Nickel-catalyzed reductive benzylation of aldehydes with benzyl halides and pseudohalides

Article abstract of DOI:10.1002/adsc.201400970

The reductive benzylation of aromatic and aliphatic aldehydes with benzylic halides is reported using a nickel/zinc catalyst system. In addition to benzylic halides, the first report on the addition of benzylic triflates, acetates, tosylates and tritylates to aldehydes is also presented. By this new method a range of alcohols was synthesized efficiently from aldehydes and benzylic substrates at room temperature in moderate to high yields. The mild reaction conditions and good functional group tolerance make this nickel-catalyzed process synthetically useful for the synthesis of diverse benzylic alcohols.

Full text of DOI:10.1002/adsc.201400970

FULL PAPERS
DOI: 10.1002/adsc.201400970
Nickel-Catalyzed Reductive Benzylation of Aldehydes with
Benzyl Halides and Pseudohalides
a
a
a,
Farhad Panahi, Marzieh Bahmani, and Nasser Iranpoor *
a
Department of Chemistry, College of Sciences, Shiraz University, Shiraz, 71454, Iran
E-mail: iranpoor@chem.susc.ac.ir
Received: October 9, 2014; Revised: February 5, 2015; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400970.
Abstract: The reductive benzylation of aromatic and ture in moderate to high yields. The mild reaction
aliphatic aldehydes with benzylic halides is reported conditions and good functional group tolerance
using a nickel/zinc catalyst system. In addition to make this nickel-catalyzed process synthetically
benzylic halides, the first report on the addition of useful for the synthesis of diverse benzylic alcohols.
benzylic triflates, acetates, tosylates and tritylates to
aldehydes is also presented. By this new method
a range of alcohols was synthesized efficiently from Keywords: alcohols; aldehydes; benzylation; nickel-
aldehydes and benzylic substrates at room tempera- catalyzed reaction; reductive coupling
Introduction
reactions. To avoid these limitations, one of the best
applicable methods is the direct addition of the in situ
[13]
The addition of organometallic reagents to aldehydes generated organometallic reagents to aldehydes.
toward the synthesis of alcohols has become a useful
and efficient strategy in organic chemistry. The most ductive coupling reactions are among the most profi-
important organometallic reagents that have been cient approaches for carbon-carbon bond formation
On the other hand, transition metal-catalyzed re-
[
1]
[
2]
[3]
[4]
[14]
used so far are lithium, magnesium, aluminum,
reactions in modern organic chemistry. The reduc-
zinc, tin, silicium, gallium, indium and bor- tive cross-coupling reactions permit us to connect two
[5]
[6]
[7]
[8]
[9]
[10
anes. Also, in recent years some other methods electrophilic reagents without the formation of a stoi-
[
15]
have been developed based on aryl CÀH addition to chiometric organometallic species. Ni-catalyzed re-
aldehydes to give the corresponding alcohols
[11]
(
Figure 1).
Despite considerable advances in the addition of
organometallic reagents to aldehydes, most of these
methods suffer from some disadvantages including
sensitivity to air and moisture, toxicity of the organo-
metallic reagent, less functional group compatibility,
limited commercial availability, and the use of harsh
[
2–10]
reaction conditions.
In view of the importance of
addition reactions to aldehydes for the synthesis of al-
cohols, a great challenge still remains regarding the
use of new catalysts, reagents and methods. Among
all of the used reagents, organoboron species have sig-
nificant practical advantages over other organometal-
[12]
lics. Nevertheless, the main practical limitations of
organoborons for addition to aldehydes are substrate
limitation, and use of expensive reagents and addi-
[
10]
tives for their preparation. Another problem associ-
ated with some of the aforementioned organometallic Figure 1. Addition of the most widely used organometallic
reagents is their instability which cause undesired side reagents to aldehydes.
Adv. Synth. Catal. 0000, 000, 0 – 0
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[a]
Table 1. Optimization of the reaction conditions.
Scheme 1. Nickel-catalyzed addition of benzylic reagents to
aldehydes.
ductive coupling reactions have thus opened up a new
direction for the direct coupling of aryl/alkyl halides
[
b]
Entry
[Ni]
Solvent
Additive
Yield [%]
[
17]
and carbonyl compounds. This strategy has consid-
erable attractive features, both from an experimental
simplicity and also step-economical points of view. In
reductive cross-coupling processes the differentiation
between electrophilic natures of the two used electro-
philes is an important factor in order to prevent the
1
2
3
4
5
6
7
8
9
NiCl ·5H O
–
NiCl (PPh )
NiCl
NiCl (dppe)
NiCl (dppp)
NiCl (dppf)
NiCl (dppf)
NiCl (dppf)
NiCl (dppf)
NiCl (dppf)
NiCl (dppf)
NiCl (dppf)
NiCl (dppf)
NiCl
NiCl (dppf)
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
NMP
MgCl2
MgCl2
MgCl2
48
0
2
2
60
70
71
75
80
30
55
38
73
2
3
2
(PCy
2
)
MgCl
3
2
2
2
MgCl2
2
MgCl2
[
18]
MgCl2
–
2
homo-coupling of either component. Since the elec-
trophilic activity differences of halides and carbonyl
compounds are remarkable, this strategy is highly effi-
2
ZnCl2
LiCl
MgBr2
MgCl2
MgCl2
MgCl2
2
10
11
12
[
19]
2
cient for the addition of halides to aldehydes. Previ-
ously, Majumdar and Cheng reported an efficient
2
[c]
0
2
[
d]
method for the arylation of aromatic aldehydes using 13
70
76
35
2
[
13b]
an Ni(II)/Zn catalyst system.
Recently, Tan et al. 14
2
reported a nickel-catalyzed asymmetric reductive ally- 15
(dppf)
2
CH
CN
MgCl
3
2
16
17
18
toluene
DMF
DMF
DMF
MgCl2
26[
77[
83
lation of aldehydes with allylic carbonates and the
procedure was efficient for 2-arylallylic carbonates in
order to generate the corresponding homoallylic com-
2
e]
f]
NiCl (dppf)
NiCl (dppf)
NiCl
MgCl2
2
MgCl2
2
g]
[
19]
19
(dppf)
2
MgCl
2
64
pounds in good to excellent yields and ees. Howev-
er, as far as we know, there is no general report in the
literature on the nickel-catalyzed reductive benzyla-
tion of aldehydes with benzylic substrates.
[a]
Reaction conditions: 4-nitrobenzyl chloride (1 mmol),
benzaldehyde (1 mmol), [Ni] (5 mol%), Zn (3 mmol),
MgCl (2 mmol), DMF (5 mL) at room temperature for
2
2
4 h.
In the current study we would like to introduce
a nickel-catalyzed addition of benzylic halides as well
as protected benzylic alcohols to aldehydes at room
temperature without the use of pre-prepared organo-
metallic reagents (Scheme 1).
[
[
[
b]
c]
d]
Isolated yield.
Zn was not used.
Mn was used instead of Zn.
Reaction was performed at 508C.
7
2
[e]
[f]
.5 mol% of the catalyst was used.
.5 mol% of the catalyst was used.
[
g]
Results and Discussion
tion mixture, the yield decreased significantly, demon-
At first, we focused on the addition of 4-nitrobenzyl strating that the presence of this salt is necessary for
[
21]
chloride (1a) to benzaldehyde (2a) as a model reac- the reaction to progress (Table 1, entry 8).
When
tion and screened different reaction conditions in other metal halides such as ZnCl , LiCl, and MgBr2
2
order to optimize the reaction yield. The obtained re- were employed as the additive instead of MgCl2,
sults are depicted in Table 1.
a sharp decrease in the reaction yield was observed
Under the first set of conditions tested (NiCl2, (Table 1, entries 9–11). In the absence of reducing
DMF, MgCl and Zn), the desired product was ob- agent the reaction did not proceed, demonstrating
2
tained in 48% yield (Table 1, entry 1). In the absence that the presence of Zn is also essential (Table 1,
of Ni catalyst, no product was observed, illustrating entry 12). Also, on change of Zn with Mn no im-
the important role of the Ni catalyst for this process provement in the reaction yield was observed, which
(
Table 1, entry 2). Regarding the important role of li- shows that Zn is more efficient than Mn for this pro-
[20] [22]
gands in metal-catalyzed reactions, we changed the cess (Table 1, entry 13).
Attempts to improve the
type of ligand in the Ni catalyst and the obtained re- yield by changing the solvent to NMP, acetonitrile
sults showed that under similar conditions, and toluene were found to be fruitless (Table 1, en-
NiCl (dppf) was superior to the other ones (Table 1, tries 14–16). Also, efforts to increase the yield by con-
2
entries 3–7). The role of metal ions in this reaction is ducting the reaction at higher temperatures resulted
important. When MgCl was not added to the reac- in a decrease in the yield of the reaction (Table 1,
2
2
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Nickel-Catalyzed Reductive Benzylation of Aldehydes with Benzyl Halides
Table 2. Direct Ni-catalyzed addition of benzylic substrates was examined to explore the scope of the reaction
[a]
to benzaldehyde.
(
Scheme 2).
Under the optimized conditions, the reactivity of
different benzylic substrates was investigated. Simple
benzyl substrates were added to different aldehydes
and good yields of the products were obtained. For
example, with a tert-butyl group (3b) and a cyano
group (3c), the reactions showed good reactivity.
Then, 4-nitrobenzylchloride was used as an easy to
handle substrate (some of the benzylic halides are
quite volatile at room temperature) in order to syn-
thesize a range of target compounds under our opti-
mized conditions. Various electron-donating and elec-
tron-withdrawing groups on the aldehyde source were
tested. Since it has been reported that the presence of
halogen atoms on the aldehyde substrate is a limita-
[
b]
Entry
X
Time [h]
Yield [%]
1
2
3
4
5
6
7
8
Cl
Br
I
OH
OTf
OTs
OTr
OAc
24
20
12
48
24
24
24
24
80
83
85
0
87
78
62
82
[
2,3]
tion in many of the previous methods,
initially, 4-
fluoro-, 4-chloro- and 4-bromobenzaldehydes were
examined which offered good yields of the corre-
sponding products (3d–f). It was found that the donat-
[
a]
Reaction conditions: 4-nitrobenzylic substrate (1 mmol),
benzaldehyde (1 mmol), NiCl (dppf) (5 mol%), Zn
3 mmol), MgCl (2 mmol), DMF (5 mL) at room tem-
2
ing groups such as Me, OMe, NMe and SMe also
(
2
2
give a remarkable yield of their resultant product
(3g–j). Significantly, the unprotected hydroxy group
was also compatible under the optimized conditions
perature for 24 h.
Isolated yield.
[
b]
(
3k and 3l). It is known that the presence of free a hy-
entry 17). Increasing the amount of the catalyst to droxy group is a limitation in organometallic reagents
.5 mol% did not increase the obtained yield of 3a especially with Mg and Li.
Table 1, entry 18). As a result of reducing the This transformation showed good compatibility
7
(
amount of catalyst, a decrease in the yield of product with electron-withdrawing groups, such as CN (3m).
was observed (Table 1, entry 19). In the light of these For substrates containing nitro, formyl and cyano
results, we established that the reaction conditions functionalities no reduced products were observed. It
shown in entry 7 (Table 1) are the optimal to offer the is worthy to note that the benzylic substrates could
highest yield of the product in our designed protocol. react with an aliphatic aldehyde, affording the corre-
Since there is no report in the literature on the ad- sponding alcohols in good yields (3n and 3o). For ex-
dition of protected benzylic alcohols to aldehydes, we ample, reactions of benzyl bromide and triflate with
decided to explore the possibility of using other ben- formalin resulted in the production of compound 3n
zylic sustrates such as benzylic triflates, acetates, tosy- in 70% and 73% yields, respectively. Also, good
lates and tritylates instead of benzylic halides in this yields of the corresponding alcohols were produced
reductive benzylation of aldehydes (Table 2).
on using acetaldehyde (3o).
As shown in Table 2, in addition to benzylic halides,
When terephthalaldehyde was used for the mono-
a range of benzylic substrates including triflate, ace- addition reaction, compound 3p which has the poten-
tate tosylate, and tritylate were used successfully in tial chance for further functionalization was obtained
this protocol. It is known that alcohols are not suita- in 68% yield. In this study a heterocyclic substrate
ble substrates to be used for the reductive addition to (thiophene-2-carbaldehyde) was also examined and
aldehydes, however, our finding makes it possible to compound 3q was obtained in 84% isolated yield.
use protected benzylic alcohols for this transforma- Compound 3r was synthesized from the reaction of 4-
tion. The order of yields for benzylic substrates was methoxybenzyl bromide carrying an electron-donating
found to be OTf>I>Br>OAc >Cl>OTs>OTr in group and 4-nitrobenzaldehyde in 81% isolated yield.
the model reaction.
In order to show the applicability of other benzylic
From this point of view our method is highlighted substrates in this protocol, 2,4,6-trimethylbenzyl chlo-
because it permits us to use diverse benzylic sub- ride was used and compound 3s was obtained in 80%
strates for the benzylation of aldehydes. This is de- isolated yield. 4-Flourobenzyl chloride as a halogen-
spite the fact that in reductive benzylation methods, substituted benzyl halide was also used in the reaction
only benzyl halides have so far been used as benzylat- with 3-methylbenzaldehyde and 4-chlorobenzalde-
[23]
ing agent.
hyde and compounds 3t and 3u were produced in 77
With the optimal conditions in hand, the reaction and 79% isolated yields, respectively.
of various aldehydes with different benzylic substrates
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In order to show further the functional group com-
patibility of this method, two aldehydes (2v and 2w)
were synthesized and used in the reaction with 4-ni-
trobenzyl chloride. Under the optimized conditions
compounds 3v and 3w were obtained in 65 and 71%
yields, respectively (Scheme 3). This experiment re-
vealed that the amide and ester groups are inert in
the presence of aldehyde group in our strategy.
Acetophenone and benzophenone failed to react
under these conditions demonstrating that ketones
are also inactive under our optimized conditions. To
further explore this chemoselectivity, we ran a compe-
tition experiment involving both ketones and alde-
hydes. As a simple test, one equiv. of 4-nitrobenzyl
chloride was reacted with one equiv. of each of ben-
zaldehyde and acetophenone and only compound 3a
was produced. This result also confirms that ketones
are inactive under the optimized conditions
(
Scheme 4).
The protocol could also be extended to secondary
or tertiary benzylic substrates to afford the desired
products. With the optimized conditions, some exam-
ples with secondary or tertiary benzylic substrates
were investigated and the corresponding products
were obtained in moderate yields. Trityl chloride was
reacted with 4-formylbenzonitrile and 3x was pro-
duced in 65% isolated yield. Additions of benzhydryl
triflate and acetate to 4-nitrobenzaldehyde resulted in
the production of 3y in 64 and 60% isolated yields, re-
spectively. Compound 3z also was synthesized in 67%
yield. Also compound 3aa was synthesized by using
the reaction of (1-bromoethyl)benzene or 1-phenyl-
ethyl tosylate as a secondary benzylic substrates with
4-nitrobenzaldehyde (Scheme 5). Thus, this strategy is
applicable for secondary or tertiary benzylic sub-
strates.
It was interesting to use 4-nitrotoluene instead of 4-
nitrobenzyl chloride in this study. When this experi-
ment was performed under our optimized conditions,
no product was obtained and 4-nitrotoluene remained
intact even in the presence of different bases. Howev-
er, when 4-nitrotoluene was reacted with benzalde-
hyde in the presence of K CO as base in a mixture of
2
3
water and PEG-200 as solvent at 808C, 4-nitrostilbene
was obtained. This finding is in agreement with the
[
24]
work of Ruby (Scheme 6).
This study clarifies that our simple procedure is ef-
fective for the synthesis of the desired alcohols with-
out the formation of eliminated products via a dehy-
dration reaction.
Some experiments were conducted to obtain
deeper insights into the reaction mechanism. Interest-
ingly, the reaction could also be performed in the
Scheme 2. The products from the nickel-catalyzed addition
of benzylic substrates to aldehydes. Reaction conditions:
presence of Ni(PPh ) (CO) as a Ni(0) catalyst system
benzylic substrate (1 mmol), aldehyde (1 mmol), NiCl (dppf)
3
2
2
2
(
Scheme 7). This experiment reveals that this is
(
5 mol%), Zn (3 mmol), MgCl (2 mmol), DMF (5 mL) at
2
room temperature for 24 h. All yields are of isolated prod- a Ni(0)-catalyzed process, since in the presence of
ucts.
Ni(0) this reaction occurs, while no progress was ob-
4
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Nickel-Catalyzed Reductive Benzylation of Aldehydes with Benzyl Halides
Scheme 3. Nickel-catalyzed addition of benzylic reagents to aldehydes in the presence of amide and ester groups.
Scheme 4. Competition experiment between ketones and aldehydes.
Scheme 6. Reaction of 4-nitrotoluene and benzalaldehyde
under different conditions.
Scheme 5. The products of the nickel-catalyzed addition of
secondary or tertiary benzylic substrates to aldehydes. All
yields are of isolated products.
Scheme 7. Ni(0)-catalyzed addition of 4-nitrobenzyl chloride
to benzaldehyde.
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Figure 2. UV spectra of NiCl and NiCl in the presence of
Zn(0).
2
2
Scheme 8. Proposed reaction mechanism.
served for the reaction in the presence of an Ni(II) Conclusions
catalyst (Table 1, entry 2).
It seems that the role of Zn in this process is the re- In conclusion, we have illustrated the first examples
duction of Ni(II). In order to find evidence in support of the 1,2-addition of aldehydes with benzylic sub-
of this reduction, the reduction of Ni(II) to Ni(0) with strates using a Ni(0) catalytic system. This strategy
Zn was studied by UV spectroscopy under our opti- represents a constructive and practical synthetic ap-
mized conditions (Figure 2). Disappearance of the proach for the assembly of a wide range of alcohols.
band around 420 nm is indicative of the reduction of Also a wide range of benzylic substrates (Cl, Br, I,
Ni(II) to Ni(0) under these conditions.
OTf, OAc, OTs and OTr) was used for addition to al-
On the basis of the literature reports, and experi- dehydes, demonstrating the wide scope of this
ments done, a plausible reaction mechanism as out- method. The reaction provides a simple option to the
lined in Scheme 8 is proposed. First, reduction of other existing methodologies that need the prepara-
[
25]
NiCl ·L with Zn affords Ni(0)·L . Subsequently, ox- tion of sensitive organometallic reagents.
2
2
2
idative addition of Ni(0)·L to the alkyl halide readily
2
1
occurs to afford the intermediate I as a h -bound
nickel complex. The intermediate I can be in equilib-
3
[26]
rium with II (h -bound nickel complex). The reduc-
tion of these intermediate (I and II) with Zn gener-
Experimental Section
[
16a]
ates the intermediate III as a Ni(I) complex.
Reac-
General
tion of III with the activated C=O bond promoted by
MgCl takes place to give intermediate IV. It should Chemicals were purchased from Fluka and Aldrich chemical
2
be mentioned that Metzger et al. have also shown companies and used without further purification. The
that the sluggish reactivity of organozinc reagents to- known products were characterized by comparison of their
spectral and physical data with those reported in the litera-
wards aldehydes, can be dramatically improved by the
1
13
[
27]
ture. H (250 MHz) and C NMR (62.9 MHz) spectra were
addition of MgCl2.
The ultimate action of IV with Zn would regener-
ate the active Ni(0)·L species and gives zinc alkoxy
complex V. The complex V then undergoes hydrolysis
with water to yield the target product.
recorded on a Bruker Avance spectrometer in CDCl solu-
3
tions with tetramethylsilane (TMS) as the internal standard.
FT-IR spectroscopy (Shimadzu FT-IR 8300 spectrophotome-
ter) was employed for characterization of the products.
Melting points were determined in open capillary tubes in
a Barnstead electro-thermal 9100 BZ circulating oil melting
point apparatus. The reaction monitoring was accomplished
by TLC on silica gel PolyGram SILG/UV254 plates.
2
[
16,22]
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Nickel-Catalyzed Reductive Benzylation of Aldehydes with Benzyl Halides
1
Column chromatography was carried out on columns of
silica gel 60 (70–230 mesh).
2-(4-Nitrophenyl)-1-(para-tolyl)ethanol (3g):
H NMR
(250 MHz, CDCl /TMS): d=1.29 (s, 1H), 2.41 (s, 3H), 3.02–
3
3
8
.05 (m, 2H), 4.75–4.80 (m, 1H), 7.47 (d, J=7.5 Hz, 2H),
1
3
.13 (d, J=5.0 Hz, 2H); C NMR (62.5 MHz, CDCl /TMS):
3
d=23.6, 45.4, 74.4, 123.7, 127.5, 129.2, 129.3, 137.2, 142.7,
General Procedure for Ni-Catalyzed Reductive
Benzylation of Aldehydes
146.5, 148.6; anal. calcd. for C H NO (257.28): C 70.02, H
1
5
15
3
5.88, N 5.44; found: C 70.08, H 5.82, N 5.49.
-(2-Methoxyphenyl)-2-(4-nitrophenyl)ethanol
H NMR (250 MHz, CDCl /TMS): d=1.18 (s, 1H), 2.99 (s,
1
1
(3h):
Into a canonical flask (50 mL), a mixture of aldehyde
3
(
(
(
1 mmol), benzyl halide (1 mmol), Zn (3 mmol), MgCl2
2
1
7
5
1
6
H), 3.82 (s, 3H), 5.05–5.09 (m, 1H), 6.84 (q, J=7.5 Hz,
2 mmol) and NiCl (dppf) (5 mol%) was stirred in dry DMF
2
H), 7.09 (t, J=7.5 Hz, 1H), 7.15–7.27 (m, 4H), 8.05 (d, J=
5 mL) for 24 h at room temperature. After completion of
13
.5 Hz, 2H); C NMR (62.5 MHz, CDCl /TMS): d=43.7,
3
the reaction as confirmed by TLC, 50 mL of ethyl acetate
and 50 mL of water were added to the reaction mixture.
After separation of the organic layer from water, the aque-
ous phases were extracted with ethyl acetate (2ꢁ25 mL)
again. The combined organic layers were then dried over
anhydrous Na SO , filtered and concentrated under vacuum
5.3, 71.3, 110.5, 120.8, 123.8, 129.1, 129.3, 130.3, 132.5,
46.7, 148.1, 155.9; anal. calcd. for C H NO (273.28): C
1
5
15
4
5.92, H 5.53, N 5.13; found: C 65.97, H 5.58, N 5.19.
1
1
-[4-(Methylthio)phenyl]-2-phenylethanol (3i): H NMR
(
250 MHz, CDCl /TMS): d=1.97 (s, 1H), 2.40 (s, 3H), 2.89–
3
2
4
2
.92 (m, 2H), 4.74–4.79 (m, 1H), 7.08–7.22 (m, 9H).
to yield the crude product. The crude product was purified
by column chromatography (n-hexane/ethyl acetate) to
1
3
C NMR (62.5 MHz, CDCl /TMS): d=38.5, 46.1, 75.6,
3
1
28.4, 128.6, 132.0, 132.1, 136.2, 137.0, 137.1; anal. calcd. for
obtain the desired purity.
1
C
15
H16OS (244.35): C 73.73, H 6.60; found: C 73.65, H, 6.54.
2-(4-Nitrophenyl)-1-phenylethanol
(3a):
H NMR
1
-[4-(Dimethylamino)phenyl]-2-(4-nitrophenyl)ethanol
(
(
(
250 MHz, CDCl /TMS): d=1.24 (s, 1H), 3.07 s, 2H), 4.94
3
1
(
3j): H NMR (250 MHz, CDCl /TMS): d=1.18 (s, 1H),
3
m, 1H), 7.25–7.29 (m, 5H), 7.46 (d, J=7.5 Hz, 2H), 8.13
1
3
2.88–3.01 (m, 8H), 4.74–4.79 (m, 2H), 6.61–6.68 (m, 2H),
d, J=7.5 Hz, 2H); C NMR (62.5 MHz, CDCl /TMS): d=
3
7
.04–7.11 (m, 2H), 7.65–7.72 (m, 2H), 8.04–8.08 (m, 2H);
4
1
5.3, 74.6, 123.8, 125.9, 128.3, 129.3, 129.9, 143.3, 146.6,
48.0; anal. calcd. for C H NO (243.26): C 69.12, H 5.39,
1
3
C NMR (62.5 MHz, CDCl /TMS): d=40.1, 40.2, 72.9,
3
1
4
13
3
1
11.6, 120.9, 123.6, 129.1, 130.5, 145.6, 148.0, 150.2; anal.
N 5.76; found: C 69.23, H 5.31, N 5.84.
-[4-(tert-Butyl)phenyl]-2-phenylethanol (3b): H NMR
250 MHz, CDCl /TMS): d=1.59 (s, 9H), 3.19 (s, 2H), 3.29
1
calcd. for C H N O (286.33): C 67.12, H 6.34, N 9.78;
16 18 2 3
1
found: C 67.20, H 6.39, N 9.86.
(
(
(
3
1
3
5-[1-Hydroxy-2-(4-nitrophenyl)ethyl]-2-methoxyphenol
s, 1H), 5.10–5.16 (m, 1H), 7.44–7.63 (m, 9H); C NMR
62.5 MHz, CDCl /TMS): d=31.8, 38.3, 46.2, 75.6, 125.7,
1
(
3k): H NMR (250 MHz, CDCl /TMS): d=1.18 (s, 1H),
3
3
2
.32 (s, 2H), 2.88 (s, 1H), 3.83 (s, 3H), 4.62–4.63 (m, 1H),
126.1, 126.3, 128.8, 129.9, 138.7, 141.1, 151.0; anal. calcd. for
6
.82 (d, J=7.5 Hz, 1H), 7.18 (d, J=5.0 Hz, 2H), 7.43 (d, J=
C H O (254.37): C 84.99, H 8.72; found: C 84.81, H 8.65.
1
8
22
1
7.5 Hz, 1H), 7.57 (d, J=7.5 Hz, 1H), 8.02 (d, J=7.5 Hz,
4
-(1-Hydroxy-2-phenylethyl) benzonitrile (3c): H NMR
1
3
2
1
H). C NMR (62.5 MHz, CDCl /TMS): d=45.1, 55.8, 66.6,
(
250 MHz, CDCl /TMS): d=2.27 (s, 1H), 2.89–3.07 (m,
3
3
10.6, 115.4, 121.5, 123.5, 129.8, 135.8, 146.2, 146.3, 150.0,
2
7
H), 4.92–4.97 (m, 1H), 7.22–7.35 (m, 3H), 7.43 (d, J=
13
165.0; anal. calcd. for C H NO (289.28): C 62.28, H 5.23,
.5 Hz, 2H), 7.61 (d, J=10.0 Hz, 2H); C NMR (62.5 MHz,
15 15 5
N 4.84; found: C 62.19, H 5.18, N 4.75.
-[1-Hydroxy-2-(4-nitrophenyl)ethyl]phenol (3l): HNMR
250 MHz, CDCl /TMS): d=1.25 (s, 1H), 2.91–3.07 (m,
CDCl /TMS): d=46.0, 74.5, 111.2, 118.9, 126.6, 127.0, 128.7,
3
1
2
1
29.5, 132.2, 136.9, 149.0; anal. calcd. for C H NO (223.27):
15 13
(
C 80.69, H 5.87, N 6.27; found: C 80.61, H 5.82, N 6.20.
-(4-Fluorophenyl)-2-(4-nitrophenyl)ethanol
H NMR (250 MHz, CDCl /TMS): d=1.17 (s, 1H), 2.96 (s,
3
3
H), 5.56 (m, 1H), 6.78–6.88 (m, 2H), 7.19–7.30 (m, 4H),
1
(3d):
1
3
1
8.14 (d, J=10.0 Hz, 2H); C NMR (62.5 MHz, CDCl3/
TMS): d=45.3, 67.1, 115.4, 121.1, 123.8, 127.4, 128.8, 129.3,
3
2
4
1
H), 4.78–4.83 (m, 1H), 7.04–7.22 (m, 4H), 7.55–8.38 (m,
13
1
14 13
29.4, 146.1, 148.0, 155.0; anal. calcd. for C H NO4
H); C NMR (62.5 MHz, CDCl /TMS): d=45.4, 74.4,
3
(
259.26): C 64.86, H 5.05, N 5.40; found: C 64.79, H 5.00, N
15.7, 123.7, 127.6, 129.3, 133.3, 145.9, 146.5, 165.7; anal.
5
.31.
-[1-Hydroxy-2-(4-nitrophenyl)ethyl]benzonitrile
H NMR (250 MHz, CDCl /TMS): d=1.58 (s, 1H), 3.06–
calcd. for C H FNO (261.08): C 64.36, H 4.63, N 5.36;
14
12
3
4
(3m):
found: C 64.43, H 4.67, N 5.46.
-(4-Chlorophenyl)-2-(4-nitrophenyl)ethanol
H NMR (250 MHz, CDCl /TMS): d=1.56 (s, 1H), 3.08 (s,
1
1
(3e):
3
1
3
.11 (m, 2H), 5.00–5.04 (m, 1H), 7.25–7.29 (m, 4H), 7.63 (d,
3
1
3
2
2
H), 5.03 (m, 1H), 7.25–7.30 (m, 4H), 7.45 (d, J=10.0 Hz,
H), 8.15 (d, J=10.0 Hz, 2H); CNMR (62.5 MHz, CDCl3/
J=7.5 Hz, 2H), 8.12 (d, J=7.5 Hz, 2H);
(62.5 MHz, CDCl /TMS): d=45.3, 74.1, 109.6, 118.6, 123.8,
126.5, 129.3, 130.4, 146.3, 147.6, 148.0; anal. calcd. for
(268.27): C 67.16, H 4.51, N 10.44; found: C
67.08, H 4.46, N 10.37.
2-Phenylethanol (3n): H NMR (250 MHz, CDCl
d=2.89–2.94 (m, 2H), 3.45 (s, 1H), 3.82–3.88 (m, 2H), 7.30–
C NMR
1
3
3
TMS): d=36.9, 73.7, 123.8, 127.7, 128.1, 129.27, 136.1, 141.6,
46.9, 148.6; anal. calcd. for C H ClNO (277.70): C 60.55,
1
C H N O
15 12 2 3
1
4
12
3
H 4.36, N 5.04; found: C 60.62, H 4.32, N 5.11.
-(4-Bromophenyl)-2-(4-nitrophenyl)ethanol
H NMR (250 MHz, CDCl /TMS): d=1.18 (s, 1H), 2.98–
1
1
(3f):
/TMS):
3
1
3
1
3
3
7
.08 (m, 2H), 4.81–4.86 (m, 1H), 7.06–7.10 (m, 2H), 7.18–
.23 (m, 2H), 7.33–7.40 (m, 2H), 8.02–8.07 (m, 2H);
7.44 (m, 5H); C NMR (62.5 MHz, CDCl /TMS): d=39.3,
3
63.5, 126.4, 128.6, 129.2, 138.9.
1-(4-Nitrophenyl)propan-2-ol (3o): H NMR (250 MHz,
1
3
1
C NMR (62.5 MHz, CDCl /TMS): d=45.4, 74.2, 123.8,
3
127.5, 129.3, 130.5, 131.6, 137.5, 146.7, 148.1; anal. calcd. for
CDCl
/TMS): d=1.18 (s, 1H), 1.40 (d, J=7.5 Hz, 3H), 3.01
3
C H BrNO (322.15): C 52.20, H 3.75, N 4.35; found: C
(s, 2H), 4.29–4.33 (m, 1H), 7.21 (d, J=10.0 Hz, 2H), 8.06
(d, J=7.5 Hz, 2H); C NMR (62.5 MHz, CDCl /TMS): d=
3
14
12
3
1
3
52.14, H 3.70, N 4.28.
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ÞÞ
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FULL PAPERS
23.5, 48.5, 61.5, 123.8, 129.3, 148.1, 148.7; anal. calcd. for
anal. calcd. for C H N O (362.38): C 69.60, H 5.01, N 7.73;
21 18 2 4
C H NO (181.19): C 59.66, H 6.12, N 7.73; found: C 59.58,
found: C 69.51, H 4.92, N 7.66.
4-Formylphenyl benzoate (2w): H NMR (250 MHz,
CDCl /TMS): d=7.53–7.56 (m, 3H), 7.64 (t, J=7.5 Hz, 2H),
7.80 (t, J=7.5 Hz, 1H), 7.98 (s, 1H), 8.04 (d, J=7.5 Hz,
9
11
3
1
H 6.07, N 7.65.
-(1-Hydroxy-2-phenylethyl)benzaldehyde (3p): H NMR
250 MHz, CDCl /TMS): d=2.08 (s, 1H), 2.93–3.11 (m,
1
4
3
(
3
1
3
2
H), 4.97–5.02 (m, 1H), 7.17–7.20 (m, 2H), 7.26–7.35 (m,
2H), 10.04 (s, 1H); C NMR (62.5 MHz, CDCl
3
/TMS): d=
3
H), 7.52 (d, J=10.0 Hz, 2H), 7.86 (d, J=7.5 Hz, 2H),
122.5, 123.6, 127.4, 127.7, 128.0, 128.6, 128.7, 130.2, 133.7,
13
10.01 (s, 1H); C NMR (62.5 MHz, CDCl /TMS): d=46.1,
151.0, 171.1, 191.3: anal. calcd. for C14
74.33, H 4.46; found: C 74.27, H 4.39.
H
10
O
3
(226.23): C
3
7
1
4.8, 126.4, 127.0, 128.7, 129.5, 129.9, 137.1, 137.5, 150.5,
92.0; anal. calcd. for C H O (226.27); C 79.62, H 6.24;
3-[1-Hydroxy-2-(4-nitrophenyl)ethyl]phenyl
benzoate
1
5
14
2
1
found: C 79.55, H 6.20.
(3w): H NMR (250 MHz, CDCl /TMS): d=1.18 (s, 1H),
3
1
2
-(4-Nitrophenyl)-1-(thiophen-2-yl)ethanol (3q): HNMR
2.83–2.91 (m, 2H), 4.97–5.05 (m, 1H), 7.36–7.58 (m, 8H),
(250 MHz, CDCl /TMS): d=1.18 (s, 1H), 3.00 (s, 2H), 5.11–
7.89 (s, 1H), 8.04 (d, J=7.5 Hz, 2H), 8.13 (d, J=7.5 Hz,
3
1
3
2
1
1
6
H); C NMR (62.5 MHz, CDCl /TMS): d=45.2, 74.3,
5
7
.15 (m, 1H), 7.15–7.23 (m, 3H), 7.28 (d, J=5.0 Hz, 1H),
3
1
3
18.0, 119.8, 122.5, 123.5, 128.7, 129.6, 130.2, 133.9, 141.7,
46.1, 151.0, 165.0; anal. calcd. for C H NO (363.36): C
9.41, H 4.72, N 3.85; found: C 69.35, H 4.66, N 3.78.
-(1-Hydroxy-2,2,2-triphenylethyl)benzonitrile
H NMR (250 MHz,CDCl /TMS): d=2.00 (s, 1H), 4.70 (s,
.46 (d, J=10.0 Hz, 1H), 8.06 (d, J=7.5 Hz, 2H); C NMR
(62.5 MHz, CDCl /TMS): d=40.2, 69.1, 120.9, 123.6, 125.5,
21 17
5
3
1
27.2, 129.1, 143.3, 145.6, 148.0; anal. calcd. for C H NO S
12 11 3
4
(3x):
(
249.29): C 57.82, H 4.45, N 5.62; found: C 57.75, H 4.41, N
1
5
.54.
-(4-Methoxyphenyl)-1-(4-nitrophenyl)ethanol
H NMR (250 MHz, CDCl /TMS): d=1.18 (s, 1H), 2.82 (s,
3
1
H), 7.15 (s, 3H), 7.26–7.34 (m, 6H), 7.48–7.54 (m, 6H),
2
(3r):
13
1
8.21 (d, J=7.5 Hz, 2H), 8.44 (d, J=7.5 Hz, 2H); C NMR
62.5 MHz, CDCl /TMS): d=63.7, 84.8, 110.6, 118.9, 127.0,
3
(
1
H), 2.89 (s, 1H), 3.72 (s, 3H), 4.87 (s, 1H), 6.76–6.89 (m,
H), 7.34 (d, J=7.5 Hz, 2H), 7.99 (d, J=10.0 Hz, 2H);
3
1
28.5, 131.6, 131.7, 132.1, 146.9, 148.6; anal. calcd. for
4
13
C H NO (375.46): C 86.37, H 5.64, N 3.73; found: C 86.30,
C NMR (62.5 MHz, CDCl /TMS): d=47.3, 55.5, 75.6,
27 21
3
H 5.58, N 3.65.
1
13.7, 123.5, 127.5, 128.5, 130.8, 147.3, 150.1, 159.2; anal.
1
1
-(4-Nitrophenyl)-2,2-diphenylethanol (3y):
H NMR
calcd. for C H NO (273.28): C 65.92, H 5.53, N 5.13;
15
15
4
(
250 MHz, CDCl /TMS): d=1.18 (s, 1H), 2.81 (s, 1H), 7.23–
found: C 65.83, H 5.44, N 5.01.
-(1-Hydroxy-2-mesitylethyl)benzonitrile (3s): H NMR
250 MHz, CDCl /TMS): d=1.98 (s, 1H), 2.23–2.26 (m,
3
1
7.33 (m, 4H), 7.94–8.03 (m, 6H), 8.21 (d, J=7.5 Hz, 2H),
4
13
8
.50 (d, J=7.5 Hz, 2H); C NMR (62.5 MHz, CDCl /TMS):
3
(
3
d=62.3, 75.4, 115.9, 125.9, 127.8, 131.5, 131.7, 138.6, 148.7,
9
7
H), 2.82 (s, 1H), 2.90 (s, 1H), 4.93 (s, 1H), 6.81 (s, 2H),
13
155.2; anal. calcd. for C H NO (319.35): C 75.22, H 5.37,
2
0
17
3
.13 (d, J=7.5 Hz, 2H), 7.48 (d, J=7.5 Hz, 2H); C NMR
N 4.39; found: C 75.15, H 5.30, N 4.31.
-(1-Hydroxy-2,2-diphenylethyl)benzonitrile
H NMR (250 MHz, CDCl /TMS): d=1.18 (s, 1H), 4.66 (s,
(62.5 MHz, CDCl /TMS): d=20.9, 21.3, 40.9, 74.0, 108.6,
3
4
(3z):
1
19.4, 125.5, 128.1, 130.1, 132.1, 139.0, 147.9, 159.8; anal.
1
3
calcd. for C H NO (265.35): C 81.47, H 7.22, N 5.28;
18
19
1
H), 4.94 (s, 1H), 7.13–7.18 (m, 6H), 7.24 (s, 4H), 7.44 (d,
found: C 81.40, H 7.14, N 5.20.
-(4-Fluorophenyl)-1-(meta-tolyl)ethanol (3t): H NMR
250 MHz, CDCl /TMS): d=2.13–2.22 (m, 4H), 2.70–2.76
13
1
J=7.5 Hz, 2H), 7.62 (d, J=7.5 Hz, 2H);
C NMR
2
(
62.5 MHz, CDCl /TMS): d=63.0, 81.4, 11.5, 118.6, 125.9,
3
(
(
(
3
1
3
127.7, 127.8, 131.5, 131.7, 138.6, 145.2; anal. calcd. for
C H NO (299.37): C 84.25, H 5.72, N, 4.68; found: C 84.19,
m, 2H), 4.48 (s, 1H), 6.95–7.12 (m, 8H); C NMR
62.5 MHz, CDCl /TMS): d=21.4, 36.6, 65.1, 115.4, 124.0,
2
1
17
3
H 5.68, N 4.61.
-(4-nitrophenyl)-2-phenylpropan-1-ol (3aa):
250 MHz, CDCl /TMS): d=0.75–0.80 (m, 3H), 1.30 (s,
1
24.3, 127.7, 128.2, 132.2, 133.6, 138.1, 141.0, 161.8; anal.
1
1
H NMR
calcd. for C H FO (230.28): C 78.24, H 6.57; found: C
7
15
15
(
3
8.17, H 6.51.
1
H), 2.63–3.02 (m, 1H), 5.05 (m, 1H), 7.22–7.39 (m, 5H),
1-(4-Chlorophenyl)-2-(4-fluorophenyl)ethanol
(3u):
13
1
7.69 (d, J=7.5 Hz, 2H), 7.65 (d, J=7.5 Hz, 2H); CNMR
62.5 MHz, CDCl /TMS): d=16.5, 47.0, 84.6, 123.1, 127.8,
H NMR (250 MHz, CDCl /TMS): d=1.94 (s, 1H), 2.75 (s,
3
(
3
1
H), 2.83 (s, 1H), 4.52 (s, 1H), 6.88–6.98 (m, 2H), 7.15–7.24
13
127.9, 129.2, 129.6, 144.6, 149.2, 150.1; anal. calcd. for
C H NO (257.28): C 70.02, H 5.88, N 5.44; found: C 69.94,
(m, 6H). C NMR (62.5 MHz, CDCl /TMS): d=36.6, 64.2,
3
1
5
15
3
1
15.4, 128.1, 128.5, 129.8, 133.1, 134.5, 139.5, 161.8; anal.
H 5.81, N 5.38.
calcd. for C H ClFO (250.70): C 67.07, H 4.82; found: C
14
12
6
6.95, H 4.74.
N-(4-Formylphenyl)benzamide (2v): H NMR (250 MHz,
CDCl /TMS): d=7.42–7.61 (m, 3H), 7.82–7.91 (m, 4H), 8.08
1
3
Acknowledgements
1
3
(
d, J=7.5 Hz, 2H), 8.61 (s, 1H), 9.90 (s, 1H); C NMR
(
1
62.5 MHz, CDCl /TMS): d=119.1, 127.3, 128.8, 131.1,
3
The financial support of the Research Council of Shiraz Uni-
versity and the grant from the Iran National Elite Foundation
is gratefully acknowledged.
33.6, 134.3, 143.8, 166.3, 191.2; anal. calcd. for C H NO
14 11 2
(
6
225.24): C 74.65, H 4.92, N 6.22; found: C 74.56, H 4.87, N
.14.
N-{4-[1-Hydroxy-2-(4-nitrophenyl)ethyl]phenyl}benza-
1
mide (3v): H NMR (250 MHz, CDCl /TMS): d=1.60 (s,
3
1
H), 2.81–3.09 (m, 2H), 4.70–4.88 (m, 1H), 7.42–7.60 (m, References
5
H), 7.77–7.86 (m, 4H), 7.94–8.07 (m, 4H), 8.34 (s, 1H);
13
C NMR (62.5 MHz, CDCl /TMS): d=34.7, 73.3, 121.5,
[1] a) L. Pu, H.-B. Yu, Chem. Rev. 2001, 101, 757–824;
b) A. Fꢂrstner, Chem. Rev. 1999, 99, 991–1045; c) D.
3
121.8, 127.0, 129.6, 131.9, 133.9, 134.3, 136.1, 144.9, 162.7;
8
asc.wiley-vch.de
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

FULL PAPERS
Nickel-Catalyzed Reductive Benzylation of Aldehydes with Benzyl Halides
Guijarro, M. Yus, Tetrahedron 2000, 56, 1135–1138;
d) J.-S. Lee, R. Velarde-Ortiz, A. Guijarro, J. R. Wurst,
R. D. Rieke, J. Org. Chem. 2000, 65, 5428–5430; e) R.
Noyori, M. Kitamura, Angew. Chem. 1991, 103, 34–55;
Angew. Chem. Int. Ed. Engl. 1991, 30, 49–69; f) Y.
Ogawa, M. Mori, A. Saiga, K. Takagi, Chem. Lett.
Thadani, D. V. Smil, Org. Lett. 1999, 1, 1683–1686;
h) C. Qin, H. Wu, J. Cheng, X. Chen, X. Liu, W.
Zhang, W. Su, J. Ding, J. Org. Chem. 2007, 72, 4102–
4107; i) Y. He, C. Cai, Chem. Commun. 2011, 47,
12319–12321; j) G. Takahashi, E. Shirakawa, T. Tsuchi-
motoa, Y. Kawakami, Chem. Commun. 2005, 1459–
1461; k) L. Zhou, X. Du, R. He, Z. Ci, Z. Bao, Tetrahe-
dron Lett. 2009, 50, 406–408; l) J. Chen, X. Zhang, Q.
Feng, M. Luo, J. Organomet. Chem. 2006, 691, 470–474;
m) N. Miyaura, Synlett 2009, 2039–2050.
1
996, 1069–1083.
[
2] a) M. R. Luderer, W. F. Bailey, M. R. Luderer, J. D.
Fair, R. J. Dancer, M. B. Sommer, Tetrahedron: Asym-
metry 2009, 20, 981–1094; b) E. Fernꢃndez-Mateos, B.
Maciꢃ, M. Yus, Eur. J. Org. Chem. 2012, 3732–3736.
3] a) C.-S. Da, J.-R. Wang, X.-G. Yin, X.-Y. Fan, Y. Liu,
S.-L. Yu, Org. Lett. 2009, 11, 5578–5581; b) E. Fernꢃn-
dez-Mateos, B. Maci, M. Yus, Adv. Synth. Catal. 2013,
[
10] F. Zhang, Y. Liu, L. Xie, X. Xu, RSC Adv. 2014, 4,
[
1
7218–17221.
[
11] a) Y. Li, X.-S. Zhang, K. Chen, K.-H. He, F. Pan, B.-J.
Li, Z.-J. Shi, Org. Lett. 2012, 14, 636–639; b) F.-F.
Wang, C.-P. Luo, Y. Wang, G. Deng, L. Yang, Org.
Biomol. Chem. 2012, 10, 8605–8608; c) B.-J. Lia, Z.-J.
Shi, Chem. Sci. 2011, 2, 488–493.
3
55, 1249–1254; c) S. M. Manolikakes, M. Jaric, K. Kar-
aghiosoff, P. Knochel, Chem. Commun. 2013, 49, 2124–
126.
2
[
4] a) H. Schumann, J. Kaufmann, S. Dechert, H.-G.
Schmalz, Tetrahedron Lett. 2002, 43, 3507–3511; b) K.
Biswas, O. Prieto, P. J. Goldsmith, S. Woodward,
Angew. Chem. 2005, 117, 2272–2274; Angew. Chem.
Int. Ed. 2005, 44, 2232–2234; c) S. Alegre, M. Diꢄguez,
O. Pꢅmies, Tetrahedron: Asymmetry 2011, 22, 834–839.
5] a) L. Pu, Tetrahedron 2003, 59, 9873–9886; b) A. M.
DeBerardinis, M. Turlington, L. Pu, Org. Lett. 2008, 10,
[
[
[
12] a) E. P. Gillis, M. D. Burke, J. Am. Chem. Soc. 2008,
1
30, 14084–14085; b) H. Ihara, M. Suginome, J. Am.
Chem. Soc. 2009, 131, 7502–7503.
13] a) A. Fꢂrstner, N. Shi, J. Am. Chem. Soc. 1996, 118,
1
2349–12357; b) K. K. Majumdar, C.-H. Cheng, Org.
Lett. 2000, 2, 2295–2298.
[
14] a) S. Venkatraman, C.-J. Li, Org. Lett. 1999, 1, 1133–
1
135; b) A. Krasovskiy, C. Duplais, B. H. Lipshutz, J.
2709–2712; c) W. A. Nugent, Org. Lett. 2002, 4, 2133–
2136; d) B. D. Dangel, R. Polt, Org. Lett. 2000, 2, 3003–
3006; e) A. D. Wouters, D. S. Ludtke, Org. Lett. 2012,
14, 3962–3965; f) P. G. Cozzi, P. Kotrusz, J. Am. Chem.
Am. Chem. Soc. 2009, 131, 15592–15593; c) M. Kimura,
D. Nojiri, M. Fukushima, S. Oi, Y. Sonoda, Y. Inoue,
Org. Lett. 2009, 11, 3794–3797; d) B. Sam, T. P. Mont-
gomery, M. J. Krische, Org. Lett. 2013, 15, 3790–3793;
e) W. M. Czaplik, M. Mayer, A. Jacobi von Wangelin,
ChemCatChem 2011, 3, 135–138.
Soc. 2006, 128, 4940–4941; g) D.-X. Liu, L.-C. Zhang,
Q. Wang, C.-S. Da, Z.-Q. Xin, R. Wang, M. C. K. Choi,
A. S. C. Chan, Org. Lett. 2001, 3, 2733–2735; h) A. M.
DeBerardinis, M. Turlington, L. Pu, Angew. Chem.
[
15] a) D. A. Everson, R. Shrestha, D. J. Weix, J. Am.
Chem. Soc. 2010, 132, 920–921; b) D. A. Everson, B. A.
Jones, D. J. Weix, J. Am. Chem. Soc. 2012, 134, 6146–
2
2
011, 123, 2416–2418; Angew. Chem. Int. Ed. 2011, 50,
368–2370; i) M.-J. Jin, Y.-M. Kim, K.-S. Lee, Tetrahe-
6
1
159; c) S. Biswas, D. J. Weix, J. Am. Chem. Soc. 2013,
35, 16192–16197; d) A. H. Cherney, S. E. Reisman, J.
dron Lett. 2005, 46, 2695–2696; j) M. L. Richmond,
C. M. Sprout, C. T. Seto, J. Org. Chem. 2005, 70, 8835–
Am. Chem. Soc. 2014, 136, 14365–14368; e) C. E. I.
Knappke, S. Grupe, D. Gꢆrtner, M. Corpet, C. Gosmi-
ni, A. Jacobi von Wangelin, Chem. Eur. J. 2014, 20,
8
840; k) M. P. Sibi, L. M. Stanley, Tetrahedron: Asym-
metry 2004, 15, 3353–3356; l) Y.-C. Qin, L. Pu, Angew.
Chem. 2006, 118, 279–283; Angew. Chem. Int. Ed. 2006,
6
828–6842.
16] a) T. Leꢇn, A. Correa, R. Martin, J. Am. Chem. Soc.
013, 135, 1221–1224; b) A. Correa, R. Martin, J. Am.
4
5, 273–277; m) S.-L. Tseng, T.-K. Yang, Tetrahedron:
[
Asymmetry 2005, 16, 773–782; n) Z. Huang, H. Lai, Y.
Qin, J. Org. Chem. 2007, 72, 1373–1378; o) A. L. Braga,
R. M. Rubim, H. S. Schrekker, L. A. Wessjohann,
M. W. G. de Bolster, G. Zenia, J. A. Sehnema, Tetrahe-
dron: Asymmetry 2003, 14, 3291–3295.
2
Chem. Soc. 2014, 136, 7253–7256; c) T. Fujihara, K.
Nogi, T. Xu, J. Terao, Y. Tsuji, J. Am. Chem. Soc. 2012,
1
34, 9106–9109; d) D. A. Everson, D. J. Weix, J. Org.
Chem. 2014, 79, 4793–4798.
[
6] H. Nakamura, H. Iwama, Y. Yamamoto, J. Am. Chem.
Soc. 1996, 118, 6641–6647.
7] a) S. Oi, M. Moro, Y. Inoue, Organometallics 2001, 20,
[
[
[
[
17] S. Z. Tasker, E. A. Standley, T. F. Jamison, Nature 2014,
5
09, 299–309.
18] T. Moragas, A. Correa, R. Martin, Chem. Eur. J. 2014,
0, 8242–8258.
[
1
036–1037; b) S. Chakraborty, J. A. Krause, H. Guan,
2
Organometallics 2009, 28, 582–586.
19] Z. Tan, X. Wan, Z. Zang, Q. Qian, W. Deng, H. Gong,
Chem. Commun. 2014, 50, 3827–3830.
20] a) A. A. C. Braga, N. H. Morgon, G. Ujaque, A.
[8] Z. Dai, C. Zhu, M. Yang, Y. Zheng, Y. Pan, Tetrahe-
dron: Asymmetry 2005, 16, 605–608.
[
9] a) J. Bouffard, K. Itami, Org. Lett. 2009, 11, 4410–4413;
b) H. Zheng, Q. Zhang, J. Chen, M. Liu, S. Cheng, J.
Ding, H. Wu, W. Su, J. Org. Chem. 2009, 74, 943–945;
c) H.-F. Duan, J.-H. Xie, W.-J. Shi, Q. Zhang, Q.-L.
Zhou, Org. Lett. 2006, 8, 1479–1481; d) T. Zou, S.-S. Pi,
J.-H. Li, Org. Lett. 2009, 11, 453–456; e) M. Kuriyama,
R. Shimazawa, T. Enomoto, R. Shirai, J. Org. Chem.
Liedos, F. Maseras, J. Organomet. Chem. 2006, 691,
4
459–4466; b) A. A. C. Braga, N. H. Morgon, G.
Ujaque, F. Maseras, J. Am. Chem. Soc. 2005, 127, 9298–
9307.
[21] Y. Dai, F. Wu, Z. Zang, H. You, H. Gong, Chem. Eur.
J. 2012, 18, 808–812.
2
008, 73, 6939–6942; f) T. Yamamoto, T. Ohta, Y. Ito,
[22] A. Correa, T. Leꢇn, R. Martin, J. Am. Chem. Soc. 2014,
136, 1062–1069.
Org. Lett. 2005, 7, 4153–4155; g) R. A. Batey, A. N.
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
9
ÞÞ
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FULL PAPERS
[
[
[
23] H.-W. Shih, M. N. V. Wal, R. L. Grange, D. W. C. Mac-
Millan, J. Am. Chem. Soc. 2010, 132, 13600–13603.
24] W. R. Ruby, Preparation of 4-nitrostilbenes. U.S. Patent
[26] E. Carmona, J. M. Marin, M. Paneque, M. L. Poveda,
Organometallics 1987, 6, 1757–1765.
[27] A. Metzger, S. Bernhardt, G. Manolikakes, P. Knochel,
Angew. Chem. 2010, 122, 4769–4773; Angew. Chem.
Int. Ed. 2010, 49, 4665–4668.
3
,514,495A, 1970.
25] a) S. Wang, Q. Qian, H. Gong, Org. Lett. 2012, 14,
352–3355; b) F. Wu, W. Lu, Q. Qian, Q. Ren, H.
3
Gong, Org. Lett. 2012, 14, 3044–3047.
10
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ÝÝ
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ÞÞ
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