Palladium(II)-Catalyzed Regio- and Stereoselective Hydroarylation of Diphenylphosphorylallenes with Arylboronic Acids in the Presence of Sodium Hydroxide and Oxygen

Article abstract of DOI:10.1002/adsc.201600160

The palladium(II)-catalyzed hydroarylation of diphenylphosphorylallenes (via 1,2-addition of the allenic double bond) with arylboronic acids in the presence of sodium hydroxide and oxygen is developed. The regioselectivities turn out to be well controlled, affording 2-aryl-3-(diphenylphosphinyl)alkenes as the only product. Moreover, the stereoselectivities for reactions of γ-substituted allenes can also be nicely controlled, resulting in the formation of Z-alkenes. The reaction shows high substituent loading capability and tolerance of various substituents. A mechanism, including transmetalation of arylboronic acid with palladium halides, insertion of the 1,2-allenic double bond to the Pd?Ar bond, and protonation to afford the final hydroarylation product is proposed. (Figure presented.).

Full text of DOI:10.1002/adsc.201600160

UPDATES
DOI: 10.1002/adsc.201600160
Palladium(II)-Catalyzed Regio- and Stereoselective Hydroaryla-
tion of Diphenylphosphorylallenes with Arylboronic Acids in the
Presence of Sodium Hydroxide and Oxygen
Yang Chen,+a Dong-Mei Ma,+a Fei-Fei Ba,+a Jing Sun,a Tian Liu,a Lei Zhu,b,*
and Ming-Dong Zhoua,*
a
School of Chemistry and Materials Science, Liaoning Shihua University, Fushun 113001, Peopleꢀs Republic of China
E-mail: mingdong.zhou@lnpu.edu.cn
College of Chemistry and Materials Science, Hubei Engineering University, Hubei 432000, Peopleꢀs Republic of China
b
E-mail: lei.zhu@hbeu.edu.cn
+
These authors contributed equally to this work.
Received: February 6, 2016; Revised: May 11, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600160.
Abstract: The palladium(II)-catalyzed hydroaryla-
tion of diphenylphosphorylallenes (via 1,2-addition
of the allenic double bond) with arylboronic acids
in the presence of sodium hydroxide and oxygen is
developed. The regioselectivities turn out to be well
controlled, affording 2-aryl-3-(diphenylphosphiny-
l)alkenes as the only product. Moreover, the stereo-
selectivities for reactions of g-substituted allenes
can also be nicely controlled, resulting in the forma-
tion of Z-alkenes. The reaction shows high substitu-
ent loading capability and tolerance of various sub-
stituents. A mechanism, including transmetalation
of arylboronic acid with palladium halides, insertion
and C=N bonds provides an efficient way for the con-
struction of C C bonds. In particular, the transition
[3]
ꢀ
metal-catalyzed hydroarylation or hydroalkenylation
of allenes with organoboronic acids is a good strategy
for obtaining various functionalized alkenes.[4–8] Ma
et al. firstly reported a palladium(0)-catalyzed addi-
tion of arylboronic acids with 2,3-allenoates in the
presence of acetic acid, in which the regio- and ste-
reoselectivities were well controlled, yielding tri- and
tetra-substituted alkenes as 2,3-addition products of
allenes.[4] Almost at the same time, Oh et al. reported
a similar reaction, and good to excellent yields were
also obtained for different allenes including allenic ni-
triles, allenoates, allenols, allenic ethyl esters and alle-
nals.[5] Subsequently, Ma et al. further extended this
reaction to other allenes including allenylphospho-
nates, allenic sulfones, allenic sulfoxides, and alkyl or
aryl-substituted allenes.[6] Yoshida et al. developed an
ionic Pd(II) catalyst-promoted hydroarylation of al-
lenes with arylboronic acids, wherein similar regiose-
lective 2,3-addition products were obtained as de-
scribed above under basic condition (Et3N).[7] More-
over, the reaction has also been successfully applied
ꢀ
of the 1,2-allenic double bond to the Pd Ar bond,
and protonation to afford the final hydroarylation
product is proposed.
Keywords: allenes; arylboronic acids; hydroaryla-
tion; palladium
Allenes are a class of unique and interesting unsatu- in the synthesis of several natural products.[8] Interest-
rated compounds with two p-orbitals perpendicular to ingly, Yoshida et al. found that the reaction resulted
each other and they are important intermediates in in completely regioselective 1,2-addition products
organic synthesis.[1] Despite the fact that control of when catalyzed by an ionic Pt(II) catalyst in the pres-
the chemo-, regio-, and stereoselectivities is challeng- ence of KOH.[7] Hayashi et al. also described a rhodi-
ing, some notable progresses have been made by Ma, um-catalyzed asymmetric hydroarylation of diphenyl-
Zimmer, Yamamoto and other groups, such as hydro-, phosphorylallenes with arylboronic acids. Similarly,
carbo-, or heteroatom metalations and cyclizations of the addition of arylboronic acids to allenes occurs at
allenes.[2] On the other hand, the transition metal-cat- the 1,2-allenic double bond, affording (S)-2-aryl-3-(di-
alyzed addition of organoboronic acids to unsaturated phenylphosphinyl)alkenes in high yields and enantio-
C=C double and C C triple bonds as well as C=O, selectivity (Scheme 1).[9] However, to the best of our
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Table 1. Optimization of the reaction conditions.[a]
En- Solvent
try
Catalyst
(mol%)
NaOH
(equiv.) [%]
Yield
1
2
3
4
5
6
THF:H2O=5:1
PdCl2 (20)
PdCl2 (20)
PdCl2 (20)
PdCl2 (20)
PdCl2 (20)
PdCl2 (20)
PdCl2 (10)
PdCl2 (5)
PdCl2 (3)
Pd(OAc)2 (5) 2.0
Pd(PPh3)4 (5) 2.0
Pd2(dba)3 (5) 2.0
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
trace
trace
59
40
32
70
69
69
54
58
21
25
trace
50
61
56
39
59
EtOH:H2O=5:1
CH2Cl2:H2O=5:1
toluene:H2O=5:1
EtOAc:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN:H2O=5:1
CH3CN
Scheme 1. The transition metal-catalyzed addition reactions
of allenes with arylboronic acids.
7
8[b]
9
10
11
12
13
14
15
16
17
18
19
20
21
knowledge, the selective 1,2-addition of functionalized
allenes with organoboronic acids to afford multi-sub-
stituted alkenes using palladium as catalyst has not
yet been reported.[10–12] In continuation of our study
on transition metal-catalyzed reactions of allenes, we
have recently studied the PdCl2-catalyzed regio- and
stereoselective addition of arylboronic acids with di-
phenylphosphorylallenes in the presence of NaOH
and O2, and we wish to report our preliminary results
here.
0
0.5
1.5
5.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
CH3CN:H2O=10:1 PdCl2 (5)
CH3CN:H2O=5:2
CH3CN:H2O=1:5
H2O
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
56
0
0
trace
trace
53
22[c] CH3CN:H2O=5:1
23[d] CH3CN:H2O=5:1
24[e] CH3CN:H2O=5:1
To explore the reactivity, the reaction using diphe-
nylphosphorylallene 1a as model substrate was fully
studied for reaction optimization (Table 1). The reac-
tions were initially carried out in various solvent sys-
tems with volume ratio of solvent:water=5:1 using
20 mol% of PdCl2 as catalyst in the presence of
NaOH and O2. Disappointingly, no products could be
isolated when using THF or EtOH (entries 1 and 2).
Further efforts showed that 32–59% yields of 2-aryl-
3-(diphenylphosphinyl)alkene 2a could be achieved
when carrying out the reactions in CH2Cl2/H2O, tolu-
ene/H2O or EtOAc/H2O system, but the yields were
still not satisfactory (entries 3–5). To our delight, up
[a]
The reaction was carried out using 1a (0.2 mmol), 4-
CH3C6H4B(OH)2 (2.0 equiv.), catalyst (5 mol%), and
NaOH in solvent (5:1 mL) under an O2 atmosphere
(1 atm.) at reflux for 16 h.
21% of 4,4’-dimethyl-1,1’-biphenyl was isolated.
The reaction was carried out in the air.
[b]
[c]
[d]
[e]
Under argon atmosphere (1 atm.).
The reaction was carried out at 408C.
to 70% of 2a could be isolated when the reaction was (entries 13–16). Moreover, the involvement of water
run in CH3CN/H2O (entry 6). Subsequently, the reac- as co-solvent proved to be very important. When car-
tion was carried out with different catalyst loadings in rying out the reaction in CH3CN (entry 17), only 39%
CH3CN/H2O. The results showed that the high yield of 2a could be obtained.
could be maintained even when decreasing the PdCl2
On varying the volume ratio between CH3CN and
amount to 5 mol% (entry 8). Under the conditions of H2O, the product yield also varied, and the favorable
5 mol% catalyst, Pd(OAc)2, Pd(PPh3)4 and Pd2(dba)3 ratio was 5:1. However, owing to the low solubility of
were also found to be effective to catalyze the exam- organic substrates in water, the reaction could not
ined reaction, but afforded relatively lower product proceed when CH3CN:H2O=1:5 or in pure water
yields as compared to PdCl2 (entries 10–12). Further (entries 21 and 22). Under an argon atmosphere or in
studies indicated that the amount of NaOH affected air, the reactions resulted in only trace amounts of
the reaction efficiency. On decreasing the NaOH product 2a, revealing that the involvement of a suffi-
amount, the yields were also significantly decreased, cient amount of O2 is necessary to promote the reac-
and 2 equiv. of NaOH proved to be most efficient tion (entries 22 and 23). Lower reaction temperature
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(408C) led to lower 2a yield (entry 24). Based on the lenes bearing alkyl groups at the a-position (R1)
above studies, standard reaction conditions (Table 2, 2a–2c). The reaction was also applicable for
A
[5 mol% of PdCl2, 2 equiv. of NaOH, CH3CN:H2O= various aryl (R1) substituted allenes (2d–2g), indicat-
5:1, O2 atmosphere (1 atm), reflux] were obtained. ing that the electron density of the aryl group has no
Under these optimal conditions, the regioselectivity of obvious influence on the reaction. Notably, good
this reaction was nicely controlled, in which the addi- yields could also be obtained when introducing alkyl
tion of allene occurred at the 1,2-allenic double bond or aryl groups to the g-position (R2) of the allene
with the aryl group of arylboronic acid adding to the moiety, and the reactions afforded only Z-alkenes as
central carbon of the allene moiety. The reaction af- the addition products (2h–2l), revealing a high stereo-
forded 2-aryl-3-(diphenylphosphinyl)alkene 2a as the selectivity of the reaction. The configuration of the
only product. It should be noted that ca. 21% of 4,4’- C=C bond in 2h was determined by the 1H-1H
dimethyl-1,1’-biphenyl could be isolated in the exam- NOESY spectrum (Scheme 2). In all tested reactions,
ined system under the optimal reaction conditions
(entry 8). Moreover, the blackening of the reaction
solution – which may be due to the decomposition of
PdCl2 to palladium nanoparticles – could also be ob-
served. These phenomena provide key information
for the mechanism (vide infra).
The scope of this reaction was then carefully stud-
ied by using various allenes and arylboronic acids as
substrates under conditions A. Products 2a–2l were
obtained by using diphenylphosphorylallenes as sub-
strates. The reaction proved to be applicable for al- Scheme 2. 1H-1H NOESY of Z-2h.
Table 2. The reactions of various allenes with p-tolylboronic acid.[a]
[a]
The reaction was carried out using allene (0.2 mmol), 4-CH3C6H4B(OH)2 (2.0 equiv.), PdCl2 (5 mol%), and NaOH
(2.0 equiv.) in CH3CN:H2O (5:1 mL) under an O2 atmosphere (1 atm.) at reflux for 16 h.
20 mol% of the chiral ligand (R)-(+)-2,2’-bis(diphenylphosphino)-1,1’-binaphthyl was applied.
[b]
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small amounts of oligomers could also be detected.
Based on literature precedents[13] and experimental
Nevertheless, only 2-aryl-3-(diphenylphosphinyl)al- observations, a plausible mechanism is proposed
kene 2a–2l products were able to be isolated. Similar (Scheme 3). Firstly, the transmetalation of the arylbor-
results can be also achieved when using diethoxyphos- onic acid with PdX2 leads to the formation of inter-
phorylallenes as substrates, affording 2m–2o in 32– mediate 3. Similar to that reported for Suzuki cou-
46% isolated yields. Moreover, the reaction was also pling reactions,[14] the presence of the strong base
carried out with the introduction of 20 mol% chiral NaOH should be helpful for this transmetalation pro-
ligand
(R)-(+)-2,2’-bis(diphenylphosphino)-1,1’-bi- cess. The involvement of NaOH may enhance the nu-
naphthyl using 1g as substrate. Unfortunately, the re-
action exhibited negligible enantioselectivity for 2g*.
The data for the PdCl2-catalyzed addition of 1g
with various organoboronic acids under conditions A
are shown in Table 3. Among various arylboronic
acids, the addition of non-substituted phenylboronic
acid with 1g resulted in the highest product yield
(Table 3, 2q). It can be seen that good yields could be
obtained for both electron-rich and electron-poor ar-
ylboronic acids.
The electron-poor arylboronic acids bearing NO2,
CN, CF3, COMe, COOMe or F substituents afforded
60–77% product yields, while a good yield could also
be achieved for the electron-rich C2H5 substituted ar-
ylboronic acid (58%). To our delight, the reaction was
found to be also applicable for vinylboronic acids. As
is shown in Table 3, the addition of (E)-hex-1-en-1-yl-
boronic acid or (E)-(3-phenylprop-1-en-1-yl)boronic
acid with 1g afforded 82% of 2x and 67% of 2y, re-
spectively. In all examined reactions, 2p–2y were iso-
lated as the only products. Thus, the reaction showed
high selectivity with good substituent-loading capabil-
ity and tolerance of various substituents.
Scheme 3. Proposed mechanism for palladium(II)-catalyzed
hydroarylation of diphenylphosphorylallenes with arylbor-
onic acids.
Table 3. The reactions of 1g with various organoboronic acids.[a]
[a]
The reaction was carried out using 1g (0.2 mmol), ArB(OH)2 (2.0 equiv.), PdCl2 (5 mol%), and NaOH (2.0 equiv.) in
CH3CN:H2O (5:1 mL) under an O2 atmosphere (1 atm.) under reflux for 16 h.
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cooled to room temperature, then extracted with dichloro-
methane and water. The combined organic layer was dried
over MgSO4. Filtration, concentration, and purification by
flash chromatography on silica gel (eluent: petroleum ether/
ethyl acetate=5/1!3/1!1/1) afforded 2.[15]
cleophilicity of the arylboronic acid, owing to its coor-
ꢀ
dination with OHꢀ to form ArB(OH)3 species. Thus,
ꢀ
the further coordination of PdX2 with ArB(OH)3
could be facilitated smoothly, affording the transmeta-
lation intermediate 3. This speculation is also in
agreement with that reported for the Pt/KOH-cata-
lyzed hydroarylation of allenes described by Yoshida
et al.[7] Subsequent highly regioselective insertion of
the 1,2-allenic double bond of 1 to the Pd–Ar bond of
3 results in the formation of intermediate 4, in which
the aryl group of the arylboronic acid is added to the
central carbon of allene moiety. The stereoselectivity
of g-substituted allenes is also determined in this step,
affording the less hindered Z-alkene derivatives. Fur-
ther protonation of 4 leads to the formation of final
product 2 and regenerates the PdX2 catalyst. On the
other hand, a second transmetalation of the arylbor-
onic acid with 3 may also lead to the formation of 5.
Therefore, the by-product Ar-Ar (6) might be ob-
tained through the reductive elimination of 5, result-
ing in the formation of a Pd(0) species. The observed
blackening of the reaction media may due to the dep-
osition of Pd(0) species to palladium nanoparticles,
which also nicely supports our speculation. Such
a side reaction might be highly active, thus the main
reaction could be strongly hindered since a significant
amount of Pd(II) catalyst is consumed in this process.
As was observed in our experiments, only trace
amounts of product could be isolated when carrying
out the reaction under argon or in air. Therefore, the
involvement of a sufficient amount of O2 is very im-
portant, which might be helpful for the recovery of
Pd(0) species back to Pd(II) species.
In summary, we have developed a highly regio- and
stereoselective PdCl2-catalyzed hydroarylation of al-
lenes with arylboronic acids in the presence of NaOH
and O2. The catalyst PdCl2 proves to be efficient for
the addition of arylboronic acids with diphenylphos-
phorylallenes, affording 2-aryl-3-(diphenylphosphiny-
l)alkenes as the 1,2-addition products. A mechanism,
including transmetalation of the arylboronic acid with
PdX2, insertion of the 1,2-allenic double bond to Pd–
Ar, and protonation to the final hydroarylation prod-
uct, is proposed. The study provides a selective and
cost-effective method for the synthesis of various sub-
stituted alkenes using allenes as substrates.
Acknowledgements
M.D.Z thanks the National Natural Science Foundation of
China (21101085), Natural Science Foundation of Liaoning
Province (2015020196), Fushun Science & Technology Pro-
gram (FSKJHT 201423), and Liaoning Excellent Talents
Program in University (LJQ2012031) for the financial sup-
port. L.Z. thanks the National Natural Science Foundation of
China (21304032) for the financial support.
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Typical Procedure for the Catalytic Reaction
A solution of allene substrate 1 (0.2 mmol), PdCl2 (1.77 mg,
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Palladium(II)-Catalyzed Regio- and Stereoselective
Hydroarylation of Diphenylphosphorylallenes with
Arylboronic Acids in the Presence of Sodium Hydroxide
and Oxygen
7
Adv. Synth. Catal. 2016, 358, 1 – 7
Yang Chen, Dong-Mei Ma, Fei-Fei Ba, Jing Sun, Tian Liu,
Lei Zhu,* Ming-Dong Zhou*
Adv. Synth. Catal. 0000, 000, 0 – 0
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ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers!