Oxovanadium(v)-catalyzed deoxygenative homocoupling reaction of alcohols

Article abstract of DOI:10.1039/c9nj01905g

Oxovanadium(v)-catalyzed transformation of alcohols in the presence of hydrazine derivatives was demonstrated. The direct hydrazination reaction of 1,3-diphenylprop-2-en-1-ol with 1,1-diphenylhydrazine in the presence of VO(OSiPh₃)₃ as a catalyst and MS3A as a dehydrating reagent proceeded to afford the corresponding hydrazination product. On the contrary, the utilization of 1,1-dimethylhydrazine instead of 1,1-diphenylhydrazine was found to induce the deoxygenative homocoupling reaction of the allyl alcohol to give the corresponding 1,5-diene as a major product. In addition to the deoxygenative homocoupling product, the allyl amine into which aniline was introduced was also obtained by using 1,2-diphenylhydrazine in the reaction of 1,3-diphenyl-2-methylprop-2-en-1-ol. Oxovanadium(v)-catalyzed deoxygenative homocoupling reaction of benzyl alcohols could also be performed in the presence of 1,1-dimethylhydrazine.

Full text of DOI:10.1039/c9nj01905g

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Oxovanadium(V)-Catalyzed Deoxygenative Homocoupling
Reaction of Alcohols†
Takashi Sakuramoto,a Yosuke Donaka,b Mamoru Tobisu a and Toshiyuki Moriuchi *a,b
Received 00th January 20xx,
Accepted 00th January 20xx
Oxovanadium(V)-catalysed transformation of alcohols in the presence of hydrazine derivatives was demostrated. Direct
hydrazination reaction of 1,3-diphenylprop-2-en-1-ol with 1,1-diphenylhydrazine in the presence of VO(OSiPh3)3 as a catalyst
and MS3A as a dehydrating reagent proceeded to afford the corresponding hydrazination product. On the contrary, the
utilization of 1,1-dimethylhydrazine instead of 1,1-diphenylhydrazine was found to induce the deoxygenative homocoupling
reaction of the allyl alcohol to give the corresponding 1,5-diene as a major product. In addition to the deoxygenative
homocoupling product, the allyl amine into which aniline was introduced was also obtained by using 1,2-diphenylhydrazine
in the reaction of 1,3-diphenyl-2-methylprop-2-en-1-ol. Oxovanadium(V)-catalyzed deoxygenative homocoupling reaction
of benzyl alcohols could be also performed in the presence of 1,1-dimethylhydrazine.
DOI: 10.1039/x0xx00000x
synthesis of coupling products through vanadium-catalysed
deoxygenative homocoupling reaction of alcohols has not been
achieved. Generally, a reducing reagent is required to promote
Introduction
Development of synthetic methods for compounds containing
1,5-diene structure is an important research topic1 because
compounds containing 1,5-diene structure serve as precursors
for the synthesis of natural products.2 The utilization of allyl
alcohols, which are provided in bulk and obtained cheaply, is
regarded as one of a reliable strategy for synthesis of 1,5-diene
structures. Formation of 1,5-diene structures from allylic
acetates have been reported,1c-e wherein two steps are needed
to synthesize 1,5-diene structures from allyl alcohols and
undesired by-products are given. From the view point of
biomass conversion, deoxygenative reaction is focused on. For
example, deoxygenative coupling of 2-arylethanols catalyzed by
Ir, Ru, or Mn catalyst has been reported.3 Synthesis of 1,5-diene
structure through deoxygenative homocoupling reaction of allyl
the catalytic deoxygenative coupling reaction.1 The
deoxygenative homocoupling reaction of alcohols utilizing
organic reductants has not been performed. We have already
reported oxovanadium(V)-catalysed direct amination of allyl
alcohols.7 During the development of the vanadium-catalyzed
transformation of allyl alcohols, hydrazine derivatives were
found to serve as reductants to induce the deoxygenative
homocoupling reaction of allyl alcohols. From these points of
view, we herein report oxovanadium(V)-catalysed direct
hydrazination of allyl alcohol and deoxygenative homocoupling
reaction of alcohols depending on hydrazine derivatives.
Results and discussion
1b
alcohols have been also demonstrated by using TiCl3,1a NbCl5
or La1f. However, addition of metal salts is necessary in these
reactions.
Our study began by evaluating the effect of hydrazine
derivatives in oxovanadium(V)-catalysed direct hydrazination of
allyl alcohols. The reaction of 1,3-diphenylprop-2-en-1-ol (1a)
with 1,1-diphenylhydrazine (1,1-DPH) in the presence of
VO(OSiPh3)3 (20 mol%) as a catalyst and MS3A (0.2 g) as a
The utilization of oxophilicity of vanadium compounds is
regarded as one of useful methods for deoxygenation of
alcohols.4 Actually, Kataoka and Tani reported vanadium(II)-
induced reductive coupling reaction of ketones.5 Also, Nicholas
group demonstrated the deoxygenative homocoupling reaction
of alcohols by using oxovanadium(V) complexes.6 In this
reaction, however, ketones were produced as by-products
through oxidation of alcohols used as substrates. Selective
VO(OSiPh3)3 20 mol%
MS3A 0.2 g
OH
Ph
Ph
N
+
Ph
toluene, N2, 100 ºC, 24 h
NH2
Ph
1a
0.20 mmol
1,1-DPH
100 mol%
Ph
N
Ph
Ph
Ph
Ph
O
a. Department of Applied Chemistry, Graduate School of Engineering, Osaka
University, Yamada-oka, Suita, Osaka 565-0871, Japan.
b. Present address: Division of Molecular Materials Science, Graduate School of
Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585,
Japan.
Ph
NH
+
+
Ph
Ph
Ph
Ph
2a
49%
3a
4a
13%
0%
†
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
Scheme 1 Direct hydrazination reaction of allyl alcohol 1a with 1,1-DPH.
DOI: 10.1039/x0xx00000x
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The effect of oxovanadium compounds was examined in the
deoxygenative homocoupling reaction of allyl alcohol (Tables 1
View Article Online
DOI: 10.1039/C9NJ01905G
VO(OSiPh3)3 20 mol%
MS3A 0.2 g
OH
Ph
+
N
Ph
toluene, N2, 100 ºC, 24 h
NH2
and 2). Allyl alcohol 1a was converted to 1,5-diene 3a and
ketone 4a in the presence of VO(OiPr)3 as a catalyst, N,N-
diisopropylethylamine (iPr2EtN) as a base and MS3A as a
dehydrating reagent at 100 °C (entry 1). The deoxygenative
homocoupling reaction was not performed in the absence of
VO(OiPr)3 (entry 2), indicating that the oxovanadium(V)
compound plays an important role in the deoxygenative
homocoupling reaction of allyl alcohol. The catalytic reaction
1a
0.20 mmol
1,1-DMH
100 mol%
Ph
Ph
Ph
Ph
O
N
NH
+
+
Ph
Ph
10
11
12
13
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Ph
Ph
2b
3a
4a
52%
6%
0%
i
Scheme 2 Deoxygenative homocoupling reaction of allyl alcohol 1a in the presence
of 1,1-DMH.
without Pr2EtN resulted in a lower yield (entry 3). MS3A was
found to serve as a key role as dehydrating reagent to remove
generated water (entry 4). The deoxygenative homocoupling
reaction of 1a proceeded successfully even at 80 °C (entry 5).
Reducing the reaction temperature to 50 °C caused a decrease
in the yield of 3a (entry 6). The utilization of VO(OSiPh3)3 instead
of VO(OiPr)3 led to lower yield than VO(OiPr)3, (Table 2, entries
1 and 2). Oxovanadium(IV) compound VO(acac)2 also showed
similar reactivity (entry 3). By using low-valent VCl3, the
formation of the oxidized product 4a could be suppressed a
little (entry 4).
To improve the yield of 1,5-diene 3a, organic reductants for
the deoxygenative homocoupling reaction of allyl alcohol 1a
was investigated. Although the use of N,N’-diphenyl-p-
phenylenediamine (DPPDA) or ascorbic acid did not show an
enhanced yield of 3a (Table 3, entries 1-3) hydrazine derivatives
dehydrating reagent at 100 °C was found to afford the
corresponding allyl hydrazine 2a in 49% yield as a major product
with the deoxygenative homocoupling product 1,5-diene 3a in
13% yield (Scheme 1). On the contrary, the deoxygenative
homocoupling reaction of allyl alcohol was occurred instead of
the hydrazination reaction in the case of 1,1-dimethylhydrazine
(1,1-DMH), resulting in the formation of 1,5-diene 3a in 52%
yield (dl/meso = 1:1) as a major product, wherein a small
amount of E-chalcone (4a), the oxidized product of allyl alcohol
1a, was obtained as a by-product (Scheme 2).
Table 1 The vanadium-catalyzed deoxygenative homocoupling reaction of
1,3-diphenylprop-2-en-1-ol (1a).a,b
VO(OiPr)3 20 mol%
iPr2EtN 100 mol%
Ph
Ph
Ph
Ph
OH
Ph
O
MS3A 0.2 g
Table 3 The vanadium-catalyzed deoxygenative homocoupling reaction of
1,3-diphenylprop-2-en-1-ol (1a) in the presence of reductants.a,b
+
toluene, N2, temp., 16 h
Ph
Ph
Ph
1a
3a
4a
VO(OiPr)3
iPr2EtN
Yield of 3ac
Yield of 4a
reductant
MS3A 0.2 g
Entry
Reaction conditions
at 100 ºC
Ph
Ph
Ph
Ph
OH
Ph
O
(%)
(%)
+
1
2
3
4
5
6
45
0
30
0
toluene, N2, 100 ºC, 16 h
Ph
Ph
Ph
without VO(OiPr)3 at 100 ºC
without iPr2EtN at 100 ºC
without MS3A at 100 ºC
at 80 ºC
1a
3a
4a
12
16
46
5
trace
13
28
5
VO(OiPr)3 iPr2EtN Yield of 3ac Yield of 4a
reductant (mol%)
Entry
(mol %) (mol %)
(%)
(%)
31
1
none
20
20
20
20
20
20
10
5
100
100
100
100
0
45
38
42
54
62
49
53
50
45
65
65
69
73
31
at 50 ºC
2
DPPDA (50 mol%)
24
29
15
7
a Reaction conditions: 0.20 mmol of 1,3-diphenylprop-2-en-1-ol (1a), 20
3
ascorbic acid (50 mol%)
1,1-DMH (50 mol%)
1,1-DMH (50 mol%)
1,1-DMH (100 mol%)
1,1-DMH (50 mol%)
1,1-DMH (50 mol%)
1,1-DMH (50 mol%)
1,2-DPH (50 mol%)
1,2-DPH (50 mol%)
1,2-DPH (50 mol%)
1,2-DPH (50 mol%)
1,2-DPH (50 mol%)
mol% of VO(OiPr)3, 100 mol% of iPr2EtN, 0.2 g MS3A, 1.0 mL toluene, under
b
c
4
nitrogen atmosphere. The yield was determined by 1H NMR. NMR yield
(%) = [product (mmol) x 2 / substrate (mmol)] x 100.
5
6
0
11
10
10
12
14
12
11
11
trace
Table 2 The effect of vanadium catalyst for deoxygenative homocoupling
reaction of 1,3-diphenylprop-2-en-1-ol (1a).a,b
7
0
8
0
V cat. 20 mol%
9
3
0
iPr2EtN 100 mol%
Ph
Ph
Ph
Ph
10
11
12
13
14
20
20
20
20
20
100
50
20
10
0
OH
Ph
O
MS3A 0.2 g
+
toluene, N2, 100 ºC, 16 h
Ph
Ph
Ph
1a
3a
4a
Yield of 3ac
Yield of 4a
Entry
V cat.
(%)
(%)
a Reaction conditions: 0.20 mmol of 1,3-diphenylprop-2-en-1-ol (1a),
VO(OiPr)3, iPr2EtN, 0.2 g MS3A, 1.0 mL toluene, under nitrogen atmosphere.
1
2
3
4
VO(OiPr)3
VO(OSiPh3)3
VO(acac)2
VCl3
45
13
46
44
30
7
b The yield was determined by 1H NMR. c NMR yield (%) = [product (mmol) x
2 / substrate (mmol)] x 100.
25
17
H
N
H
a Reaction conditions: 0.20 mmol of 1,3-diphenylprop-2-en-1-ol (1a), 20
N
N
N
mol% of VO(OiPr)3, 100 mol% of iPr2EtN, 0.2 g MS3A, 1.0 mL toluene, under
NH2
H
N
H
b
c
nitrogen atmosphere. The yield was determined by 1H NMR. NMR yield
DPPDA
1,1-DMH
1,2-DPH
(%) = [product (mmol) x 2 / substrate (mmol)] x 100.
2 | J. Name., 2012, 00, 1-3
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were disclosed to be effective for the deoxygenative
homocoupling reaction. When the
The applicability for the deoxygenative hVoiemwoArctioclue pOlnilninge
deoxygenative reaction was investigated by using 1,1D-DOMI: 1H0.1a0s39a/C9reNdJ0u1c9t0a5nGt
homocoupling reaction of 1a was performed with 50 mol% of (Table 4). Starting from the α-methylated alcohol 1b, 1,5-diene
1,1-DMH, 1,5-diene 3a was obtained in 54% yield and the yield 3b (dl/meso = 1:1) was obtained in 46% yield (entry 1). This
of 4a got lower than the condition without 1,1-DMH (entry 4). catalytic system could be applied to the deoxygenative
The reaction without iPr2EtN proceeded well to afford 1,5-diene homocoupling reaction of diphenylmethanol (1c) to give the
3a in 62% yield as shown in entry 5. However, increasing the desired coupling product 3c in 65% yield (entry 2). The catalytic
amount of 1,1-DMH to 100 mol% resulted in lower yield (entry deoxygenative homocoupling reaction of 1-phenylethan-1-ol
6). A decrease in the catalyst loading of VO(OiPr)3 resulted in a (1d) proceeded moderately to yield the corresponding coupling
decrease in the yield of 3a (entries 7-9). The utilization of 1,2- product 3d (dl/meso = 1:1) as shown in entry 3. 9H,9'H-9,9'-
diphenylhydrazine (1,2-DPH) instead of 1,1-DMH was found to Bifluorene (3e) could be obtained in 36% yield from 9H-fluoren-
be efficacious to the deoxygenative homocoupling reaction in 9-ol (1e) by using this catalytic system.
5
6
7
8
9
10
11
12
13
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the condition with 100 mol% of iPr2EtN (entry 10). The yield of
3a was improved by reducing the amount of iPr2EtN in the case
Table 4 Substrate scope in the vanadium-catalyzed deoxygenative
homocoupling reaction of alcohols.a,b
of 1,2-DPH (entries 11 and 12). Eventually, 1,5-Diene 3a was
VO(OiPr)3 20 mol%
obtained in 73 % yield in the condition with 10 mol% of iPr2EtN
1,1-DMH 50 mol%
MS3A 0.2 g
i
R
R
R'
R'
(entry 13). However, the reaction without Pr2EtN showed a
OH
R'
O
+
significant decrease in the yield of 3a (entry 14). It is worth
mentioning that gram-scale oxovanadium(V)-catalysed
deoxygenative homocoupling reaction of 1a with 1,2-DPH as a
reductant could be performed to afford the 1,5-diene 3a in 70%
isolated yield (Scheme 3).
toluene, N2, 140 ºC, 16 h
R
R
R'
O
1
3
4
Substrate
OH
Products
Ph
Entry
Ph
Ph
VO(OiPr)3 20 mol%
iPr2EtN 10 mol%
1,2-DPH 50 mol%
1
2
3
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
OH
Ph
O
MS3A 0.2 g
1b
3b
4b
13%
+
46%c
toluene (25 mL), N2,
100 ºC, 20 h
Ph
Ph
Ph
(dl/meso = 1:1)
1a
3a
4a
10%
Ph
Ph
Ph
OH
O
5.0 mmol
(1.05 g)
70%
(1.75 mmol, 677 mg) (NMR yield)
Ph
Ph
Ph
Ph
Ph
Scheme 3 Gram-scale oxovanadium(V)-catalyzed deoxygenative
homocoupling reaction of allyl alcohol 1a in the presence of 1,2-DPH.
1c
3c
65%c
4c
26%
To explore the validity of this catalytic system, the substrate
scope of allyl alcohols was examined under the optimized
reaction conditions as shown in entry 13 of Table 3. When 1,3-
diphenyl-2-methylprop-2-en-1-ol (1b) was used as allyl alcohol,
1,5-diene 3b (dl/meso = 1:1) was given in 26% yield (Scheme 4).
In addition to the deoxygenative homocoupling product, allyl
amine 5 into which aniline was introduced was also detected as
a by-product in 23% yield. In this reaction, 1,2-DPH appears to
serve as an aniline source.
Ph
Ph
OH
O
Ph
Ph
1d
3d
4d
5%
42%c
(dl/meso = 1:1 )
OH
O
4
VO(OiPr)3 20 mol%
iPr2EtN 10 mol%
MS3A 0.2 g
1e
3e
4e
trace
OH
36%c
H
N
+
N
H
a Reaction conditions: 0.20 mmol of alcohols, 20 mmol% of VO(OiPr)3, 50
Ph
Ph
toluene, N2, 100 ºC, 16 h
mmol% of 1,1-DMH, 0.2
g
MS3A, 1.0 mL toluene, under nitrogen
b
c
atmosphere. The yield was determined by 1H NMR. NMR yield (%) =
1b
0.20 mmol
1,2-DPH
[product (mmol) x 2 / substrate (mmol)] x 100.
50 mol%
O
Ph
Ph
Ph
Ph
To gain insight into the reaction mechanism, 51V NMR
measurement was examined (Fig. S1, ESI). The 51V chemical shift
NH
Ph
+
+
Ph
Ph
Ph
i
of VO(OiPr)3 in the presence of 1,2-DPH, Pr2NEt and MS3A in
toluene-d8 was detected at -630 ppm. Increasing the
temperature to 100 °C, the peak intensity of VO(OiPr)3
decreased, indicating that V(V) species was reduced to a low-
valent vanadium species, such as V(IV) or V(III). Proposed
catalytic cycle for deoxygenative homocoupling reaction of
3b
4b
5
26%
16%
23%
Scheme 4 Deoxygenative homocoupling reaction of allyl alcohol 1b in the
presence of 1,2-DPH.
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solvent signal as an internal standard. High resVoieluwtAiortinclemOnalisnes
O
H
N
DOI: 10.1039/C9NJ01905G
spectra (HRMS) were measured on
a JEOL JMS-700
V(V)
N
H
O
O
spectrometer using electron impact (EI) or fast atom
bombardment (FAB) mode. Column chromatography was
performed with SiO2 (Wakogel C-200 or Silica Gel 60 (spherical)
NH2).
N
N
OH
V(IV)
OH
Materials
or
O
10
11
12
13
14
15
16
17
18
19
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R1
R2
Allyl alcohol 1b (65564-83-2)7 and VO(OSiPh3)38 were prepared
according to the literature method. The other reagents and
solvents were purchased from commercial sources and were
further purified by the standard methods, if necessary.
V(III)
OH
V(III)
OH
O
V(IV)
O
R1
R2
Procedure for direct hydrazination of allyl alcohol 1a with 1,1-
diphenylhydrazine.
In a 5 mL screw-capped vial, 1,3-diphenylprop-2-ene-1-ol (1a)
(42 mg, 0.20 mmol), 1,1-diphenylhydrazine (1,1-DPH) (33 μL,
0.20 mmol), VO(OSiPh3)3 (36 mg, 0.040 mmol), MS3A (0.2 g) and
toluene (2.0 mL) were placed at a glove box filled with nitrogen.
The mixture was stirred at 100 °C for 24 h, followed by
treatment with water, and extraction with ether. The organic
layer was dried over Na2SO4, filtrated, and evaporated.
R1
R1
R2
R2
R1
R2
R1
R2
Scheme 5 Proposed catalytic cycle for deoxygenative homocoupling
reaction of alcohols.
alcohols based on the above-mentioned results is illustrated in
Scheme 5. The reaction of the reduced V(III) species, which is
likely to be generated by the reaction of the V(V) species with
1,2-DPH, with the alcohol produces the V(IV) species and the
1
Triphenyl methane was added as an internal standard, and H
NMR analysis was performed to determine an NMR yield.
(E)-2-(1,3-Diphenylallyl)-1,1-diphenylhydrazine (2a). 1H
NMR (400 MHz, CDCl3) δ 7.46-6.99 (m, 20H), 6.47-6.38 (m, 2H),
4.67 (d, J = 5.9 Hz, 1H), 4.40 (br s, 1H); 13C NMR (100 MHz, CDCl3)
147.8, 141.1, 137.0, 131.9, 130.9, 129.2, 128.7, 128.6, 128.1,
127.9, 127.7, 126.6, 122.4, 120.7, 64.9 ppm; HRMS (FAB) m/z
Calcd. for C27H24N2 (M+), 376.1934; Found, 376.1944.
radical
intermediate,
affording
the
deoxygenative
homocoupling product. The V(IV) species disproportionates to
give the V(V) and V(III) species. The regenerated V(III) species
begins a new catalytic cycle.
Procedure for deoxygenative homocoupling reaction of alcohols.
Conclusions
In a 5 mL screw-capped vial, alcohol (1) (0.20 mmol), 1,1-
dimethylhydrazine (1,1-DMH) (7.6 μL, 0.10 mmol), VO(OiPr)3
(9.2 μL, 0.040 mmol), MS3A (0.2 g) and toluene (1.0 mL) were
placed at a glove box filled with nitrogen. The mixture was
stirred at 100 or 140 °C for 24 h, followed by filtration through
Celite® with ethyl acetate. The solvent was removed. Triphenyl
methane was added as an internal standard, and 1H NMR
analysis was performed to determine an NMR yield.
Catalytic direct hydrazination of allyl alcohol and deoxygenative
homocoupling reaction of alcohols depending on hydrazine
derivatives were performed by utilizing oxovanadium(V)
catalysts. The oxovanadium(V)-catalysed reaction of 1,3-
diphenylprop-2-en-1-ol with 1,1-diphenylhydrazine was found
to afford the corresponding allyl hydrazine as a major product
whereas the utilization of 1,1-dimethylhydrazine instead of 1,1-
diphenylhydrazine induced the deoxygenative homocoupling
reaction of the allyl alcohol to give the corresponding 1,5-diene
as a major product. Furthermore, gram-scale oxovanadium(V)-
catalysed deoxygenative homocoupling reaction proceeded
1,3,4,6-Tetraphenyl-1,5-hexadiene [CAS Registry No.
204578-86-9] (3a). Mixture of stereoisomers: 1H NMR (400
MHz, CDCl3) δ 7.33-7.07 (m, 20H), 6.57-6.51 (m, 1H), 6.40 (d, J =
15.8 Hz, 1H), 6.34-6.28 (m, 1H), 6.20 (d, J = 15.8 Hz, 1H), 3.92-
3.85 (m, 2H); 13C NMR (100 MHz, CDCl3) 142.6, 142.4, 137.5,
137.4, 132.1, 131.9, 131.3, 131.1, 128.6, 128.42, 128.37, 128.35,
128.32, 128.2, 127.1, 127.0, 126.5, 126.2, 126.14, 126.09, 55.3,
55.2 ppm; HRMS (EI) m/z Calcd. for C30H26 (M+), 386.2029;
Found, 386.2025.
successfully.
Oxovanadium(V)-catalyzed
deoxygenative
homocoupling reaction of benzyl alcohols could be also
performed in the presence of 1,1-dimethylhydrazine. Studies on
the reaction mechanism and synthetic versatility are now in
progress.
Experimental
2,5-Dimethyl-1,3,4,6-tetraphenyl-1,5-hexadiene
(3b).
Mixture of stereoisomers: 1H NMR (400 MHz, CDCl3) δ 7.41-7.05
(m, 18H), 6.91-6.89 (m, 2H), 6.72 (s, 1H), 6.35 (s, 1H), 4.29 (s,
1H), 4.16 (s, 1H), 1.78 (s, 3H), 1.65 (s, 3H); 13C NMR (100 MHz,
CDCl3) 142.0, 141.0, 140.2, 139.0, 138.28, 138.26, 129.0, 128.8,
General
1H NMR and 13C NMR spectra were recorded in CDCl3 on a JEOL
JNM-ECS 400 (400 and 100 MHz, respectively) spectrometer.
Chemical shifts are given in δ (ppm) relative to the residual
4 | J. Name., 2012, 00, 1-3
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128.7, 128.5, 128.1, 127.99, 127.95, 127.8, 127.5, 126.7, 126.2,
126.1, 126.0, 125.9, 56.7, 56.0, 16.1, 14.5 ppm; HRMS (EI) m/z
Calcd. for C32H30 (M+), 414.2348; Found, 414.2340.
ARTICLE
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Conflicts of interest
There are no conflicts to declare.
View Article Online
DOI: 10.1039/C9NJ01905G
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1,1,2,2-Tetraphenyl-ethane [CAS Registry No. 632-50-8]
(3c). 1H NMR (400 MHz, CDCl3) δ 7.17 (d, J = 7.3 Hz, 8H), 7.11 (t,
J = 7.3 Hz, 8H), 7.01 (t, J = 7.3 Hz, 4H), 4.77 (s, 2H); 13C NMR (100
MHz, CDCl3) 143.4, 128.5, 128.1, 125.8, 56.3 ppm; HRMS (EI)
m/z Calcd. for C26H22 (M+), 334.1716; Found, 334.1718.
Acknowledgements
Thanks are due to the Analytical Center, Graduate School of
Engineering, Osaka University.
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Notes and references
2,3-Diphenyl-buthane [CAS Registry No. 5789-35-5] (3d).
Mixture of stereoisomers: 1H NMR (400 MHz, CDCl3) δ 7.34-7.00
(m, 20H), 2.98-2.90 (m, 1H), 2.84-2.76 (m, 1H), 1.28 (d, J = 6.9
Hz, 3H), 1.02 (d, J = 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) 146.5,
145.8, 128.3, 127.8, 127.7, 127.6, 126.0, 125.7, 47.2, 46.4, 21.0,
17.9 ppm; HRMS (EI) m/z Calcd. for C16H18 (M+), 210.1403;
Found, 210.1406.
1
(a) J. E. McMurry and M. Silvestri, J. Org. Chem., 1975, 40,
2687-2688; (b) M. Sato and K. Oshima, Chem. Lett., 1982, 11,
157-160; (c) S. Sasaoka, T. Yamamoto, H. Kinoshita, K. Inomata
and H. Kotake, Chem. Lett., 1985, 14, 315-318; (d) J. Yoshida,
H. Funahashi, H. Iwasaki and N. Kawabata, Tetrahedron Lett.,
1986, 27, 4469-4472; (e) Y. Masuyama, K. Maekawa, T.
Kurihara and Y. Kurusu, Bull. Chem. Soc. Jpn., 1991, 64, 2311-
2313; (f) T. Nishino, Y. Nishiyama and N. Sonoda, Bull. Chem.
Soc. Jpn., 2003, 76, 635-641.
For reviews see: (a) J. A. Marshall, Synthesis, 1971, 1971, 229-
235; (b) N. S. Sheikh, Org. Biomol. Chem., 2014, 12, 9492-
9504; (c) J. Adrian, L. J. Gross and C. B. W. Stark, Beilstein J.
Org. Chem., 2016, 12, 2104-2123; (d) S. Katayama, T. Koge, S.
Katsuragi, S. Akai and T. Oishi, Chem. Lett., 2018, 47, 1116-
1118.
9H,9'H-9,9'-Bifluorene [CAS Registry No. 1530-12-7] (3e).
2
1H NMR (400 MHz, CDCl3) δ 7.69-6.97 (m, 16H), 4.85 (s, 2H); 13
C
NMR (100 MHz, CDCl3) 144.7, 141,7, 127.4, 126.9, 124.2, 119.8,
49.9 ppm; HRMS (FAB) m/z Calcd. for C26H18 (M+), 330.1409;
Found, 330.1410.
3
4
(a) Y. Obora, Y. Anno, R. Okamoto, T. Matsu-ura and Y. Ishii,
Angew. Chem. Int. Ed., 2011, 50, 8618-8622; (b) S. Manojveer,
S. J. K. Forrest and M. T. Johnson, Chem. Eur. J., 2018, 24, 803-
807; (c) Y. Wang, Z. Shao, K. Zhang and Q. Liu, Angew. Chem.
Int. Ed., 2018, 57, 15143-15147.
For reviews see: (a) T. Hirao, Chem. Rev., 1997, 97, 2707-2724;
(b) P. P. Reddy, C. Y. Chu, D. R. Hwang, S. K. Wang and B. J.
Uang, Coord. Chem. Rev., 2003, 237, 257-269; (c) J. A. L. da
Silva, J. J. R. F. da Silva and A. J. L. Pombeiro, Coord. Chem.
Rev., 2011, 255, 2232-2248; (d) D. Wischang, O. Brücher and
J. Hartung, Coord. Chem. Rev., 2011, 255, 2204-2217; (e) S.
Takizawa, H. Groger and H. Sasai, Chem. Eur. J., 2015, 21,
8992-8997.
Procedure for a gram scale deoxygenative homocoupling reaction
of allyl alcohol 1a
In a 100 mL three-necked flask with a reflux condenser, 1,3-
diphenylprop-2-ene-1-ol (1a) (1.1 g, 5.0 mmol), 1,2-
diphenylhydrazine (1,2-DPH) (0.46 g, 2.5 mmol), VO(OiPr)3 (0.23
i
mL, 1.0 mmol), Pr2EtN (87 μL, 0.50 mmol), MS3A (5.0 g) and
toluene (25 mL) were placed at a glove box filled with nitrogen.
The mixture was stirred at 100 °C for 20 h, followed by filtration
through Celite® with ethyl acetate. The solvent was removed.
The residue was heated under a reduced pressure to remove
azobenzene and 1,2-diphenylhydrazine. The residue
chromatographed on a silica gel column eluting with hexane
and chloroform (7/3, v/v) to give 677 mg (70% yield) of 3a
5
6
(a) Y. Kataoka, I. Makihira, H. Akiyama and K. Tani,
Tetrahedron Lett., 1995, 36, 6495-6498; (b) Y. Kataoka, H.
Akiyama, I. Makihira and K. Tani, J. Org. Chem., 1996, 61,
6094-6095; (c) Y. Kataoka, H. Akiyama, I. Makihira and K. Tani,
J. Org. Chem., 1997, 62, 8109-8113.
(a) E. Steffensmeier and K. M. Nicholas, Chem. Commun.,
2018, 54, 790-793; (b) E. Steffensmeier, M. T. Swann and K.
M. Nicholas, Inorg. Chem., 2019, 58, 844-854.
Procedure for synthesis of allyl amine from allyl alcohol 1b and
1,2-diphenylhydrazine.
In a 5 mL screw-capped vial, 1,3-diphenyl-2-methylprop-2-ene-
1-ol (1b) (45 mg, 0.20 mmol), 1,2-diphenylhydrazine (1,2-DPH)
(18 mg, 0.10 mmol), VO(OiPr)3 (9.2 μL, 0.040 mmol), iPr2EtN (3.5
μL, 0.020 mmol), MS3A (0.2 g) and toluene (1.0 mL) were placed
at a glove box filled with nitrogen. The mixture was stirred at
100 °C for 16 h, followed by filtration through Celite® with ethyl
acetate. Triphenyl methane was added as an internal standard,
7
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T. Sakuramoto, T. Hirao, M. Tobisu and T. Moriuchi,
ChemCatChem, 2019, 11, 1175-1178.
F. Preuss and H. Noichl, Z. Naturforsch., B: Chem. Sci., 1987,
42, 121-129.
1
and H NMR analysis was performed to determine an NMR
yield.
1
(E)-N-(1,3-Diphenyl-2-methylallyl)aniline (5). H NMR (400
MHz, CDCl3) δ 7.46-7.15 (m, 12H), 6.78 (s, 1H), 6.72 (t, J = 7.8 Hz,
1H), 6.63 (d, J = 7.8 Hz, 2H), 4.87 (s, 1H), 4.10 (s, 1H), 1.84 (s,
3H); 13C NMR (100 MHz, CDCl3) 147.4, 141.4, 137.7, 137.3,
129.1, 129.0, 128.7, 128.1, 127.60, 127.59, 126.5, 126.4, 117.6,
113.4, 66.3, 15.8 ppm; HRMS (FAB) m/z Calcd. for C22H21N (M+),
299.1669; Found,299.1672.
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Catalytic direct hydrazination of allyl alcohol and deoxygenative
homocoupling reaction of alcohols depending on hydrazine
derivatives were performed by utilizing oxovanadium(V) catalysts.
Ph
N
NH2
Ph