, J = 32.2 Hz), 128.69, 126.1, 125.6 (q, J = 3.8 Hz), 124.5 (q, J = 271.8 Hz),
33.2, 32.0, 29.4, 29.3, 22.8, 14.3. 19F{1H} NMR (376 MHz, CDCl3) δ 62.38. HRMS (EI-TOF)
m/z: [M]+ Calcd for C16H21F3 270.1590; Found 270.1592.
(E)-1-fluoro-4-(non-1-en-1-yl)benzene (3h) and (E)-non-1-enylbenzene (3h').17 1H NMR (400
MHz, CDCl3): δ 7.37–7.25 (m, 2.73H), 7.18 (t, J = 7.2 Hz, 0.42H), 6.97 (t, J = 8.7 Hz, 1.12H),
6.42–6.29 (m, 0.99H), 6.22 (dt, J = 15.8, 6.8 Hz, 0.42H), 6.13 (dt, J = 15.8, 6.9 Hz, 0.58H),
2.24–2.14 (m, 2H), 1.51–1.40 (m, 2H), 1.36–1.23 (m, 8 H), 0.89 (t, J = 6.9 Hz, 3H). 13C{1H}
NMR (101 MHz, CDCl3) for 3h: δ 162.0 (d, J = 245.4 Hz), 134.2 (d, J = 3.3 Hz), 131.1 (d, J =
2.2 Hz), 128.6, 127.4 (d, J = 7.8 Hz), 115.4 (d, J = 21.5 Hz), 33.3, 32.2, 29.7, 29.6, 23.0, 14.5.
13C{1H} NMR (101 MHz, CDCl3) for 3h': δ 138.3, 131.6, 130.0, 128.8, 127.1, 126.2, 33.4, 32.2,
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29.8, 29.6, 23.0, 14.5. F{1H} NMR (376 MHz, CDCl3): δ –116.00. HRMS (EI-TOF) for 3h:
m/z: [M]+ Calcd for C15H21F 220.1622; Found 220.1621.
(E)-1-hexyl-4-(non-1-en-1-yl)benzene (3i). Eluent: petroleum ether. Colorless oil, 56.4 mg (99%).
1H NMR (400 MHz, CDCl3): δ 7.25 (d, J = 8.1 Hz, 2H), 7.09 (d, J = 8.1 Hz, 2H), 6.34 (d, J =
15.8 Hz, 1H), 6.17 (dt, J = 15.8, 6.9 Hz, 1H), 2.56 (t, J = 7.7 Hz, 2H), 2.22–2.14 (m, 2H), 1.63–
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1.54 (m, 2H), 1.50–1.40 (m, 2H), 1.36–1.24 (m, 14H), 0.92–0.84 (m, 6H). C{1H} NMR (101
MHz, CDCl3): δ 141.7, 135.5, 130.4, 129.7, 128.7, 125.9, 35.8, 33.2, 32.0, 31.9, 31.6, 29.6, 29.4,
29.3, 29.1, 22.83, 22.77, 14.3. HRMS (EI-TOF) m/z: [M]+ Calcd for C21H34 286.2655; Found
286.2657.
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(E)-6-(non-1-en-1-yl)-2,3-dihydrobenzo[b][1,4]dioxine (3j). Eluent: petroleum ether / ethyl
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acetate = 60:1. Colorless oil, 43.5 mg (85%). H NMR (400 MHz, CDCl3): δ 6.87 (s, 1H), 6.84
(dd, J = 8.4, 1.8 Hz, 1H), 6.79 (d, J = 8.3 Hz, 1H), 6.26 (d, J = 15.8 Hz, 1H), 6.07 (dt, J = 15.7,
6.9 Hz, 1H), 4.25 (s, 4H), 2.17 (q, J = 7.2 Hz, 2H), 1.50–1.40 (m, 2H), 1.38–1.23 (m, 8H), 0.90
(t, J = 6.5 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 143.6, 142.7, 132.0, 129.8, 129.0, 119.4,
117.3, 114.5, 64.53, 64.50, 33.1, 32.0, 29.6, 29.34, 29.32, 22.8, 14.3. HRMS (EI-TOF) m/z: [M]+
Calcd for C17H24O2 260.1771; Found 260.1770.
(E)-5-(non-1-en-1-yl)benzo[d][1,3]dioxole (3k). Eluent: petroleum ether/ethyl acetate = 60:1.
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Colorless oil, 33.4 mg (69%). H NMR (400 MHz, CDCl3): δ 6.90 (s, 1H), 6.79–6.71 (m, 2H),
6.29 (d, J = 15.8 Hz, 1H), 6.05 (dt, J = 15.7, 6.9 Hz, 1H), 5.93 (s, 2H), 2.22–2.11 (m, 2H), 1.49–
1.39 (m, 2H), 1.36–1.23 (m, 8H), 0.89 (t, J = 6.8 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ
148.0, 146.6, 132.6, 129.7, 129.3, 120.3, 108.3, 105.5, 101.0, 33.1, 32.0, 29.6, 29.3, 22.8, 14.3.
HRMS (EI-TOF) m/z: [M]+ Calcd for C16H22O2 246.1614; Found 246.1614.
(E)-2-(non-1-en-1-yl)naphthalene (3l). Eluent: petroleum ether. Colorless oil, 49.3 mg (99%)
(coupling product:reductive product = 96:4). 1H NMR (400 MHz, CDCl3): δ 7.80–7.70 (m, 3H),
7.65 (s, 1H), 7.56 (dd, J = 8.5, 1.6 Hz, 1H), 7.45–7.35 (m, 2H), 6.52 (d, J = 15.8 Hz, 1H), 6.34
(dt, J = 15.8, 6.9 Hz, 1H), 2.30–2.19 (m, 2H), 1.54–1.44 (m, 2H), 1.39–1.27 (m, 8H), 0.94–0.86
(m, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 135.6, 133.9, 132.8, 131.9, 129.9, 128.2, 127.9,
127.8, 126.2, 125.5, 125.4, 123.7, 33.4, 32.0, 29.6, 29.4, 29.38, 22.8, 14.3. HRMS (EI-TOF) m/z:
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[M]+ Calcd for C19H24 252.1873; Found 252.1873.
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(E)-(3-methylnon-1-en-1-yl)benzene (3m).18 Eluent: petroleum ether. Colorless oil, 22.9 mg
(53%). 1H NMR (400 MHz, CDCl3): δ 7.39–7.32 (m, 2H), 7.29 (t, J = 7.6 Hz, 2H), 7.21–7.16 (m,
1H), 6.33 (d, J = 15.9 Hz, 1H), 6.09 (dd, J = 15.9, 8.0 Hz, 1H), 2.31–2.23 (m, 1H), 1.31–1.22 (m,
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10H), 1.07 (d, J = 6.7 Hz, 3H), 0.87 (t, J = 6.7 Hz, 3H). C{1H} NMR (101 MHz, CDCl3): δ
138.1, 137.3, 128.6, 128.0, 126.9, 126.1, 37.4, 37.3, 32.0, 29.6, 27.5, 22.8, 20.8, 14.3.
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(E)-non-1-en-1-ylcyclohexane (3n).19 Eluent: petroleum ether. Colorless oil, 30.0 mg (72%). H
NMR (400 MHz, CDCl3): δ 5.40–5.28 (m, 2H), 2.00–1.93 (m, 2H), 1.76–1.63 (m, 5H), 1.34–
1.19 (m, 16H), 0.88 (t, J = 6.8 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 136.5, 127.9, 40.9,
33.5, 32.8, 32.0, 29.9, 29.4, 29.3, 26.4, 26.3, 22.8, 14.3.
(E)-4-(non-1-en-1-yl)tetrahydro-2H-pyran (3o). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 31.9 mg (76%). 1H NMR (400 MHz, CDCl3): δ 5.47–5.27 (m, 2H), 4.00–3.89 (m,
2H), 3.40 (dt, J = 11.7, 2.2 Hz, 2H), 2.22–2.07 (m, 1H), 2.02–1.94 (m, 2H), 1.63–1.54 (m, 2H),
1.50–1.39 (m, 2H), 1.36–1.22 (m, 10H), 0.88 (t, J = 6.9 Hz, 3H). 13C{1H} NMR (101 MHz,
CDCl3): δ 134.5, 129.1, 67.9, 38.0, 33.1, 32.7, 32.0, 29.7, 29.3, 29.2, 22.8, 14.2. HRMS (EI-
TOF) m/z: [M]+ Calcd for C14H26O 210.1978; Found 210.1973.
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(E)-undec-3-en-1-ylbenzene (3p).20 Eluent: petroleum ether. Colorless oil, 44.7 mg (97%). H
NMR (400 MHz, CDCl3): δ 7.29–7.24 (m, 2H), 7.21–7.13 (m, 3H), 5.50–5.37 (m, 2H), 2.70–
2.62 (m, 2H), 2.35–2.25 (m, 2H), 2.02–1.92 (m, 2H), 1.32–1.22 (m, 10H), 0.88 (t, J = 6.9 Hz,
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3H). C{1H} NMR (101 MHz, CDCl3): δ 142.3, 131.3, 129.4, 128.6, 128.4, 125.8, 36.3, 34.6,
32.7, 32.0, 29.7, 29.4, 29.3, 22.8, 14.3.
(E)-1-(dodec-4-en-1-yl)-4-methoxybenzene (3q). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 54.3 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.08 (d, J = 8.7 Hz, 2H), 6.81 (d, J
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= 8.7 Hz, 2H), 5.45–5.35 (m, 2H), 3.78 (s, 3H), 2.60–2.49 (m, 2H), 2.09–1.88 (m, 4H), 1.70–
1.58 (m, 2H), 1.34–1.20 (m, 10H), 0.88 (t, J = 6.9 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ
157.8, 134.9, 131.1, 129.9, 129.4, 113.8, 55.4, 34.6, 32.8, 32.2, 32.0, 31.7, 29.8, 29.4, 29.3, 22.8,
14.3. HRMS (EI-TOF) m/z: [M]+ Calcd for C19H30O 274.2291; Found 274.2294.
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(E)-2-(5-(3-methoxyphenyl)pent-4-en-1-yl-1,1-d2)naphthalene
(3s).
Eluent:
petroleum
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ether/ethyl acetate = 60:1. Colorless oil, 45.6 mg (75%). H NMR (400 MHz, CDCl3): δ 7.84–
7.77 (m, 3H), 7.65 (d, J = 1.0 Hz, 1H), 7.50–7.40 (m, 2H), 7.36 (dd, J = 8.4, 1.7 Hz, 1H), 7.23 (t,
J = 7.9 Hz, 1H), 6.96 (d, J = 7.7 Hz, 1H), 6.93–6.87 (m, 1H), 6.81–6.74 (m, 1H), 6.40 (d, J =
15.8 Hz, 1H), 6.27 (dt, J = 15.8, 6.8 Hz, 1H), 3.82 (s, 3H), 2.35–2.25 (m, 2H), 1.90 (t, J = 7.4 Hz,
2H). 13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.9, 139.4, 133.8, 132.1, 131.0, 130.3, 129.6,
128.0, 127.7, 127.54, 127.52, 126.6, 126.0, 125.2, 118.8, 112.6, 111.4, 55.3, 32.6, 30.8. HRMS
(EI-TOF) m/z: [M]+ calcd for C22H20D2O 304.1791; Found 304.1793.
(E)-1-methoxy-3-(pent-1-en-1-yl)benzene (3aa).21 Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 32.7 mg (95%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H), 6.94 (d, J
= 7.6 Hz, 1H), 6.88 (s, 1H), 6.75 (dd, J = 8.2, 2.2 Hz, 1H), 6.35 (d, J = 15.8 Hz, 1H), 6.22 (dt, J
= 15.8, 6.8 Hz, 1H), 3.81 (s, 3H), 2.24–2.13 (m, 2H), 1.54–1.43 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H).
13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.6, 131.5, 129.9, 129.6, 118.7, 112.5, 111.4, 55.3,
35.2, 22.7, 13.9.
(E)-1-(hex-1-en-1-yl)-3-methoxybenzene (3ab). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 34.2 mg (93%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H), 6.93 (d, J
= 7.5 Hz, 1H), 6.88 (s, 1H), 6.74 (dd, J = 8.2, 2.1 Hz, 1H), 6.34 (d, J = 15.8 Hz, 1H), 6.22 (dt, J
= 15.8, 6.8 Hz, 1H), 3.80 (s, 3H), 2.25–2.16 (m, 2H), 1.48–1.40 (m, 2H), 1.40–1.32 (m, 2H),
0.92 (t, J = 7.2 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.6, 131.7, 129.7, 129.5,
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118.7, 112.5, 111.4, 55.3, 32.8, 31.6, 22.4, 14.1. HRMS (EI-TOF) m/z: [M]+ Calcd for C13H18O
190.1352; Found 190.1351.
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(E)-1-(hept-1-en-1-yl)-3-methoxybenzene (3ac). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 39.9 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H), 6.94 (d, J
= 7.6 Hz, 1H), 6.88 (s, 1H), 6.75 (dd, J = 8.3, 2.4 Hz, 1H), 6.35 (d, J = 15.9 Hz, 1H), 6.23 (dt, J
= 15.8, 6.7 Hz, 1H), 3.80 (s, 3H), 2.24–2.15 (m, 2H), 1.51–1.41 (m, 2H), 1.37–1.29 (m, 4H),
0.90 (t, J = 6.6 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.6, 131.7, 129.7, 129.5,
118.7, 112.5, 111.4, 55.3, 33.1, 31.6, 29.2, 22.7, 14.2. HRMS (EI-TOF) m/z: [M]+ Calcd for
C14H20O 204.1509; Found 204.1508.
(E)-1-methoxy-3-(undec-1-en-1-yl)benzene (3ad).22 Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 50.3 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H), 6.94 (d, J
= 7.6 Hz, 1H), 6.88 (s, 1H), 6.74 (dd, J = 8.2, 2.5 Hz, 1H), 6.34 (d, J = 15.8 Hz, 1H), 6.22 (dt, J
= 15.7, 6.7 Hz, 1H), 3.80 (s, 3H), 2.26–2.14 (m, 2H), 1.51–1.40 (m, 2H), 1.36–1.20 (m, 12H),
0.88 (t, J = 6.7 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.6, 131.7, 129.7, 129.5,
118.7, 112.5, 111.4, 55.3, 33.2, 32.1, 29.74, 29.69, 29.5, 29.49, 29.4, 22.8, 14.3.
(E)-1-methoxy-3-(5-phenylpent-1-en-1-yl)benzene (3ae). Eluent: petroleum ether/ethyl acetate =
1
100:1. Colorless oil, 36.9 mg (73%). H NMR (400 MHz, CDCl3): δ 7.32–7.25 (m, 2H), 7.23–
7.14 (m, 4H), 6.94 (d, J = 7.6 Hz, 1H), 6.88 (s, 1H), 6.75 (dd, J = 8.2, 2.4 Hz, 1H), 6.36 (d, J =
15.9 Hz, 1H), 6.23 (dt, J = 15.8, 6.8 Hz, 1H), 3.80 (s, 3H), 2.67 (t, J = 7.6 Hz, 2H), 2.29–2.21 (m,
13
2H), 1.86–1.75 (m, 2H). C{1H} NMR (75 MHz, CDCl3): δ 160.0, 142.5, 139.5, 131.0, 130.3,
129.6, 128.6, 128.5, 125.9, 118.8, 112.7, 111.5, 55.3, 35.5, 32.6, 31.1. HRMS (EI-TOF) m/z:
[M]+ Calcd for C18H20O 252.1509; Found 252.1508.
(E)-1-methoxy-3-(6-phenylhex-1-en-1-yl)benzene (3af). Eluent: petroleum ether/ethyl acetate =
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100:1. Colorless oil, 49.2 mg (92%). H NMR (400 MHz, CDCl3): δ 7.27 (t, J = 7.6 Hz, 2H),
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7.23–7.13 (m, 4H), 6.93 (d, J = 7.6 Hz, 1H), 6.87 (s, 1H), 6.75 (dd, J = 8.2, 2.4 Hz, 1H), 6.34 (d,
J = 15.9 Hz, 1H), 6.20 (dt, J = 15.6, 6.8 Hz, 1H), 3.80 (s, 3H), 2.63 (t, J = 7.7 Hz, 2H), 2.28–2.17
(m, 2H), 1.73–1.63 (m, 2H), 1.54–1.45 (m, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 159.9,
142.7, 139.5, 131.3, 130.0, 129.6, 128.6, 128.4, 125.8, 118.7, 112.6, 111.4, 55.3, 36.0, 33.0, 31.2,
29.1. HRMS (EI-TOF) m/z: [M]+ Calcd for C19H22O 266.1665; Found 266.1666.
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(E)-1-(but-1-en-1-yl)-3-methoxybenzene (3ag). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 29.6 mg (91%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H), 6.94 (d, J
= 7.7 Hz, 1H), 6.88 (s, 1H), 6.74 (dd, J = 8.2, 2.5 Hz, 1H), 6.35 (d, J = 15.9 Hz, 1H), 6.26 (dt, J
= 15.8, 6.1 Hz, 1H), 3.80 (s, 3H), 2.30–2.15 (m, 2H), 1.09 (t, J = 7.5 Hz, 3H). 13C{1H} NMR
(101 MHz, CDCl3): δ 159.9, 139.5, 133.1, 129.5, 128.8, 118.7, 112.5, 111.3, 55.3, 26.2, 13.7.
HRMS (EI-TOF) m/z: [M]+ Calcd for C11H14O 162.1039; Found 162.1038.
(E)-1-methoxy-3-(4-phenylbut-1-en-1-yl)benzene (3ah). Eluent: petroleum ether/ethyl acetate =
1
60:1. Colorless oil, 44.7 mg (94%). H NMR (400 MHz, CDCl3): δ 7.30 (t, J = 7.5 Hz, 2H),
7.25–7.16 (m, 4H), 6.93 (d, J = 7.7 Hz, 1H), 6.87 (s, 1H), 6.75 (dd, J = 8.1, 2.3 Hz, 1H), 6.39 (d,
J = 15.9 Hz, 1H), 6.26 (dt, J = 15.8, 6.7 Hz, 1H), 3.80 (s, 3H), 2.79 (t, J = 9.8 Hz, 2H), 2.59–2.46
(m, 2H). 13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 141.9, 139.3, 130.5, 130.4, 129.6, 128.6,
128.5, 126.0, 118.8, 112.6, 111.5, 55.3, 36.0, 35.0. HRMS (EI-TOF) m/z: [M]+ Calcd for
C17H18O 238.1352; Found 238.1352.
(E)-1-(5,5-dimethylhex-1-en-1-yl)-3-methoxybenzene (3ai). Eluent: petroleum ether/ethyl acetate
= 100:1. Colorless oil, 36.9 mg (85%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H),
6.93 (d, J = 7.6 Hz, 1H), 6.88 (s, 1H), 6.74 (dd, J = 8.2, 2.6 Hz, 1H), 6.36 (d, J = 15.8 Hz, 1H),
6.23 (dt, J = 15.8, 6.7 Hz, 1H), 3.80 (s, 3H), 2.25–2.11 (m, 2H), 1.41–1.31 (m, 2H), 0.93 (s, 9H).
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13C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.6, 132.4, 129.6, 129.3, 118.7, 112.5, 111.3, 55.3,
43.8, 30.5, 29.5 28.5. HRMS (EI-TOF) m/z: [M]+ Calcd for C15H22O 218.1665; Found 218.1665.
(E)-(4-(3-methoxyphenyl)but-3-en-1-yl)trimethylsilane (3aj). Eluent: petroleum ether/ethyl
acetate = 100:1. Colorless oil, 46.5 mg (99%). 1H NMR (400 MHz, CDCl3): δ 7.22 (t, J = 7.9 Hz,
1H), 6.95 (d, J = 7.7 Hz, 1H), 6.90 (s, 1H), 6.76 (dd, J = 7.9, 2.2 Hz, 1H), 6.36 (d, J = 15.9 Hz,
1H), 6.28 (dt, J = 15.7, 6.0 Hz, 1H), 3.82 (s, 3H), 2.32–2.15 (m, 2H), 0.78–0.65 (m, 2H), 0.04 (s,
9H). 13C{1H} NMR (75 MHz, CDCl3): δ 160.0, 139.7, 134.3, 129.5, 128.4, 118.8, 112.5, 111.5,
55.3, 27.5, 16.4, –1.4. HRMS (EI-TOF) m/z: [M]+ Calcd for C14H22OSi 234.1434; Found
234.1432.
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(E)-1-(3-cyclopropylprop-1-en-1-yl)-3-methoxybenzene (3ak). Eluent: petroleum ether/ethyl
acetate = 100:1. Colorless oil, 15.5 mg (42%). 1H NMR (400 MHz, CDCl3): δ 7.22 (t, J = 7.9 Hz,
1H), 6.97 (d, J = 7.7 Hz, 1H), 6.91 (s, 1H), 6.76 (dd, J = 8.1, 2.4 Hz, 1H), 6.42 (d, J = 15.9 Hz,
1H), 6.30 (dt, J = 15.8, 6.4 Hz,1H), 3.82 (s, 3H), 2.12 (t, J = 6.5 Hz, 2H), 0.91–0.77 (m, 1H),
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0.56–0.45 (m, 2H), 0.15 (q, J = 4.9 Hz, 2H). C{1H} NMR (101 MHz, CDCl3): δ 159.9, 139.5,
130.6, 129.8, 129.6, 118.8, 112.6, 111.4, 55.3, 37.8, 10.5, 4.4. HR-MS (EI-TOF) m/z: [M]+
Calcd for C13H16O 188.1196; Found 188.1195.
General procedure for the catalytic reduction of allylic alcohols with n-HexMgCl. Allylic
alcohol (1.0 mL, 0.2 M solution in THF, 0.2 mmol), Ni(PCy3)Cl2 (13.8 mg, 10 mol %), and
dcype (8.5 mg, 10 mol%) were successively charged to a Schlenk tube under nitrogen. To the
mixture was added n-HexMgCl (0.35 mL, 2 M solution in THF, 0.7 mmol) at room temperature.
The mixture was stirred for 5 min. and then solvent was removed in vacuo. Toluene (2 mL) was
added and the resultant mixture was stirred at 100 °C for 12 h. The mixture was cooled to room
temperature, diluted with EtOAc (5 mL) and filtered through a plug of silica gel which was
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rinsed with EtOAc (20 mL). The filtrate was concentrated and the residue was purified by silica
gel chromatography to give the desired product.
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(E)-1-methoxy-3-(prop-1-en-1-yl)benzene (4a).23 Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 25.9 mg (87%). 1H NMR (400 MHz, CDCl3): δ 7.20 (t, J = 7.9 Hz, 1H), 6.92 (d, J
= 7.7 Hz, 1H), 6.87 (t, J = 2.0 Hz, 1H), 6.75 (dd, J = 8.5, 2.2 Hz, 1H), 6.37 (dd, J = 15.7, 1.5 Hz,
1H), 6.24 (dq, J = 15.7, 6.5 Hz, 1H), 3.81 (s, 3H), 1.88 (dd, J = 6.5, 1.5 Hz, 3H). 13C{1H} NMR
(101 MHz, CDCl3): δ 159.9, 139.5, 131.0, 129.6, 126.2, 118.6, 112.5, 111.3, 55.3, 18.6.
(E)-1-phenoxy-3-(prop-1-en-1-yl)benzene (4b). Eluent: petroleum ether/ethyl acetate = 60:1.
Colorless oil, 34.2 mg (81%). 1H NMR (400 MHz, CDCl3): δ 7.37–7.29 (m, 2H), 7.24 (t, J = 7.9
Hz, 1H), 7.12–7.04 (m, 2H), 7.04–6.95 (m, 3H), 6.84 (dd, J = 8.1, 1.5 Hz, 1H), 6.35 (dd, J = 15.8,
1.2 Hz, 1H), 6.21 (dq, J = 15.7, 6.5 Hz, 1H), 1.86 (dd, J = 6.5, 1.4 Hz, 3H). 13C{1H} NMR (101
MHz, CDCl3): δ 157.53, 157.45, 140.0, 130.6, 129.8, 126.8, 123.3, 121.1, 118.9, 117.4, 116.3,
18.6. HRMS (EI-TOF) m/z: [M]+ Calcd for C15H14O 210.1039 ; Found 210.1038.
(E)-2-(prop-1-en-1-yl)-1,1'-biphenyl (4c). Eluent: petroleum ether/ethyl acetate = 100:1.
Colorless oil, 34.6 mg (89%). 1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 7.4 Hz, 1H), 7.45–7.38
(m, 2H), 7.37–7.32 (m, 3H), 7.32–7.28 (m, 1H), 7.28–7.21 (m, 2H), 6.37 (dd, J = 15.7, 1.5 Hz,
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1H), 6.16 (dq, J = 15.7, 6.6 Hz, 1H), 1.79 (dd, J = 6.6, 1.6 Hz, 3H). C{1H} NMR (101 MHz,
CDCl3) : δ 141.3, 140.2, 136.0, 130.3, 129.9, 129.9, 128.1, 127.5, 127.0, 126.8, 126.6, 125.9,
18.8. HRMS (EI-TOF) m/z: [M]+ Calcd for C15H14 194.1090; Found 194.1088.
(E)-1-(tert-butyl)-4-(prop-1-en-1-yl)benzene (4d).24 Eluent: petroleum ether. Colorless oil, 30.3
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mg (86%). H NMR (400 MHz, CDCl3): δ 7.31 (d, J = 8.4 Hz, 2H), 7.26 (d, J = 8.4 Hz, 2H),
6.37 (dd, J = 15.7, 1.3 Hz, 1H), 6.19 (dq, J = 15.7, 6.6 Hz, 1H), 1.86 (dd, J = 6.6, 1.5 Hz, 3H),
1.30 (s, 9H). 13C{1H} NMR (101 MHz, CDCl3): δ 149.8, 135.3, 130.9, 125.7, 125.5, 125.0, 34.6,
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