Palladium-Catalyzed sp2-sp3 Coupling of Chloromethylarenes with Allyltrimethoxysilane: Synthesis of Allyl Arenes

Article abstract of DOI:10.1021/acs.joc.7b00678

Palladium-catalyzed remote sp²-sp³ coupling reaction of chloromethylarenes with allyltrimethoxysilane is described in this work. The allylation reaction regioselectively occurred on the para-positions of 1-(chloromethyl)naphthalenes

Full text of DOI:10.1021/acs.joc.7b00678

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Note
Palladium-catalyzed sp2–sp3 coupling of chloromethylarenes
with allytrimethoxysilane: Synthesis of allyl arenes
Sheng Zhang, Jinfang Cai, Yoshinori Yamamoto, and Ming Bao
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 09 May 2017
Downloaded from http://pubs.acs.org on May 9, 2017
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Palladium-catalyzed sp2–sp3 coupling of chloromethylarenes with
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allytrimethoxysilane: Synthesis of allyl arenes
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Sheng Zhang,† Jinfang Cai,† Yoshinori Yamamoto,†,‡ and Ming Bao*†
†
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian
116023, China
‡ WPIꢀAIMR (WPIꢀAdvanced Institute for Materials Research), Tohoku University,
Sendai 980ꢀ8577, Japan
mingbao@dlut.edu.cn (M. Bao)
ABSTRACT: Palladiumꢀcatalyzed remote sp2–sp3 coupling reaction of
chloromethylarenes with allyltrimethoxysilane is described in this work. The allylation
reaction regioselectively occurred on the paraꢀpositions of 1ꢀ(chloromethyl)naphthalenes
and benzyl chlorides to form new C(sp2)–C(sp3) bonds. The reaction proceeds smoothly
under mild conditions to produce allyl arenes in moderate to excellent yields.
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The transition metalꢀcatalyzed crossꢀcoupling reaction between organometallic
reagents and organic halides or pseudoꢀhalides containing a C–X bond (X = I, Br, Cl, OTf,
OTs, etc.) is one of the most important carbon–carbon bondꢀforming methods in the
organic synthesis.1 Over the past decades, many kinds of organometallic reagents, such as
organomagnesiums,2 organozincs,3 organostannanes,4 organosilanes,5 organoboranes,6
and organobismuths,7 have been developed and applied for this purpose. Among
organometallic reagents utilized, organosilanes have attracted considerable attention
because of their commercial availability, relatively low toxicity, and high tolerance to
functional groups. New carbon–carbon bonds could be successfully constructed through
the palladiumꢀcatalyzed crossꢀcoupling between organosilanes and organic halides as
well as pseudoꢀhalides, namely the Hiyamacoupling, with different coupling patterns,
including sp–sp (between ethynylsilanes and ethynyl halides),8 sp–sp2 (between
ethynylsilanes and alkenyl halides),9 sp2–sp2 (between alkenylsilanes and aryl halides or
alkenyl halides),10 sp2–sp3 (between allylsilanes and aryl halides),11 and sp3–sp3 (between
allylsilanes and allyl acetates)12 coupling. Although the palladiumꢀcatalyzed
crossꢀcoupling reactions of allylsilanes with aryl halides and allyl acetates have been
widely applied for allylic functionalization of organic molecules, the crossꢀcoupling
reaction of allylsilanes with chloromethylarenes in the presence of palladium catalyst, to
the best of our knowledge, has not yet been reported so far. Recently, the palladium
nanoparticleꢀcatalyzed Hiyama coupling of benzyl halides with aryltrialkoxysilanes was
reported by Sarkar and coꢀworkers; the diarylmethanes were obtained in good to
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excellent yields.13 Our research on palladium catalysis showed that the
palladiumꢀcatalyzed sp3–sp3 coupling between allylsilanes and chloromethylarenes did
not occur at all; instead, a remote sp2–sp3 coupling reaction unexpectedly took place to
produce paraꢀallylated products (Scheme 1).14 The results are reported in this work.
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Scheme 1. Palladiumꢀcatalyzed remote crossꢀcoupling reaction of chloromethylarenes
with allysilanes.
sp3-sp3 coupling
Cl
R
cat. Pd
R
TBAF
+
sp2-sp3 coupling
Si(OMe)3
R
para-allylation
This Work
In the initial study, the crossꢀcoupling reactions of 1ꢀ(chloromethyl)naphthalene (1a)
with different allylsilane reagents including allyltrimethylsilane (2a),
allyltrimethoxysilane (2b), and allyltriethoxysilane (2c) were performed in the presence
of PdCl2(PPh3)2 as precatalyst and tetrabutylammonium fluoride (TBAF) as fluoride ion
source in tetrahydrofuran (THF) at room temperature for 12 h followed by the treatment
under acidic condition to investigate the reactivity of allylsilane reagents. The results
obtained indicated that the reactivity of 2b higher than that of others. Therefore, the
crossꢀcoupling reaction of 1a with 2b was selected to optimize the reaction conditions,
and the results are summarized in Table 1. The palladium catalyst was first screened using
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dichloromethane (DCM) as solvent and TBAF as fluoride ion source at room temperature.
The desired paraꢀallylated product 3a was isolated in the range of 26% to 76% yield
when the Pd(II) precatalysts [PdCl2(PPh3)2, PdCl2(OAc)2, Pd(acac)2, and PdCl2] were
examined in the absence or presence of PPh3 (entries 1–4). The yield of 3a could not be
improved by using Pd2(dba)3 as a precatalyst in the presence of PPh3 (entry 5, 68%). To
our delight, an excellent yield of 3a was achieved when Pd(PPh3)4 was employed as the
catalyst (entry 6, 92%). The solvent was subsquently screened using Pd(PPh3)4 as catalyst
and TBAF as fluoride ion source. Among the examined solvents, DCM proved to be the
best solvent (entry 6 vs. entries 7–9). A fluoride ionꢀcontaining additive is usually
necessary in the Hiyama reaction to activate organosilane reagents. Therefore, the
additive was finally screened by using the frequently used fluoride ion sources, including
TBAF,15 CsF,16 AgF,17 and KF/18ꢀcrownꢀ6.18 No reaction or low yield (13%) was
observed when CsF, AgF, and KF/18ꢀcrownꢀ6 were examined (entries 10–12); TBAF was
selected as the fluoride source because it provided the highest yield of 3a. It was found
that the yield of 3a decreased along with the decrease of Pd(PPh3)4 or TBAF loading
(entries 13 and 14). No reaction was observed in the absence of TBAF (entry 15).
Therefore, the subsequent crossꢀcoupling reactions of various chloromethylarenes with
allyltrimethoxysilane were conducted in the presence of Pd(PPh3)4 (10 mol%) and TBAF
(3.0 equiv.) in DCM solvent at room temperature.
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Table 1. Reaction Condition Screeninga
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entry
catalyst
solvent
DCM
additive
yield
(%)
76
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1
2
PdCl2(PPh3)2
TBAF
TBAF
TBAF
TBAF
TBAF
TBAF
TBAF
TBAF
TBAF
CsF
Pd(OAc)2/PPh3 DCM
Pd(acac)2/PPh3 DCM
53
3
37
4
PdCl2/PPh3
DCM
26
5
Pd2(dba)3/PPh3 DCM
68
6
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
DCM
THF
92
7
41
8
acetone
hexane
DCM
DCM
39
9
NRb
NRb
NRb
13
58c
61d
NRb
10
11
12
13
14
15
AgF
DCM KF/18ꢀcrownꢀ6
DCM
DCM
DCM
TBAF
TBAF
none
aReaction conditions: 1a (0.2 mmol), 2b (0.4 mmol), catalyst (10 mol%), additive (0.6 mmol), solvent
(3 mL), then TsOH·H2O (0.4 mmol). b1a was recovered. c Pd(PPh3)4 (5 mol%). dTBAF (0.4 mmol).
The crossꢀcoupling reactions of chloromethylarenes 1a–1r with allylsilane reagent 2b
were conducted under optimized conditions. The results are summarized in Table 2.
Reactions of 1ꢀ(chloromethyl)naphthalene substrates 1a–1e proceeded smoothly to
produce the paraꢀallylated products 3a–3e in moderate to excellent yields (entries 1–5,
60%–92%). Interestingly, the reactions of substrates 1c, 1d, and 1e took place on the
naphthalene ring, rather than on the benzene ring. It could be that this regioselectivity is
due to the lower resonance energy of the naphthalene ring compared with that of the
benzene ring (entries 3–5). The benzyl chloride substrates were then examined under the
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optimized conditions. Allyl benzene derivatives 3f–3j were obtained in range of 65% to
92% yields from the reactions of orthoꢀsubstituted benzyl chloride substrates 1f–1j
(entries 6–10). These results suggested that the electron property and steric hindrance of
orthoꢀsubstituent did not exert significant influence on reactivity. Halogen atoms (F, Cl,
and Br) linked to the benzene rings of substrates were notably maintained in the
structures of products 3d, 3e, 3g, and 3h, suggesting that further manipulation may
produce a more useful compounds.19 The substrates metaꢀmethyl benzyl chloride (1k),
metaꢀphenyl benzyl chloride (1l), and metaꢀallyl benzyl chloride (1m) underwent the
expected allylation reaction also smoothly to produce the paraꢀallylated benzene
derivatives 3k–3m in satisfactory to good yields (entries 11–13, 72%–88%). The product
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3m
having
two
adjacent
allyl
groups
could
be
converted
to
6ꢀmethylꢀ1,4ꢀdihydronaphthalene via rutheniumꢀcatalyzed metathesis reaction.20 The
reactivities of benzyl chloride substrates 1n–1p having two methyl groups linked on
benzene rings were subsequently investigated. The paraꢀallylated benzene derivatives
3n–3p were obtained in also satisfactory to good yields (entries 14–16, 73%–83%). The
allylated product 3q was obtained in 80% yield when the reaction mixture of
1ꢀ(chloromethyl)ꢀ2ꢀmethoxybenzene (1q) with a strong electronꢀdonating group (OMe)
and 2b was treated for a prolonged time under the optimal reaction conditions (entry 17).
The desired products 3r and 3s were also obtained in satisfactory yields (72% and 70%,
respectively) when the benzyl chloride substrates 1r and 1s bearing a strong
electronꢀwithdrawing group (CN or COOMe) on orthoꢀposition (entries 18 and 19). A
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moderate yield of 3t was observed when the substrate (chloromethylene)dibenzene (1t)
was employed in this type of coupling reaction (entry 20, 60%). The substrate
9ꢀ(chloromethyl)anthracene (1u) was finally examined, and the expected product
9ꢀallylꢀ10ꢀmethylanthracene (3u) was obtained in 65% yield (entry 21). All the new
products 3 were identified through their NMR and HRMS data as well as IR spectra.
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Table 2. Palladiumꢀcatalyzed regioselective allylation reaction between benzyl chlorides
and allytrimethoxysilanea
Entr
y
Substrate
1
Time
(h)
Product
3
Yield
(%)
1
2
3
12
12
14
92
78
85
1a
3a
1b
1c
3b
3c
Ph
4
14
69
1d
3d
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1e
3e
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6
18
18
18
12
18
18
12
18
79
76
82
92
65
72
77
88
1f
3f
7
1g
1h
1i
3g
3h
3i
8
9
10
11
12
13
1j
3j
1k
1l
3k
3l
1m
3m
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73
77
83
80
72
1n
1o
1p
1q
1r
3n
3o
3p
3q
3r
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Cl
CN
19
20
21
12
18
20
70
62
65
1s
1t
3s
3t
1u
3u
aReaction conditions: 1 (0.2 mmol), 2b (0.4 mmol), Pd(PPh3)4 (10 mol%), TBAF (0.6 mmol) in DCM
(3 mL), then TsOH·H2O (0.4 mmol).
Then, 1a was used as an electrophile to determine the scope of allylsilanes under the
optimized reaction conditions. The results are shown in Scheme 2. The reaction of 1a
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with (2ꢀmethylallyl)trimethoxysilane (2d) proceeded smoothly to produce the desired
product 4a in 88% yield (eq. 1). A 2.8/1 mixture of 4b and 4c was obtained in 70% total
yield when the crotyltrimethoxysilane (2e) was examined (eq. 2). These results indicated
that a substituted allylsilane reagent can also be employed in this type of allylation
reaction.
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Scheme 2. Palladiumꢀcatalyzed regioselective allylation reaction between
1ꢀ(chloromethyl)naphthalene and substituted allyltrimethoxysilanes
Control experiments were conducted to gain insights into the mechanism of this type of
allylation reaction (Scheme 3). Methyl group as a blocking group was placed in the para
position of the benzyl chloride. The reaction was also exclusively occurred at the
paraꢀposition to produce the dearomatization product 5 in 60% yield (eq. 1).
Dearomatization product 6 was successfully separated in 90% yield from the reaction of
1c with 2b in the absence of acid; the product 6 was subsequently transformed to more
stable rearomatized product 3c by acid treatment process (eq. 2).
Scheme 3. Control experiments.
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On the basis of our experimental outcomes and previous report,21 a plausible
mechanism for the remote sp2–sp3 coupling reaction is shown in Scheme 4.21 The
oxidative addition of 1a to a Pd(0) species would produce the η3ꢀallylpalladium chloride
intermediate A, which would undergo transmetalation with allyltrimethoxysilane in the
presence of TBAF to generate the intermediate B. Isomerization of intermediate B would
occur to produce intermediate C. Reductive elimination of intermediate C through
coupling of the Cꢀ3 terminus of the η1ꢀallyl ligand with the Cꢀ4 of the η3ꢀbenzyl ligand
would occur to produce the allylative dearomatization intermediate D and regenerating a
Pd(0) species. Finally, reꢀaromatization reaction of intermediate D would occur under
acidic conditions to produce paraꢀallylated naphthalene derivative 3a.
Scheme 4. A proposed mechanism.
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In summary, we have developed a new method for obtaining allyl aromatic compounds
using chloromethylarenes and allylsilanes as coupling partners. The palladiumꢀcatalyzed
remote sp2–sp3 coupling reaction proceeded smoothly under mild conditions to
exclusively produce paraꢀallylated aromatic compounds. This work represents a
significant expansion in the scope of the Hiyama reaction.
EXPERIMENTAL SECTION
General Information.
All reactions were carried out under a nitrogen atmosphere unless otherwise noted.
1
Solvents were purified by standard techniques without special instructions. H and 13C
NMR spectra were recorded on either a Varian Inovaꢀ400 spectrometer (400 MHz for 1H,
13
1
100 MHz for C) or a Bruker Avance IIꢀ400 spectrometer (400 MHz for H, 100 MHz
1
for 13C) or Bruker Avance IIIꢀ500 spectrometer (500 MHz for H, 125 MHz for 13C);
CDCl3 and TMS were used as a solvent and an internal standard, respectively. The
chemical shifts are reported in ppm downfield (δ) from TMS, the coupling constants J are
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given in Hz. The peak patterns are indicated as follows: s, singlet; d, doublet; t, triplet; q,
quartet; m, multiplet. IR spectra were recorded on a NEXUS FTꢀIR spectrometer. High
resolution mass spectra were recorded on a GCꢀTOF mass spectrometry. TLC was carried
out on SiO2 (silica gel 60 F254, Merck), and the spots were located with UV light,
iodoplatinate reagent or 1% aqueous KMnO4. Flash chromatography was carried out on
SiO2 (silica gel 60, 200ꢀ300 mesh). All the starting materials were commercially
available and used without further purification.
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Representative procedure for sp2–sp3 coupling of chloromethylarenes with
allytrimethoxysilane
1ꢀ(Chloromethyl)naphthalene (1a, 35.3 mg, 0.2 mmol), allyltrimethoxysilane (2b, 64.9
mg, 0.4 mmol), and TBAF (1.0 M in THF; 0.6 mL, 0.6 mmol) were added into a solution
of Pd(PPh3)4 (23.1 mg, 0.02 mmol) in dry dichloromethane (3.0 mL). After the reaction
mixture was stirred under N2 atmosphere at room temperature for 12 h, TsOH•H2O (76.1
mg, 0.4 mmol) was added and the mixture was stirred for 10 min to obtain a pure
paraꢀallylated benzene derivative. The solvent was removed under a reduced pressure.
The residue obtained was purified via silica gel chromatography (eluent: petroleum ether),
obtaining 92% yield (33.5 mg) of 1ꢀallylꢀ4ꢀmethylnaphthalene (3a) in the form of a
colorless oil.
1
1ꢀAllylꢀ4ꢀmethylnaphthalene (3a): colorless oil (33.5 mg, 92% yield). H NMR (CDCl3,
400 MHz) δ 8.04–7.98 (m, 2H), 4.49 (ddd, J = 8.4, 7.2, 4.4 Hz, 2H), 7.22 (dd, J = 9.6, 7.2
Hz, 2H), 6.13–6.06 (m, 1H), 5.09–5.05 (m, 2H), 3.79 (d, J = 6.0 Hz, 2H), 2.65 (s, 3H);
13C{1H}NMR (100 MHz, CDCl3) δ 137.4, 134.4, 133.1, 133.0, 132.1, 126.5, 125.5, 124.9,
124.7, 116.1, 37.4, 19.5; IR (neat) 3072, 3033, 2976, 1637, 1597, 1423, 912, 828, 750
cmꢀ1; HRMS (EI, m/z) calcd for C14H14: 182.1096 [M]+; found: 182.1104.
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4ꢀAllylꢀ1,2ꢀdimethylnaphthalene (3b): colorless oil (30.6 mg, 78% yield). H NMR
(CDCl3, 400 MHz) δ 8.00 (dd, J = 22.0, 8.4 Hz, 2H), 7.47–7.42 (m, 2H), 7.15 (s, 1H),
6.13–6.06 (m, 1H), 5.10–5.06 (m, 2H), 3.77 (d, J = 6.4 Hz, 2H), 2.56 (s, 3H), 2.44 (s, 1H);
13C{1H}NMR (100 MHz, CDCl3) δ 141.4, 139.0, 137.9, 137.7, 129.1, 128.8, 126.6, 126.2,
115.8, 41.7, 40.0, 18.6; IR (neat) 3073, 2975, 2864, 1638, 1514, 1382, 993, 911, 753 cmꢀ1;
HRMS (EI, m/z) calcd for C15H16: 196.1252 [M]+; found: 196.1256.
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1ꢀAllylꢀ4ꢀbenzylnaphthalene (3c): colorless oil (43.9 mg, 85% yield). H NMR (CDCl3,
400 MHz) δ 8.07 (dd, J = 17.6, 8.0 Hz, 2H), 7.54–7.46 (m, 2H), 7.33–7.20 (m, 7H),
6.20–6.13 (m, 1H), 5.17–5.13(m, 2H), 4.47 (s, 2H), 3.87 (d, J = 6.4 Hz, 2H);
13C{1H}NMR (100 MHz, CDCl3) δ 140.9, 137.2, 135.5, 135.2, 132.6, 128.9, 128.6, 127.3,
126.2, 125.8, 125.6, 125.1, 124.9, 116.3, 39.3, 37.5; IR (neat) 3078, 3020, 2976, 2853,
1638, 1497, 913, 755, 689 cmꢀ1; HRMS (EI, m/z) calcd for C20H18: 258.1409 [M]+; found:
258.1414.
1ꢀAllylꢀ4ꢀ(2'ꢀchlorobenzyl)naphthalene (3d): colorless oil (40.3 mg, 69% yield). 1H NMR
(CDCl3, 400 MHz) δ 8.05 (d, J = 8.0 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.49–7.39 (m,
3H), 7.25 (d, J = 8.8 Hz, 1H), 7.14–7.10 (m, 2H), 7.02 (ddd, J = 8.8, 7.6, 1.2 Hz, 1H),
6.84 (dd, J = 7.6, 1.2 Hz, 1H), 6.16–6.06 (m, 1H), 5.12–5.07 (m, 2H), 4.48 (s, 2H), 3.82
(d, J = 6.0 Hz, 2H); 13C{1H}NMR (100 MHz, CDCl3) δ 138.3, 137.1, 135.3, 134.2, 133.9,
132.5, 130.7, 129.4, 127.6, 127.1, 126.8, 126.1, 125.8, 125.6, 124.8, 116.2, 37.4, 36.4; IR
(neat) 3075, 3005, 2975, 1595, 1486, 1071, 914, 750 cmꢀ1; HRMS (EI, m/z) calcd for
C20H17Cl: 292.1019 [M]+; found: 292.1017.
1ꢀAllylꢀ4ꢀ(4'ꢀbromobenzyl)naphthalene (3e): colorless oil (40.3 mg, 60% yield). 1H NMR
(CDCl3, 400 MHz) δ 8.04 (d, J = 8.4 Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H), 7.45 (ddd, J =
21.2, 14.8, 7.2 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 7.2 Hz, 1H), 7.19 (d, J = 7.2
Hz, 1H), 7.02 (d, J = 8.4 Hz, 2H), 6.15–6.05 (m, 1H), 5.12–5.07 (m, 2H), 4.34 (s, 2H),
3.82 (d, J = 6.0 Hz, 2H); C{1H}NMR (100 MHz, CDCl3) δ 139.8, 137.0, 135.4, 134.7,
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131.5, 130.4, 127.3, 126.0, 125.8, 125.6, 124.8, 124.8, 119.9, 116.3, 38.6, 37.4; IR (neat)
3073, 3008, 2975, 1594, 1472, 1443, 1040, 914, 749 cmꢀ1; HRMS (EI, m/z) calcd for
C20H17Br: 336.0514 [M]+; found: 336.0518.
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4ꢀAllylꢀ1,2ꢀdimethylbenzene (3f): colorless oil (23.1 mg, 79% yield). H NMR (CDCl3,
400 MHz) δ 7.06 (d, J = 7.6 Hz, 1H), 6.97 (s, 1H), 6.93 (d, J = 7.6 Hz, 1H), 5.99–5.91 (m,
1H), 5.10–5.03 (m, 2H), 3.32 (d, J = 6.8 Hz, 2H), 2.24 (s, 3H), 2.23 (s, 3H);
13C{1H}NMR (100 MHz, CDCl3) δ 137.9, 137.5, 136.6, 134.2, 130.0, 129.7, 126.0, 115.5,
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39.9, 19.8, 19.4; IR (neat) 2916, 2849, 1735, 1658, 1576, 1468, 1384, 1132 cmꢀ1; HRMS
(EI) calcd for C11H14: 146.1096 [M]+; found: 146.1090.
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4ꢀAllylꢀ2ꢀfluoroꢀ1ꢀmethylbenzene (3g): colorless oil (22.8 mg, 76% yield). H NMR
(CDCl3, 400 MHz) δ 7.10–7.06 (m, 1H), 6.86–6.82 (m, 2H), 5.98–5.88 (m, 1H),
5.10–5.06 (m, 2H), 3.33 (d, J = 6.4 Hz, 2H), 2.23 (s, 3H); 13C{1H}NMR (100 MHz,
CDCl3) δ 161.3 (d, J = 242.9 Hz), 139.7 (d, J = 7.2 Hz), 136.9, 131.2 (d, J = 5.4 Hz),
123.9 (d, J = 3.2 Hz), 122.3 (d, J = 17.2 Hz), 116.1, 115.0 (d, J = 21.8 Hz), 39.6 (d, J =
1.5 Hz), 14.2 (d, J = 3.5 Hz); IR (neat) 3080, 3026, 2926, 1578, 1508, 1422, 1253, 1116,
996, 816 cmꢀ1; HRMS (EI, m/z) calcd for C10H11F: 150.0845 [M]+; found: 150.0843.
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4ꢀAllylꢀ2ꢀchloroꢀ1ꢀmethylbenzene (3h): colorless oil (27.2 mg, 82% yield). H NMR
(CDCl3, 400 MHz) δ 7.20–7.13 (m, 2H), 6.99 (dd, J = 7.6, 1.2 Hz, 1H), 6.00–5.89 (m,
1H), 5.12–5.08 (m, 2H), 3.34 (d, J = 6.4 Hz, 2H), 2.36 (s, 3H); 13C{1H}NMR (100 MHz,
CDCl3) δ 139.4, 137.0, 134.0, 131.0, 129.2, 127.0, 116.3, 39.5, 19.7; IR (neat) 3077,2978,
2923,1639, 1493, 1437, 1051,916, 815cmꢀ1; HRMS (EI, m/z) calcd for C10H11Cl:
166.0549 [M]+; found: 166.0557.
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4ꢀAallylꢀ2ꢀphenylꢀ1ꢀmethylbenzene (3i): colorless oil (38.3 mg, 92% yield). H NMR
(CDCl3, 400 MHz) δ 7.42–7.39 (m, 2H), 7.35–7.31 (m, 3H), 7.20 (d, J = 7.6 Hz, 1H),
7.10–7.07 (m, 2H), 6.02–5.95 (m, 1H), 5.12–5.04 (m, 2H), 3.39 (d, J = 6.4 Hz，2H), 2.24
(s, 3H); 13C{1H}NMR (100 MHz, CDCl3) δ 142.0, 141.9, 137.5, 134.6, 133.0, 130.4,
130.0, 129.2, 128.0, 127.4, 126.7, 115.8, 39.8, 20.0; IR (neat) 3056, 2923, 2854, 1638,
1486, 1441, 913, 701 cmꢀ1; HRMS (EI, m/z) calcd for C16H16: 208.1252 [M]+; found:
208.1258.
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4ꢀAllylꢀ1ꢀmethylꢀ2ꢀ(phenylethynyl)benzene (3j): colorless oil (30.2 mg, 65% yield). H
NMR (CDCl3, 400 MHz) δ 7.53–7.51 (m, 2H), 7.33–7.30 (m, 4H), 7.14 (d, J = 7.6 Hz,
1H), 7.04 (dd, J = 8.0 , 1.6 Hz, 1H), 5.98–5.89 (m, 1H), 5.10–5.05 (m, 2H), 3.33 (d, J =
7.2 Hz, 2H), 2.47 (s, 3H); 13C{1H}NMR (100 MHz, CDCl3) δ 138.0, 137.5, 137.4, 132.1,
131.7, 129.7, 128.9, 128.5, 128.3, 123.8, 123.2, 116.1, 93.3, 88.7, 39.7, 20.4; IR (neat)
3423, 3073, 2976, 1638, 1597, 1494, 914, 754 cmꢀ1; HRMS (EI, m/z) calcd for C18H16:
232.1252 [M]+; found: 232.1247.
4ꢀAllylꢀ1,3ꢀdimethylbenzene (3k)22: Colorless oil (21.0 mg, 72% yield). 1H NMR (CDCl3,
400 MHz) δ 7.02 (d, J = 7.2 Hz, 1H), 6.96–6.94 (m, 2H), 5.98–5.88 (m, 1H), 5.04–4.96
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(m, 2H), 3.32 (d, J = 6.0 Hz, 2H), 2.28 (s, 3H), 2.25 (s, 3H); C{1H}NMR (100 MHz,
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CDCl3) δ 136.9, 136.2, 135.8, 135.1, 131.0, 129.1, 126.7, 115.4, 37.4, 20.9, 19.3.
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4ꢀAllylꢀ3ꢀphenylꢀ1ꢀmethylbenzene (3l): colorless oil (32.1 mg, 77% yield). H NMR
(CDCl3, 400 MHz) δ 7.40–7.36 (m, 2H), 7.34–7.29 (m, 3H), 7.18 (d, J = 8.0 Hz, 1H),
7.12 (dd, J = 8.0, 1.6 Hz, 1H), 7.07 (s, 1H), 5.90–5.83 (m, 1H), 5.00–4.88 (m, 2H), 4.29
(d, J = 6.4 Hz, 2H), 2.35 (s, 3H); 13C{1H}NMR (100 MHz, CDCl3) δ 141.8, 141.7, 138.0,
135.6, 134.2, 130.8, 129.7, 129.2, 128.2, 128.0, 126.8, 115.5, 37.1, 21.0; IR (neat) 3058,
2919, 2837, 1637, 1487, 912, 823, 701 cmꢀ1; HRMS (EI, m/z) calcd for C16H16: 208.1252
[M]+; found: 208.1250.
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1,2ꢀDiallylꢀ4ꢀmethylbenzene (3m): colorless oil (30.3 mg, 88% yield). H NMR (CDCl3,
400 MHz) δ 7.05–6.97 (m, 3H), 6.00–5.90 (m, 2H), 5.09–4.96 (m, 4H), 3.36–3.34 (m,
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4H), 3.00 (s, 3H); C{1H}NMR (100 MHz, CDCl3) δ 137.8, 137.4, 137.2, 135.9, 134.9,
130.3, 129.5, 127.2, 115.6, 115.5, 37.1, 36.7, 21.0; IR (neat) 3003, 2955, 2923, 2853,
1637, 1457, 911, 823 cmꢀ1; HRMS (EI, m/z) calcd for C13H16: 172.1252 [M]+; found:
172.1254.
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2ꢀAllylꢀ1,3,5ꢀtrimethylbenzene (3n)23: colorless oil (23.4 mg, 73% yield). H NMR
(CDCl3, 400 MHz) δ 6.91 (s, 1H), 6.90 (s, 1H), 5.96–5.87 (m, 1H), 5.04–4.96 (m, 2H),
3.30 (d, J = 6.4 Hz, 2H), 2.22 (s, 3H), 2.20 (s, 6H).
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3ꢀAllylꢀ2,4,5ꢀtrimethylbenzene (3o)24: colorless oil (24.6 mg, 77% yield). H NMR
(CDCl3, 400 MHz) δ 6.87 (s, 2H), 5.94–5.88 (m, 1H), 5.02–4.87 (m, 2H), 3.39 (d, J = 5.6
Hz, 2H), 2.32 (s, 3H), 2.31 (s, 3H), 2.29 (s, 3H).
5ꢀAllylꢀ1,2,3ꢀtrimethylbenzene (3p): colorless oil (26.5 mg, 83% yield). 1H NMR (CDCl3,
400 MHz) δ 6.84 (s, 2H), 5.99–5.89 (m, 1H), 5.10–5.02 (m, 2H), 3.28 (d, J = 6.8 Hz, 2H),
2.25 (s, 6H), 2.13 (s, 3H); 13C{1H}NMR (100 MHz, CDCl3) δ 138.0, 136.9, 136.5, 132.7,
127.8, 115.4, 39.9, 20.6, 15.0; IR (neat) 3077, 2924, 2853, 1639, 1485, 1460, 1377, 993,
911, 858 cmꢀ1; HRMS (EI) calcd for C12H16: 160.1252 [M]+; found: 160.1256.
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4ꢀAllylꢀ2ꢀmethoxyꢀ1ꢀmethylbenzene (3q): colorless oil (26.0 mg, 80% yield). H NMR
(CDCl3, 500 MHz) δ 7.05 (d, J = 7.5 Hz, 1H), 6.69 (d, J = 7.5 Hz, 1H), 6.66 (s, 1H),
6.01–5.93 (m, 1H), 5.11–5.05 (m, 2H), 3.82 (s, 3H), 3.36 (d, J = 7.0 Hz, 2H), 2.18 (s, 3H);
13C{1H}NMR (125 MHz, CDCl3) δ 157.7, 138.9, 137.7, 130.5, 124.2, 120.3, 115.6, 110.4,
55.2, 40.3, 15.8; IR (neat) 3077, 3001, 2923, 2834, 1638, 1613, 1584, 1509, 1465, 1414,
1255, 1133, 1043, 995, 913, 813, 747 cmꢀ1; HRMS (EI) calcd for C11H14O: 162.1045
[M]+; found: 162.1043.
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5ꢀAllylꢀ2ꢀmethylbenzonitrile (3r): colorless oil (22.6 mg, 72% yield). H NMR (CDCl3,
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400 MHz) δ 7.42 (d, J = 1.6 Hz, 1H), 7.30 (dd, J = 8.0, 1.6 Hz, 1H), 7.23 (d, J = 7.6 Hz,
1H), 5.96–5.86 (m, 1H), 5.14–5.06 (m, 2H), 3.37 (d, J = 6.8 Hz, 2H), 2.51 (s, 3H);
13C{1H}NMR (125 MHz, CDCl3) δ 139.6, 138.3, 136.1, 133.1, 132.4, 130.3, 118.3, 116.9,
112.7, 39.1, 20.0; IR (neat) 3079, 2920, 2226, 1639, 1418, 1436, 1384, 1288, 995, 918,
829, 766, 478 cmꢀ1; HRMS (EI) calcd for C11H11N: 157.0891 [M]+; found: 157.0891.
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Methyl 5ꢀallylꢀ2ꢀmethylbenzoate (3s): colorless oil (26.6 mg, 70% yield). H NMR
(CDCl3, 400 MHz) δ 7.73 (d, J = 1.6 Hz, 1H), 7.22 (dd, J = 7.6, 1.6 Hz, 1H), 7.17 (d, J =
7.6 Hz, 1H), 6.00–5.90 (m, 1H), 5.10–5.06 (m, 2H), 3.88 (s, 3H), 3.38 (d, J = 6.8 Hz, 2H),
2.56 (s, 3H); 13C{1H}NMR (125 MHz, CDCl3) δ 168.2, 137.9, 137.5, 137.0, 132.3, 131.8,
130.6, 129.5, 116.1, 51.8, 39.5, 21.3; IR (neat) 3079, 2978, 2951, 2929, 2848, 2226, 1724,
1499, 1435, 1298, 1260, 1197, 1082, 994, 916, 785 cmꢀ1; HRMS (EI) calcd for C12H14O2:
190.0994 [M]+; found: 190.0990.
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1ꢀAllylꢀ4ꢀbenzylbenzene (3t): colorless oil (25.8 mg, 62% yield). H NMR (CDCl3, 400
MHz) δ 7.26–7.24 (m, 2H), 7.18–7.16 (m, 2H), 7.10 (m, 3H), 5.99–5.89 (m, 1H),
5.08–5.02 (m, 2H), 3.94 (s, 2H), 3.34 (d, J = 6.4 Hz, 2H); 13C{1H}NMR (100 MHz,
CDCl3) δ 137.5, 133.6, 133.0, 130.9, 129.8, 125.5, 124.6, 124.5, 124.5, 116.1, 37.4, 20.9;
IR (neat) 3082, 3025, 2977, 2849, 1638, 1511, 1494, 913, 697cmꢀ1; HRMS (EI, m/z)
calcd for C16H16: 208.1252 [M]+; found: 208.1256.
9ꢀAllylꢀ10ꢀmethylanthracene (3u): green solid (30.2 mg, 65% yield), mp 98.3–99.2 ºC.
1H NMR (CDCl3, 400 MHz) δ 8.39–8.36 (m, 2H), 8.32–8.28 (m, 2H), 7.57–7.53 (m, 4H),
6.31–6.21 (m, 1H), 5.13–4.97 (m, 2H), 4.40 (dd, J = 4.0, 2.0 Hz, 2H), 3.14 (s, 3H);
13C{1H}NMR (100 MHz, CDCl3) δ 136.7, 130.1, 129.8, 125.5, 125.2, 125.1, 124.8, 116.0,
32.1, 14.3; IR (KBr) 3073, 2975, 2869, 1637, 1443, 917, 745 cmꢀ1; HRMS (EI, m/z) calcd
for C18H16: 232.1252 [M]+; found: 232.1254.
1ꢀMethylꢀ4ꢀ(2ꢀmethylallyl)naphthalene (4a): colorless oil (34.5 mg, 88% yield). 1H NMR
(CDCl3, 500 MHz) δ 8.03–8.00 (m, 2H), 7.51–7.46 (m, 2H), 7.24–7.21 (m, 2H), 4.84 (s,
1H), 4.62 (s, 1H), 3.75 (s, 2H), 2.67 (s, 3H), 1.77 (s, 3H); 13C{1H}NMR (125 MHz,
CDCl3) δ 144.9, 133.9, 133.0, 132.5, 126.9, 126.3, 125.34, 125.30, 124.9, 124.7, 112.1,
41.6, 22.8, 19.5; IR (neat) 3071, 2968, 3035, 2930, 1650, 1597, 1515, 1443, 1393, 1022,
889, 817, 797, 749 cmꢀ1; HRMS (EI) calcd for C15H16: 196.1252 [M]+; found: 196.1254.
(E)ꢀ1ꢀ(Butꢀ2ꢀenꢀ1ꢀyl)ꢀ4ꢀmethylnaphthalene
(4b)
and
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1ꢀ(butꢀ3ꢀenꢀ2ꢀyl)ꢀ4ꢀmethylnaphthalene (4c): colorless oil (27.5 mg, 70% yield). H NMR
(CDCl3, 500 MHz) δ for 4b 8.05–7.24 (m, 6H), 5.68–5.59 (m, 2H), 3.81 (d, J = 5.5 Hz,
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2H), 2.67 (s, 3H), 1.80 (d, J = 6.0 Hz, 3H); for 4c 8.16–7.24 (m, 6H), 6.18–6.12 (m, 1H),
5.13–5.09 (m, 2H), 4.29–4.26 (m, 1H), 2.67 (s, 3H), 1.50 (d, J = 7.0 Hz, 3H).
3ꢀAllylꢀ3ꢀmethylꢀ6ꢀmethylenecyclohexaꢀ1,4ꢀdiene (5)14b: colorless oil (17.5 mg, 60%
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yield). H NMR (400 MHz, CDCl3) δ 6.19 (d, J = 9.6 Hz, 2H), 5.62–5.74 (m, 3H),
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4.97–5.01 (m, 2H), 4.81 (s, 2H), 2.14 (d, J = 7.2 Hz, 2H), 1.10 (s, 3H).
(E)ꢀ1ꢀAllylꢀ4ꢀbenzylideneꢀ1,4ꢀdihydronaphthalene (6)14a: colorless oil (46.5 mg, 90%
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yield). H NMR (CDCl3, 400 MHz) δ for 7.85–7.83 (m, 1H), 7.41–7.34 (m, 4H),
7.28–7.24 (m, 4H), 7.14 (s, 1H), 6.95 (d, J = 10.0 Hz, 1H), 6.13–6.08 (m, 1H), 5.80–5.70
(m, 1H), 5.02–4.98 (m, 2H), 3.69–3.65 (m, 1H), 2.56–2.40 (m, 2H).
ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China (No. 21372035,
21573032, and 21602026) and the China Postdoctoral Science Foundation (No.
2016M590226) for financial support.
SUPPORTING INFORMATION
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Copies of H and C{1H}NMR spectra. This material is available free of charge via
the Internet at http://pubs.acs.org.
REFERENCES
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(14) Similar results were observed in the palladiumꢀcatalyzed crossꢀcoupling of benzyl
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Bao, M. Tetrahedron 2010, 66, 6013–6018; (b) Bao, M.; Nakamura, H.; Yamamoto,
Y. J. Am. Chem. Soc. 2001, 123, 759–760. Palladiumꢀcatalyzed carboxylative
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