Silver-catalyzed benzylation and allylation of tertiary alkyl bromides with organozinc reagents

Article abstract of DOI:10.1002/asia.201000068

Silver salts catalyze the benzylation and allylation of tertiary alkyl bromides with organozinc reagents. The reactions create quaternary carbon centers efficiently. Treatment of gem-dibromoalkanes with benzylic or allylic zinc reagents under silver catalysis leads to dibenzylation or diallylation. The functional-group compatibility of the present reactions is wider than that of the previous reactions with Grignard reagents.

Full text of DOI:10.1002/asia.201000068

DOI: 10.1002/asia.201000068
Silver-Catalyzed Benzylation and Allylation of Tertiary Alkyl Bromides with
Organozinc Reagents
Yukihiro Mitamura, Yoshihiro Asada, Kei Murakami, Hidenori Someya,
Hideki Yorimitsu,* and Koichiro Oshima*[a]
Abstract: Silver salts catalyze the benzylation and allylation of tertiary alkyl bro-
mides with organozinc reagents. The reactions create quaternary carbon centers ef-
Keywords: alkyl halides · allylation ·
ficiently. Treatment of gem-dibromoalkanes with benzylic or allylic zinc reagents
benzylation · organozinc reagents ·
under silver catalysis leads to dibenzylation or diallylation. The functional-group
silver
compatibility of the present reactions is wider than that of the previous reactions
with Grignard reagents.
Introduction
by organometallic species directly[5] or after undergoing rad-
ical addition to alkenes.[6]
Creating quaternary carbon centers[1] poses a significant
challenge in organic synthesis,[2] and new synthetic ap-
proaches have to be developed. The most popular ionic pro-
cess that generates quaternary carbon atoms has been the
reactions of tertiary alkyl metals with carbon electrophiles.
On the other hand, examples of the polarity-inversed pro-
cess, nucleophilic substitution reactions at tertiary carbon
atoms bearing a suitable leaving group with organometallic
reagents, are relatively rare because b-elimination usually
competes.
Classical nucleophilic substitution reactions of tertiary
alkyl halides with organometallic reagents utilizes stoichio-
metric amounts of Lewis acidic organometallic reagents,
such as organoaluminums and organotitaniums.[3] Recently,
a Group 13 metal was proven to catalyze the reaction of ter-
tiary alkyl halides with organosilicon reagents.[3c,4] Another
approach to quaternary carbon atoms from tertiary alkyl
halides and organometallic reagents employs a single-elec-
tron transfer process to generate the corresponding tertiary
alkyl radical and halide anion.[5,6] The radicals are trapped
We have been interested in the catalytic activities of
silver[7,8] and copper[9,10] salts in the reactions of tertiary
alkyl halides with Grignard reagents. Notably, silver salts
have been proven to catalyze the benzylation and allylation
of tertiary alkyl halides with benzylic and allylic Grignard
reagents.[7a,c] The reactions offer a highly efficient access to
quaternary carbon centers. However, the use of Grignard re-
agents leads to poor functional-group compatibility. Here
we report that benzylic and allylic zinc reagents are also ef-
fective for the silver-catalyzed reaction with better function-
al-group compatibility.
Results and Discussion
Benzylation of tertiary alkyl bromides: The reaction of tert-
butyl bromide with benzylzinc chloride·lithium chloride
complex[11] was performed, and the effects of solvents and
silver salts were surveyed (Table 1). In the absence of a
silver salt, the reaction in acetonitrile did not proceed
(Table 1, entry 1). Silver halides promoted the benzylation
sluggishly (entries 2 and 3). Highly cationic silver salts were
effective to yield neopentylbenzene in good yields (en-
tries 4–7). Among them, silver trifluoromethanesulfonate
showed the highest catalytic activity. Although the choice of
solvent was not critical, acetonitrile proved to be the best
(entries 7–11).
[a] Y. Mitamura, Y. Asada, K. Murakami, H. Someya,
Prof. Dr. H. Yorimitsu, Prof. Dr. K. Oshima
Department of Material Chemistry
Graduate School of Engineering,
Kyoto University
Kyoto-daigaku Katsura, Nishikyo, Kyoto 615-8510 (Japan)
Fax : (+81)75-383-2438
E-mail: yori@orgrxn.mbox.media.kyoto-u.ac.jp
oshima@orgrxn.mbox.media.kyoto-u.ac.jp
The use of the zinc reagent complexed with lithium chlo-
ride was essential (Table 2). The reaction of 2-methyl-2-bro-
modecane (1a) with benzylzinc bromide, conventionally pre-
Chem. Asian J. 2010, 5, 1487 – 1493
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FULL PAPERS
Table 1. Benzylation.
benzylzinc bromide prior to the benzylation changed the re-
activity of the benzylzinc reagent and 2a was obtained in
25% yield (entry 2). When benzylzinc bromide·lithium chlo-
ride complex was prepared from benzyl bromide, zinc
powder, and lithium chloride according to Knochelꢁs proce-
dure,[11] the yield of 2a was improved up to 48% (entry 3).
Benzylzinc chloride·lithium chloride complex showed the
highest reactivity affording 2a in 81% yield without forming
3 and 4 (entry 4). It is worth noting that the benzylzinc
chloride·lithium chloride complex is less basic than the con-
ventional benzylzinc bromide and did not react with 1a in
the absence of AgOTf.
Entry
Ag salt
Solvent
Yield [%]
1
none
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CH2CN
THF
0
11
24
44
59
58
64
50
37
33
47
2
AgBr
3
AgCl
4
5
6
7
8
9
10
11
AgOAc
AgNO3
AgBF4
AgOTf
AgOTf
AgOTf
AgOTf
AgOTf
The scope of the alkyl halides is summarized in Table 3.
Cyclic tertiary alkyl bromide 1b underwent benzylation effi-
ciently (Table 3, entry 2). Functional groups, such as me-
1,4-dioxane
DMF
Table 2. Choice of benzylzinc reagent.
Table 3. Scope of alkyl halides in the benzylation reaction.
À
R X
Entry
1
1
2
Yield [%]
81
1a
2a
Entry Benzylzinc
1
Yield 2a [%] Yield 3 [%] Yield 4 [%]
2
3
4
1b
1c
1d
2b
2c
2d
78
79
68
0
25
48
63
17
12
26
9
2
3
8
5
1e
1 f
2e
2 f
90
82
4
81
0
0
6[a]
pared from benzyl bromide and zinc powder in the absence
of lithium chloride, failed to afford the corresponding prod-
uct 2a (Table 2, entry 1). Dehydrobromination took place to
yield 2-methyl-2-decene (3) and 2-methyl-1-decene (4). We
confirmed that the dehydrobromination also occurred in the
absence of AgOTf. These results indicate that the conven-
tional benzylzinc bromide is too basic to coexist with 1a. In-
terestingly, an addition of lithium chloride to a solution of
7[b]
8[c]
1g
1h
2g
2h
3
57
[a] AgOAc was used instead of AgOTf. [b] Performed for 1.5 h. [c] Per-
formed with 2.0 equiv of the benzylzinc reagent for 24 h.
thoxy, fluoro, and benzoyloxy groups were compatible under
the reaction conditions (entries 4–6). Unfortunately, 1-bro-
moadamantane (1g) failed to undergo the benzylation
(entry 7). Secondary alkyl bromide was less reactive, and
the reaction of 2-bromooctane (1h) with 2.0 equivalents of
the benzylzinc reagent required 24 h to complete (entry 8).
Tertiary alkyl chlorides were completely unreactive. Tertiary
alkyl iodides were smoothly converted to the corresponding
alkenes by dehydroiodination.
Abstract in Japanese:
Other benzylic zinc reagents were applicable to the reac-
tion (Table 4). Sterically demanding benzylic zinc reagents
showed moderate reactivities, requiring a longer reaction
time (Table 4, entries 2 and 3). Vinyl, methoxy, and bromo
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Tertiary Alkyl Bromides
Table 4. Benzylic zinc reagents.
stance, an ester group reacted smoothly with allylzinc chlori-
de·lithium chloride complex.
Dibenzylation and diallylation of gem-dibromoalkanes:
Geminal dihaloalkanes are readily available, easy to handle,
and reactive under proper reaction conditions, and hence
represent a useful class of compounds in organic synthesis.[12]
According to our previous report,[7c] we expected that gem-
dibromoalkanes would undergo successive silver-catalyzed
dibenzylation or diallylation with organozinc reagents to
create quaternary carbon centers. The reactions indeed oc-
curred with 2.5 mol% of silver acetate and 4.0 equivalents
of organozinc reagents.
Entry
R
t [h]
3
Yield [%]
1
2
3
4
5
6
7
8
9
4-Me
2-Me
(1-naphthyl)
4-vinyl
3-MeO
3-Br
4-F
3-COOEt
3-CN
3
6
6
3
3
6
6
3
3
3a
3b
3c
3d
3e
3 f
3g
3h
3i
81
57
60
61
68
64
23[a]
4
5
The dibenzylation proceeded in acetonitrile with moder-
ate efficiency (Table 6). Major byproducts could not be fully
identified. However, the byproducts seemed to result from a
failure in the second benzylation reaction according to
[a] Performed with 2.0 equiv of the benzylic zinc reagent.
groups were compatible under the reaction conditions (en-
tries 4–6). However, benzylic zinc reagents bearing an elec-
tron-withdrawing group were much less reactive (entries 7–
9).
Table 6. Dibenzylation of gem-dibromoalkanes with
a
benzylzinc re-
agent.
Allylation of tertiary alkyl bromides: We next exploited the
silver-catalyzed allylation reaction with allylic zinc reagents.
However, an attempted silver-catalyzed allylation in acetoni-
trile failed to afford the corresponding allylated product.
After some investigation, we found that the desired allyla-
tion reaction proceeded smoothly in THF (Table 5, entry 1).
The conditions are applicable to methallylation, crotylation,
and prenylation (entries 2–4). Unfortunately, the crotylation
and prenylation afforded mixtures of regioisomers in moder-
ate yields. Because of the high reactivity of allylic zinc re-
agents, functional-group compatibility is narrow. For in-
Entry
R
5
6
Yield [%]
1
2
5a
5b
6a
6b
46
51
3
4
5c
5d
6c
6d
36
50
Table 5. Tertiary alkyl bromides with allylic zinc reagents.
5
6
5e
5 f
6e
6 f
46
47
Entry
1
1
Allylic zinc reagent
4
Yield [%]
96
1a
NMR spectroscopic and mass spectrometric analyses of the
crude reaction mixture.[13] Functional-group compatibility is
as high as expected: siloxy, ester, amide, bulky ketone, and
cyano moieties survived under the reaction conditions. The
scope of the dibenzylation with the zinc reagent is wider
than that of the dibenzylation with benzylmagnesium, al-
though the yields are lower.[7c]
2
3
1a
1a
90
66
4c/4d 63:37
The diallylation in THF afforded the corresponding 1,6-
heptadienes in higher yields (Table 7) than the dibenzyla-
tion. The allylzinc reagent may be more reactive than the
benzylzinc reagent, thus undergoing the second allylation
more efficiently. On the other hand, the carbonyl group of
5e and the cyano group of 5 f reacted with the allylzinc re-
agent, which shows the lower functional-group compatibility.
The products will be able to undergo ring-closing metathe-
42
4
5
1a
1e
4e/4 f 71:29
86
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H. Yorimitsu, K. Oshima et al.
FULL PAPERS
Table 7. Diallylation of gem-dibromoalkanes with an allylzinc reagent.
effect benzylation (Table 8). A reaction mixture prepared
from equimolar amounts of AgOAc and benzylzinc chlori-
de·lithium chloride failed to promote the benzylation reac-
Table 8. Reaction of 1a with benzylsilver reagents.
Entry
R
5
t [h]
5
7
Yield [%]
1
2
5a
5b
7a
7b
58
66
6
Entry
X [mmol]
2a [%]
1a [%]
Diphenylethane [mmol]
3
4
5c
5d
4
4
7c
7d
62
69
1
2
3
4
0.30
0.60
0.90
1.20
6
40
0
0
0.13
0.14
0.15
0.15
84
93
96
0
5[a]
6[a]
5g
5h
3
3
7e
7 f
72
66
tion of 1a and afforded considerable amounts of dehydro-
bromination products 3 and 4 (Table 8, entry 1). In contrast,
a 1:2 mixture of AgOAc and the benzylzinc reagent was
highly reactive to yield 2a in an 84% yield (entry 2). Three
or four equivalents of the benzylzinc reagent did not im-
prove the efficiency significantly (entries 3 and 4).
[a] AgOTf was used.
sis[14] to form cyclopentene derivatives and hence serve as
useful intermediates in organic synthesis.
We propose a draft mechanism as shown in Scheme 1, for
which an electron-rich silver–ate complex promotes single-
electron transfer to the tertiary alkyl halide as cobalt- and
manganese–ate complexes do.[16] Formation of the silver(0)–
ate complex initially takes place (Scheme 1, step A). The ate
complex effects single-electron transfer to the tertiary alkyl
halide to form the corresponding tertiary alkyl radical
(step B). The radical is trapped by benzyl- or allylsilver(I) to
yield the oxidative adduct (step C). Reductive elimination
gives the coupling product (step D), and the initial silver–
ate complex is regenerated by the action of the remaining
organozinc reagent (step E).
The mechanistic study on silver-catalyzed reactions by
Tamura and Kochi is also worth noting (Scheme 2).[8a,17] Ac-
cording to their study, organozinc initially reduces monova-
lent silver to zerovalent silver (Scheme 2, step F). Single-
electron transfer from the naked silver to tertiary alkyl bro-
mide takes place to form the corresponding alkyl radical R’
and silver bromide (step G). The radical is trapped by an-
other zerovalent silver to form alkylsilver R’Ag (step H).
The silver bromide reacts with organozinc RZnCl·LiCl to
yield benzyl- or allylsilver RAg (step I). Reductive coupling
Possible reaction mechanisms: In general, a nucleophilic
substitution reaction of tertiary alkyl halide proceeds
through an SN1 process. In the present reactions, a coopera-
tive Lewis acid catalysis of silver and zinc can promote the
formation of the corresponding tertiary carbocation, which
reacts with a benzylic or allylic metal. Similar mechanisms
are proposed in the literature.[4]
Alternatively, we can consider that the zinc reagents
would initially reduce the silver salt to an electron-rich
silver species, which can play an important role in the reac-
tion. Treatment of AgOAc (0.30 mmol) with benzylzinc
chloride·lithium chloride complex (0.90 mmol) in acetoni-
trile at 258C for 30 min afforded 1,2-diphenylethane
(0.13 mmol) [Eq. (1)]. The formation of diphenylethane, the
amount of which is roughly equal to a half of AgOAc used,
indicates that AgI would be reduced to Ag0. In addition, a
silver mirror did not appear inside the reaction flask. We
are thus tempted to propose the formation of a benzylic
silver(0)–ate complex[15] [Eq. (2)].
Although the number of the benzyl groups on the silver
atom of the benzylic silver is not clear, the following experi-
ments revealed that monobenzylsilver is reactive enough to
Scheme 1. On the basis of our study. (R=benzyl or allyl, R’=tertiary
alkyl).
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Tertiary Alkyl Bromides
performed on commercial glass plates bearing a 0.25 mm layer of Merck
Silica gel 60F254. Silica gel (Wakogel 200 mesh) was used for column
chromatography. Elemental analyses were carried out at the Elemental
Analysis Center of Kyoto University.
Unless otherwise noted, materials obtained from commercial suppliers
were used without further purification. AgOTf and AgOAc were pur-
chased from Aldrich and were handled under argon. Benzylic and allylic
zinc reagents were prepared according to the literature.[11] Acetonitrile
was dried over molecular sieves 3 ꢂ. THF was purchased from Kanto
Chemical, stored under nitrogen, and used as it is. All reactions were car-
ried out under an argon atmosphere. Tertiary alkyl bromides were pre-
pared by bromination of the corresponding tertiary alcohols with phos-
phorus tribromide in ether at À208C. gem-Dibromoalkanes were pre-
pared from ketones via the hydrazones.[20]
Scheme 2. On the basis of the study by Tamura and Kochi. (R=benzyl or
allyl, R’=tertiary alkyl).
Typical procedure for the benzylation or allylation of tertiary alkyl bro-
mide: The reaction of 2-bromo-2-methyldecane (1a) is representative
(Table 3, entry 1). AgOTf (13 mg, 0.050 mmol) was placed in a 20 mL re-
action flask under argon and then acetonitrile (2.0 mL) and benzylzinc
chloride·lithium chloride complex (0.79m in THF, 1.52 mL, 1.2 mmol)
were sequentially added. The resulting mixture was stirred for 5 min and
then alkyl bromide 1a (0.24 g, 1.0 mmol) was added. The whole mixture
was stirred for 3 h at 258C. The reaction was quenched with saturated
ammonium chloride solution. Organic compounds were extracted with
ether (10 mLꢃ3). The combined organic phase was dried over anhydrous
sodium sulfate and concentrated. Silica-gel column purification (hexane)
afforded 2,2-dimethyl-1-phenyldecane (2a, 0.20 g, 0.81 mmol, 81%).
of the benzyl- or allylsilver with the alkyl silver affords the
product R,R’ and regenerates zerovalent silver (step J), al-
though the exact mechanism of the reductive coupling is not
clear.
The mechanism of the reaction of gem-dibromoalkane is
also unclear. However, we confirmed that the dibenzylation
consists of
a couple of nucleophilic benzylation steps
(Scheme 3) as we observed the corresponding monobenzy-
lated tertiary alkyl bromides as intermediates. The reaction
course is totally different from that of the typical reactions
of gem-dihaloalkanes with organometallic reagents, which
includes sequential halogen metal exchange, 1,2-migration
of a ligand on the metal, and trapping with various electro-
philes.[18,19]
Typical procedure for the benzylation or allylation of gem-dibromoal-
kanes: The reaction of 5d is representative (Table 6, entry 4). AgOAc
(2.1 mg, 0.013 mmol) was placed in a 20 mL reaction flask under argon
and then acetonitrile (2.0 mL) and benzylzinc chloride·lithium chloride
complex (0.86m in THF, 2.33 mL, 2.0 mmol) were sequentially added.
The resulting mixture was stirred for 5 min and then gem-Dibromoalkane
5d (0.23 g, 0.50 mmol) was added. The whole mixture was stirred for 6 h
at 258C. The reaction was quenched with saturated ammonium chloride
solution. Organic compounds were extracted with hexane (10 mLꢃ3).
The combined organic phase was dried over anhydrous sodium sulfate
and concentrated. Silica-gel column purification (hexane/ethyl acetate
20:1) of the crude product provided the corresponding dibenzylated
product 6d (0.12 g, 0.25 mmol, 50%).
Characterization data of products: Compounds 2a,[7a] 2c,[21] 2h,[7a] 3b,[7a]
3e,[7a] 3g,[7a] 4a–f,[7a,16a,b] and 7e[7c] produced spectra that were identical to
those shown in the literature. Other compounds were characterized as
shown below.
1-Methyl-1-benzylcyclohexane (2b): IR (neat): n˜ =3062, 3028, 2849, 1601,
Scheme 3. The reaction of gem-dibromoalkane. (R=benzyl or allyl).
1
1496, 1452, 1376, 1031, 758, 704 cmÀ1; H NMR (CDCl3): d=0.83 (s, 3H),
1.22–1.33 (m, 4H), 1.41–1.51 (m, 4H), 1.52–1.56 (m, 2H), 2.53 (s, 2H),
7.11–7.14 (m, 2H), 7.17–7.21 (m, 1H), 7.24–7.27 ppm (m, 2H); 13C NMR
(CDCl3): d=22.34, 24.76, 26.66, 34.24, 37.82, 49.00, 125.82, 127.71, 130.90,
139.38 ppm; elemental analysis calcd (%) for C14H20: C 89.29, H 10.71;
found: C 84.49, H 10.96.
Conclusions
Silver catalysis allows the coupling reaction of tertiary alkyl
bromides with benzylic and allylic zinc reagents. Dibenzyla-
tion and diallylation proceed in the reaction of gem-dibro-
moalkanes. Although the exact mechanism is not clear at
this stage, the method is useful for constructing quaternary
carbon centers with moderate functional-group compatibili-
ty.
4-(2,2-Dimethyl-3-phenylpropyl)-1-methoxybenzene (2d): IR (neat): n˜ =
2912, 2834, 1610, 1497, 1441, 1384, 1364, 1301, 1177, 1039, 809, 774, 757,
731, 704 cmÀ1 1H NMR (CDCl3): d=0.81 (s, 6H), 2.52 (s, 2H), 2.56 (s,
;
2H), 3.79 (s, 3H), 6.80–6.83 (m, 2H), 7.03–7.06 (m, 2H), 7.12–7.14 (m,
2H), 7.19–7.22 (m, 1H), 7.25–7.28 ppm (m, 2H); 13C NMR (CDCl3): d=
26.18, 35.59, 48.64, 49.39, 55.38, 113.25, 125.97, 127.81, 130.93, 131.34,
131.79, 139.39, 158.04 ppm; elemental analysis calcd (%) for C18H22O: C
84.99, H 8.72; found: C 84.81, H 8.85.
4-(2,2-Dimethyl-3-phenylpropyl)-1-fluorobenzene (2e): IR (neat): n˜ =
3028, 2929, 2851, 1604, 1497, 1470, 1452, 1385, 1366, 1223, 1158, 829, 759,
733, 703 cmÀ1 1H NMR (CDCl3): d=0.81 (s, 6H), 2.55 (s, 2H), 2.56 (s,
;
Experimental Section
2H), 6.94–6.98 (m, 2H), 7.05–7.09 (m, 2H), 7.12–7.14 (m, 2H), 7.20–7.23
(m, 1H), 7.25–7.29 ppm (m, 2H); 13C NMR (CDCl3): d=26.14, 35.51,
48.56, 49.46, 114.62 (d, J=21.2 Hz), 126.09, 127.88, 130.91, 132.14 (d, J=
7.8 Hz), 134.86 (d, J=2.9 Hz), 139.12, 161.66 ppm (d, J=244 Hz); ele-
mental analysis calcd (%) for C17H19F: C 84.26, H 7.90; found: C 84.40,
H 8.08.
General: 1H (500 MHz) and 13C NMR (125.7 MHz) spectra were taken
on a Varian UNITY INOVA 500 spectrometer and were obtained in
CDCl3 with tetramethylsilane as an internal standard. IR spectra were
taken on a SHIMADZU FTIR-8200PC spectrometer. Mass spectra were
determined on a JEOL Mstation 700 spectrometer. TLC analyses were
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H. Yorimitsu, K. Oshima et al.
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6,6-Dimethyl-7-phenylheptyl benzoate (2 f): IR (neat): n˜ =2932, 2862,
29.71, 29.87, 30.58, 33.49, 38.03, 38.30, 46.44, 48.26, 50.11, 125.99, 126.59,
127.55, 127.79, 127.88, 128.51, 128.79, 129.15, 131.00, 136.90, 137.80,
139.36, 173.95 ppm; elemental analysis calcd (%) for C39H47NO: C 85.82,
H 8.68; found: C 85.52, H 8.80.
1720, 1605, 1450, 1389, 1273, 1111, 710 cmÀ1 1H NMR (CDCl3): d=0.85
;
(s, 6H), 1.18–1.26 (m, 2H), 1.36–1.49 (m, 4H), 1.79 (tt, J=7.5, 2.0 Hz,
2H), 2.45 (s, 2H), 4.33 (t, J=7.0 Hz, 2H), 7.10–7.12 (m, 2H), 7.19 (tt, J=
7.5, 2.0 Hz, 1H), 7.23–7.27 (m, 2H), 7.44 (tt, J=7.5, 1.5 Hz, 2H), 7.56 (tt,
J=7.5, 1.5 Hz, 1H), 8.03–8.07 ppm (m, 2H); 13C NMR (CDCl3) d=24.15,
27.01, 27.18, 29.06, 34.37, 42.25, 48.65, 65.35, 125.93, 127.83, 128.55,
129.76, 130.75, 130.80, 133.02, 139.65, 166.92 ppm; HRMS (EI): m/z:
calcd for C22H28O2: 324.2089; found: 324.2093.
9,9-Dibenzyldecyl 2,4,6-trimethylbenzoate (6d): IR (neat): n˜ =2932, 2855,
1720, 1612, 1458, 1265, 1173, 1088, 702 cmÀ1 1H NMR (CDCl3): d=0.79
;
(s, 3H), 1.13–1.17 (m, 2H), 1.22–1.28 (m, 2H), 1.29–1.36 (m, 4H), 1.37–
1.46 (m, 4H), 1.74 (tt, J=7.0, 7.0 Hz, 2H), 2.28 (s, 3H), 2.30 (s, 6H), 2.58
(td, J=16.5, 3.0 Hz, 4H), 4.31 (t, J=7.0 Hz, 2H), 6.85 (s, 2H), 7.10–7.13
(m, 4H), 7.20 (tt, J=7.5, 1.5 Hz, 2H), 7.26 ppm (tt, J=7.5, 1.5 Hz, 4H);
13C NMR (CDCl3): d=19.95, 21.33, 24.15, 24.46, 26.30, 28.90, 29.49,
29.86, 30.52, 38.04, 38.31, 46.47, 65.23, 126.01, 127.89, 128.58, 131.00,
131.51, 135.20, 139.35, 170.52, 209.03 ppm; HRMS (EI): m/z: calcd for
C34H44O2: 484.3341; found: 484.3336.
2,2-Dimethyl-1-(4-methylphenyl)decane (3a): IR (neat): n˜ =2927, 2854,
1513, 1468, 1384, 1364, 1022, 813 cmÀ1 1H NMR (CDCl3): d=0.82 (s,
;
6H), 0.89 (t, J=7.0 Hz, 3H), 1.15–1.18 (m, 2H), 1.22–1.32 (m, 12H), 2.32
(s, 3H), 2.45 (s, 2H), 7.00 (d, J=7.5 Hz, 2H), 7.07 ppm (d, J=7.5 Hz,
2H); 13C NMR (CDCl3): d=14.33, 21.20, 22.88, 24.37, 27.01, 29.57, 29.93,
30.78, 32.12, 34.28, 42.31, 48.11, 128.47, 130.66, 135.22, 136.66 ppm; ele-
mental analysis calcd (%) for C19H32: C 87.62, H 12.38; found: C 87.32,
H 12.61.
10,10-Dibenzyl-1-(2,4,6-trimethylphenyl)-1-undecanone (6e): IR (neat):
n˜ =2932, 2855, 1697, 1605, 1458, 1034, 910, 849, 702 cmÀ1
(CDCl3): d=0.78 (s, 3H), 1.15 (m, 2H), 1.20–1.28 (m, 2H), 1.30–1.45ACHTUNGTRENNUNG
;
1H NMR
(m,
2,2-Dimethyl-1-(4-vinylphenyl)decane (3d): IR (neat): n˜ =2853, 1631,
8H), 1.70 (tt, J=7.0, 7.0 Hz, 2H), 2.19 (s, 6H), 2.27 (s, 3H), 2.58 (td, J=
16.5, 3.5 Hz, 4H), 2.69 (t, J=7.5 Hz, 2H), 6.83 (s, 2H), 7.09–7.13 (m,
4H), 7.20 (tt, J=7.5, 1.5 Hz, 2H), 7.26 ppm (tt, J=8.0, 2.5 Hz, 4H);
13C NMR (CDCl3): d=19.34, 21.24, 23.65, 24.18, 24.47, 29.50, 29.75,
29.83, 30.58, 38.06, 38.33, 45.10, 46.48, 126.00, 127.88, 128.68, 131.01,
132.69, 138.39, 139.37, 140.13, 211.17 ppm; HRMS (EI): m/z: calcd for
C34H44O: 468.3392; found: 468.3376;.
1609, 1469, 1437, 1406, 1385, 1170, 1017, 988, 902, 829, 762 cmÀ1
;
1H NMR (CDCl3): d=0.83 (s, 6H), 0.89 (t, J=7.0 Hz, 3H), 1.15–1.18 (m,
2H), 1.22–1.32 (m, 12H), 2.48 (s, 2H), 5.19 (dd, J=11.0, 1.0 Hz, 1H),
5.71 (dd, J=17.5, 1.0 Hz, 1H), 6.70 (dd, J=17.5, 11.0 Hz, 1H) 7.07 (d,
J=8.0 Hz, 2H), 7.31 ppm (d, J=8.0 Hz, 2H); 13C NMR (CDCl3): d=
14.33, 22.89, 24.37, 27.03, 29.57, 29.93, 30.76, 32.12, 34.46, 42.34, 48.28,
113.02, 125.65, 130.93, 135.22, 136.95, 139.65 ppm; elemental analysis
calcd (%) for C20H32: C 88.16, H 11.84; found: C 88.09, H 12.09.
11,11-Dibenzyldodecanenitrile (6 f): IR (neat): n˜ =3024, 2932, 2855, 2245,
1605, 1458, 910, 702 cmÀ1 1H NMR (CDCl3): d=0.79 (s, 3H), 1.13–1.18
;
2,2-Dimethyl-1-(3-bromophenyl)decane (3 f): IR (neat): n˜ =2927, 2854,
(m, 2H), 1.22–1.35 (m, 8H), 1.37–1.48 (m, 4H), 1.66 (tt, J=7.5, 7.5 Hz,
2H), 2.34 (t, J=7.0 Hz, 2H), 2.58 (td, J=16.5, 3.25 Hz, 4H), 7.10–7.13
(m, 4H), 7.20 (tt, J=7.5, 2.5 Hz, 2H), 7.26 ppm (tt, J=7.5, 1.5 Hz, 4H);
13C NMR (CDCl3): d=17.35, 24.16, 24.46, 25.60, 28.88, 28.99, 29.56,
29.83, 30.54, 38.04, 38.31, 46.47, 120.06, 126.01, 127.89, 131.00,
139.35 ppm; elemental analysis calcd (%) for C26H35N: C 86.37, H 9.76;
found: C 86.59, H 9.71.
1685, 1594, 1566, 1560, 1507, 1473, 1458, 1424, 1073, 889, 785, 698 cmÀ1
;
1H NMR (CDCl3): d=0.83 (s, 6H), 0.89 (t, J=7.0 Hz, 3H), 1.15–1.17 (m,
2H), 1.22–1.32 (m, 12H), 2.45 (s, 2H), 7.02–7.05 (m, 1H), 7.11–7.14 (m,
1H), 7.26–7.27 (m, 1H), 7.31–7.34 ppm (m, 1H); 13C NMR (CDCl3): d=
14.33, 22.88, 24.32, 26.95, 29.56, 29.90, 30.70, 32.10, 34.42, 42.31, 48.12,
121.93, 128.97, 129.31, 129.38, 133.58, 142.18 ppm; elemental analysis
calcd (%) for C18H29Br: C 66.45, H 8.98; found: C 66.50, H 9.10.
1-(tert-Butyldimethylsilyloxy)-9-methyl-9-(2-propenyl)-11-dodecene (7a):
4-(2,2-Dimethyl-4-pentenyl)-1-fluorobenzene (4g): IR (neat): n˜ =2962,
IR (neat): n˜ =2932, 2855, 1466, 1250, 1103, 995, 910, 841, 779 cmÀ1
;
2915, 2855, 1640, 1471, 1437, 1416, 1385, 1366, 1158, 1095, 1016, 995, 915,
1H NMR (CDCl3): d=0.05 (s, 6H), 0.82 (s, 3H), 0.90 (s, 9H), 1.14–1.34
(m, 12H), 1.51 (tt, J=7.0, 6.5 Hz, 2H), 1.96–2.00 (m, 4H), 3.60 (t, J=
7.0 Hz, 2H), 4.98–5.05 (m, 4H), 5.75–5.84 ppm (m, 2H); 13C NMR
(CDCl3): d=À5.03, 18.61, 23.60, 24.79, 26.03, 26.22, 29.68, 29.87, 30.67,
33.11, 36.04, 39.42, 44.09, 63.57, 117.01, 135.69 ppm; elemental analysis
calcd (%) for C22H44OSi: C 74.92, H 12.58; found: C 74.80, H 12.86.
892, 838 cmÀ1 1H NMR (CDCl3): d=0.84 (s, 6H), 1.96–1.98 (m, 2H),
;
2.48 (s, 2H), 5.00–5.05 (m, 1H), 5.06–5.08 (m, 1H), 5.83–5.92 (m, 1H),
6.92–7.00 (m, 2H), 7.05–7.09 ppm (m, 2H); 13C NMR (CDCl3): d=26.67,
34.58, 46.73, 47.63, 114.59 (d, J=21.2 Hz), 117.41, 132.03 (d, J=7.67 Hz),
134.98 (d, J=3.91 Hz), 135.66, 161.61 ppm (d, J=244 Hz); elemental
analysis calcd (%) for C13H17F: C, 81.21; H, 8.91; found: C 81.33, H 9.07.
N-Benzyl-N-[9-methyl-9-(2-propenyl)-11-dodecenyl]-4-methylphenylsul-
fonamide (7b): IR (neat): n˜ =2924, 2855, 1458, 1342, 1157, 910, 810, 733,
1-(tert-Butyldimethylsilyloxy)-9,9-dibenzyldecane (6a): IR (neat): n˜ =
2932, 2855, 1466, 1250, 1103, 841, 779, 702 cmÀ1
;
1H NMR (CDCl3): d=
659 cmÀ1 1H NMR (CDCl3): d=0.82 (s, 3H), 1.04–1.20 (m, 12H), 1.24–
;
0.05 (s, 6H), 0.78 (s, 3H), 0.90 (s, 9H), 1.13–1.18 (m, 2H), 1.21–1.35 (m,
8H), 1.37–1.44 (m, 2H), 1.52 (tt, J=6.5, 6.5 Hz, 2H), 2.58 (td, J=17.0,
4.0 Hz, 4H), 3.60 (t, J=6.5 Hz, 2H), 7.10–7.13 (m, 4H), 7.20 (tt, J=7.0,
2.0 Hz, 2H), 7.26 ppm (tt, J=7.5, 2.0 Hz, 4H); 13C NMR (CDCl3): d=
À5.11, 18.62, 24.20, 24.48, 26.06, 26.22, 29.72, 30.00, 30.59, 33.12, 38.06,
38.32, 46.46, 63.58, 126.00, 127.88, 131.01, 139.39 ppm; elemental analysis
calcd (%) for C30H48OSi: C 79.58, H 10.69; found: C 79.55, H 10.87.
1.35 (m, 2H), 1.91–1.99 (m, 4H), 2.44 (s, 3H), 3.07 (t, J=7.5 Hz, 2H),
4.31 (s, 2H), 4.97–5.05 (m, 4H), 5.79 (ddt, J=8.5, 5.0, 7.0 Hz, 2H), 7.25–
7.33 (m, 7H), 7.71–7.74 ppm (m, 2H); 13C NMR (CDCl3): d=21.73,
23.55, 24.78, 26.82, 28.11, 29.27, 29.63, 30.54, 36.02, 39.38, 44.08, 48.29,
52.05, 117.04, 127.41, 127.89, 128.49, 128.71, 129.87, 135.65, 136.84, 137.45,
143.30 ppm; elemental analysis calcd (%) for C30H43NO2S: C 74.80, H
9.00; found: C 74.62, H 9.04.
N-Benzyl-N-(9,9-dibenzyldecyl)-4-methylphenylsulfonamide (6b): IR
N,N-Dibenzyl-10-methyl-10-(2-propenyl)-12-tridecenamide
(7c):
IR
;
(neat): n˜ =2932, 2855, 1597, 1458, 1342, 1157, 910, 733, 656 cmÀ1
;
(neat): n˜ =2924, 2855, 1651, 1450, 1358, 1211, 995, 910, 702 cmÀ1
1H NMR (CDCl3): d=0.78 (s, 3H), 1.02–1.18 (m, 10H), 1.25–1.38 (m,
4H), 2.43 (s, 3H), 2.57 (td, J=16.0, 3.0 Hz, 4H), 3.07 (t, J=7.5 Hz, 2H),
4.31 (s, 2H), 7.08–7.13 (m, 4H), 7.20 (tt, J=7.5, 2.5 Hz, 2H), 7.26 (tt, J=
7.5, 2.0 Hz, 6H), 7.28–7.32 (m, 5H), 7.73 ppm (dt, J=4.0, 2.0 Hz, 2H);
13C NMR (CDCl3): d=21.73, 24.13, 24.46, 26.83, 28.14, 29.30, 29.74,
30.45, 38.03, 38.30, 46.46, 48.31, 52.08, 126.02, 127.42, 127.89, 128.49,
128.72, 129.87, 130.99, 136.85, 137.43, 139.34, 143.31, 231.99 ppm; HRMS
(FAB): m/z: calcd for C38H46NO2S: 580.3249; found: 580.3264 [MÀH]À.
1H NMR (CDCl3): d=0.82 (s, 3H), 1.14–1.34 (m, 12H), 1.71 (tt, J=7.5,
7.5 Hz, 2H), 1.92–1.99 (m, 4H), 2.41 (t, J=7.5 Hz, 2H), 4.45 (s, 2H), 4.60
(s, 2H), 4.96–5.05 (m, 4H), 5.79 (ddt, J=8.5, 5.25, 7.5 Hz, 2H), 7.15 (d,
J=3.5 Hz, 2H), 7.22 (d, J=3.5 Hz, 2H), 7.25–7.28 (m, 1H), 7.29–7.34 (m,
3H), 7.37 ppm (t, J=7.5 Hz, 2H); 13C NMR (CDCl3): d=23.60, 24.79,
25.69, 29.67, 29.74, 30.67, 33.51, 36.03, 39.41, 44.09, 48.27, 50.13, 109.98,
117.02, 126.61, 127.55, 127.79, 128.52, 128.79, 129.15, 135.69, 136.92,
137.82, 173.97 ppm; elemental analysis calcd (%) for C31H43NO: C 83.54,
H 9.72; found: C 83.71, H 9.92.
10,10,N,N-Tetrabenzylundecanamide (6c): IR (neat): n˜ =3032, 2932,
1
2855, 1651, 1450, 1211, 1080, 949, 702 cmÀ1; H NMR (CDCl3): d=0.78 (s,
9-Methyl-9-(2-propenyl)-11-dodecenyl 2,4,6-trimethylbenzoate (7d): IR
3H), 1.12–1.16 (m, 2H), 1.18–1.35 (m, 8H), 1.35–1.43 (m, 2H), 1.72 (tt,
J=7.0, 7.5 Hz, 2H), 2.42 (t, J=7.5 Hz, 2H), 2.58 (td, J=16.5, 3.5 Hz,
4H), 4.45 (s, 2H), 4.61 (s, 2H), 7.10–7.12 (m, 4H), 7.15 (d, J=3.5 Hz,
2H), 7.17–7.23 (m, 4H), 7.24–7.29 (m, 5H), 7.29–7.34 (m, 3H), 7.37 ppm
(t, J=7.5 Hz, 2H); 13C NMR (CDCl3): d=24.19, 24.45, 25.68, 29.66,
(neat): n˜ =2932, 2855, 1728, 1612, 1458, 1265, 1173, 1088, 910 cmÀ1
;
1H NMR (CDCl3): d=0.82 (s, 3H), 1.14–1.36 (m, 10H), 1.37–1.44 (m,
2H), 1.73 (tt, J=7.5, 7.5 Hz, 2H), 1.92–2.00 (m, 4H), 2.28 (s, 3H), 2.29
(s, 6H), 4.30 (t, J=7.0 Hz, 2H), 4.98–5.05 (m, 4H), 5.78 (ddt, J=8.5,
5.25, 7.5 Hz, 2H), 6.85 ppm (s, 2H); 13C NMR (CDCl3): d=19.95, 21.33,
1492
www.chemasianj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 1487 – 1493

Tertiary Alkyl Bromides
23.57, 24.78, 26.29, 28.90, 29.47, 29.75, 30.61, 36.02, 39.39, 44.08, 65.24,
117.04, 128.58, 131.50, 135.20, 135.66, 139.35, 170.52 ppm; elemental anal-
ysis calcd (%) for C26H40O2: C 81.20, H 10.48; found: C 81.28, H 10.66.
Chem. 2002, 653, 11–19; b) M. Tamura, J. K. Kochi, Synthesis 1971,
303–305; c) T. Nagano, T. Hayashi, Chem. Lett. 2005, 34, 1152–
1153; d) M. Tamura, J. K. Kochi, Bull. Chem. Soc. Jpn. 1972, 45,
1120–1127.
4-Methyl-4-(2-phenylethyl)-1,6-heptadiene (7e): IR (neat): n˜ =3074,
2920, 1638, 1498, 1454, 996, 913, 743, 698 cmÀ1 1H NMR (CDCl3): d=
;
[9] a) M. Sai, H. Someya, H. Yorimitsu, K. Oshima, Org. Lett. 2008, 10,
2545–2547; b) M. Sai, H. Yorimitsu, K. Oshima, Bull. Chem. Soc.
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[10] Copper-catalyzed reactions of secondary and tertiary alkyl halides
with organometallic reagents reported by other groups: D. H. Burns,
J. D. Miller, H. K. Chan, M. O. Delaney, J. Am. Chem. Soc. 1997,
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[11] A. Metzger, M. A. Schade, P. Knochel, Org. Lett. 2008, 10, 1107–
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[12] G. J. Rowlands in Science of Synthesis (Houben-Weyl), Vol. 29 (Ed.:
S. I. Warriner), Thieme, Stuttgart, 2007, Chapter 29.2.
[13] The plausible by-products are the following:
0.93 (s, 3H), 1.47–1.52 (m, 2H), 2.02–2.10 (m, 4H), 2.56 (dt, J=4.5,
4.5 Hz, 2H), 5.04–5.10 (m, 4H), 5.79–5.90 (m, 2H), 7.14–7.23 (m, 3H),
7.24–7.32 ppm (m, 2H); 13C NMR (CDCl3): d=24.79, 30.35, 36.23, 41.76,
44.02, 117.43, 125.80, 128.53, 128.54, 135.29, 143.53 ppm; elemental analy-
sis calcd (%) for C16H22: C 89.65, H 10.35; found: C 89.51, H 10.07.
4-Heptyl-4-methyl-1,6-heptadiene (7 f): IR (neat): n˜ =3076, 2929, 2856,
1
1639, 1466, 1442, 1377, 995, 912 cmÀ1; H NMR (CDCl3): d=0.83 (s, 3H),
0.88 (t, J=7.0 Hz, 3H), 1.14–1.34 (m, 12H), 1.92–2.00 (m, 4H), 4.97–5.04
(m, 4H), 5.80 ppm (ddt, J=8.0, 2.5, 7.5 Hz, 2H); 13C NMR (CDCl3): d=
14.33, 22.91, 23.64, 24.80, 29.58, 30.71, 32.14, 36.04, 39.44, 44.10, 117.10,
135.71 ppm; elemental analysis calcd (%) for C15H28: C 86.46, H 13.54;
found: C 86.54, H 13.84.
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