Regioselective β-Arylation of α-Angelica Lactone through Isomerization/Addition under Mild Conditions

Article abstract of DOI:10.1002/cssc.201902761

The conversion of biomass-based platform molecules into various high-value chemicals greatly promotes the utilization of renewable biomass resources. Herein, an example of Rh-catalyzed β-arylation of levulinic-acid-derived α-angelica lactone was reported, providing the γ-lactone-structure products with high regioselectivity. Both arylboronic and alkenylboronic acids could be applied in this transformation. This reaction tolerated a variety of synthetically important functional groups. Moreover, the obtained γ-lactone products could be readily converted to high-value products such as 1,4-diols and γ-methoxy-carboxylates.

Full text of DOI:10.1002/cssc.201902761

Accepted Article
Title: Regioselective β-Arylation of α-Angelica Lactone via
Isomerization/Addition under Mild Conditions
Authors: Kai-Feng Zhuo, Shang-Hai Yu, Tian-Jun Gong, and Yao Fu
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10.1002/cssc.201902761
ChemSusChem
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Regioselective β-Arylation of α-Angelica Lactone via
Isomerization/Addition under Mild Conditions
Kai-Feng Zhuo, Shang-Hai Yu, Tian-Jun Gong,* and Yao Fu*
Abstract: The conversion of biomass-based platform molecules into
various high-value chemicals greatly promote the utilization of
renewable biomass resources. Herein, we reported an example of
Rh-catalyzed β-arylation of levulinic acid derived α-angelica lactone,
providing the γ-lactone structure products with high regioselectivity.
Both arylboronic and alkenylboronic acids can be applied in this
transformation. This reaction tolerated a variety of synthetically
important functional groups. Moreover, the obtained γ-lactone
products can be readily converted to high-valuable products, such as
1, 4-diol and γ-methoxy-carboxylate.
On the other hand, rhodium-catalyzed 1,4-addition of
organoboron reagents to α, β-unsaturated carbonyl compounds
offer a straightforward way of constructing C-C bond.[8. 9] Various
acyclic and cyclic α, β-unsaturated carbonyl compounds (enones,
esters and amides) have been used for the Rh(I)-catalyzed 1,4-
addition reaction. More recently, transition metal catalyzed
isomerization/1,4-addition reactions were developed by
Hayashi’s group.[10] To the best of our knowledge, no example of
addition of organoboron reagents to α-angelica lactone has been
reported. Herein, we reported the first example of Rh(I)-
catalyzed isomerization/1,4-addition of arylboronic and
alkenylboronic acids to α-angelica lactone under mild conditions
(Scheme 2).
The catalytic conversion of renewable biomass, particularly
inedible lignocellulosic biomass, into fuel and chemicals has
drawn much attention.[1] Levulinic acid (LA), which is produced
from hemicellulose and cellulose, is one of most important
renewable platform chemicals as it is a vital resource for C5
compounds. Recently, many efforts have been devoted to the
conversion of LA into highly valuable chemicals, such as
hydrogenation to produce γ-valerolactone (GVL), 2-
methyltetrahydrofuran (2-MTHF), and valerate esters (VAEs),
intramolecular condensation leads to angelica lactone.[2] These
important achievements encourage chemists to seek more
innovative ways to leverage LA to synthesize highly value-added
chemicals. Among then, α-angelica lactone, which is readily
available from levulinic acid by intramolecular dehydration, has
attracted extensive attention [3-6] as a butenolide variant because
[7]
of its potential in the construction of γ-substituted butenolides
natural products and biologically active molecules (Scheme 1).
Types of reactions were reported by using α-angelica lactone as
nucleophile, such as Michael addition, Morita-Baylis-Hillman[5f]
and Pd-catalyzed cross-coupling reaction[5i]. Quite surprisingly,
most of the reaction taken at γ- or α-position, while β-site
Scheme 2. Site-selective functionalization of α-angelica lactone.
In continuation of our team’s efforts in biomass conversion,
especially the conversion of levulinic acid.[11] We chose α-
angelica lactone, which can be easily obtained from levulinic
acid under acid condition, as model substrates. When α-angelica
lactone and phenylboronic acid were treated with [Rh(COD)Cl]2,
rac-BINAP, and NEt3 in EtOH at 60°C for 12 h, we were
[4g-j, 6]
selected transformation has rarely been reported until now.
delighted
to
obtain
the
racemic
trans-4-phenyl-5-
methylhydrofuran-2(3H)-one (3a) in 40% yield (entry 1, Table 1),
without observed α- or γ-arylation products. Then kinds of
ligands were tested in this reaction (i.e. XantPhos, Dppf, DPPM,
DPPE, DPPP and DPE-Phos), it was found that rac-BINAP was
the best ligand. Lowering the temperature to room temperature
increased the yield to 56% due to the reduce dimerization of
angelica lactone (entry 8). Moreover, examining the effect of the
commonly solvent in Rh(I)-catalyzed 1,4-addition reactions (i.e.
THF, CH3CN, toluene, and DCE), we found that the yields were
not improved (entries 9-12). Kinds of rhodium catalysts were
also tested (i.e. [Rh(COD)OH]2, [Rh(COE)2Cl]2, [Rh(C2H4)2Cl]2
and [Rh(CO)2Cl]2), it was found that [Rh(C2H4)2Cl]2 was the best
catalyst, ascribe its easy and irreversible ligand exchange.
Scheme 1. Active molecules containing γ-lactone structure.
[a]
K.-F. Zhuo, S.-H. Yu, Dr. T.-J. Gong, Prof. Y, Fu
Hefei National Laboratory for Physical Sciences at the Microscale,
CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province
Key Laboratory of Biomass Clean Energy, iChEM, University of
Science and Technology of China,
Hefei, 230026, (China)
E-mail: gongtj@ustc.edu.cn
fuyao@ustc.edu.cn
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cssc.201902761
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COMMUNICATION
Table 1. Optimization of the reaction conditions.a
Solvent
EtOH
[Rh]
(2 mol%)
Ligand
(2 mol%)
Yield
(%) b
entry
T (C)
60
40
1
2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)OH]2
[Rh(COE)2Cl]2
[Rh(C2H4)2Cl]2
[Rh(CO)2Cl]2
BINAP
XantPhos
Dppf
60
60
60
60
60
60
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
23
10
20
15
12
5
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
toluene
THF
3
4
DPPM
DPPE
5
6
DPPP
7
DPE-Phos
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
56
34
24
19
16
33
37
74
28
8
9
10
11
12
13
14
15
16
CH3CN
DCE
Scheme 3. Substrate scope. α-angelica lactone (0.2 mmol), arylboronic acids
(0.4 mmol), NEt3 (0.4 mmol), [Rh(C2H4)2Cl]2 (2 mol%), BINAP (4 mol%), EtOH
(1 mL), 12 h under Ar atmosphere. Isolated yield.
EtOH
EtOH
EtOH
EtOH
BINAP
BINAP
BINAP
[a] All the reactions were carried out with 0.2 mmol of α-angelica lactone and
0.4 mmol of 2a in 1 mL solvent for 12h. [b] Isolated yield.
With the optimized reaction conditions in hand, we
examined the substituent effect of the arylboronic acids
(Scheme 3). Both electron-donating and withdrawing arylboronic
acids were tested and exhibited good reactivities. For electron-
donating arylboronic acids, such as 4-tolylboronic acid and 4-
biphenylboronic acid, could be well compatible in this reaction.
Naphthyl-substituted boronic acids smoothly survived in the
process. Notably, 4-vinyl-phenylboronic acid reacted smoothly
with moderate yield (3e). 4-NO2, 4-Ac, 4-COOMe and 4-CF3
substituted boronic acids could be employed in this reaction
afford the products in moderate yields. It was noteworthy that
various halogen substituents (Br, Cl, and F) could be well
compatible, which made additional functionalization possible at
these positions. Both meta- and ortho-substituted arylboronic
acids can be smoothly survived in the arylation process.
In addition to aryl boronic acids, alkenylboronic acid was
also compatible with this reaction (3q), the olefin can be used for
further transformation (eq.1). Moreover, 5-phenylfuran-2(3H)-
one was also efficient partner for this transformation obtained
the desired product in 74% yield. When R-BINAP was used in
this reaction, 3b was obtained in 54% yield with excellent
enantioselectivity (85% ee).
To understand the reaction mechanism, isomerization
experiments of α-angelica lactone were carried out, which was
1
characterized by H NMR spectroscopy (Figure 1). The peaks at
δ ≈ 5.13 ppm (m, 1H) was observed for commercially available
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10.1002/cssc.201902761
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α-angelica lactone. Then, NEt3 (1 equiv)/EtOH (1 equiv) were
added, after 2 hours later, the characteristic peaks at δ≈ 7.48
ppm (dd, J = 5.7, 1.5 Hz, 1H) and 6.10 ppm (dd, J = 5.7, 2.0 Hz,
1H) appeared, which were assigned to hydrogen atoms of β-AL.
These results certify base-promoted α-AL isomerization to
produced β-AL. Extend reaction time to 6 and 12 hours, more β-
Figure 1. Evidence for the isomerization of α-angelica lactone using NEt3 + EtOH (1H NMR)
On the basis of the mechanistic studies and related
literature, we proposed that the mechanism of the Rh-catalyzed
1, 4-addition reaction is as follows: First, base-promoted α-
angelica lactone isomerization to produced β-angelica lactone.
Meanwhile, transmetalation of an aryl group of arylboronic acids
with rhodium catalyst produces the reactive arylrhodium I. Then
the β-angelica lactone coordinates with I and subsequently
inserts into Rh-Ar bond to form the adduct II. Finally, protonated
to generate the product 3. The rhodium catalyst then go back to
the catalytic cycle.
AL was obtained. To further examine the reaction mechanism
progress, 2,3-dihydrofuran was tested in the arylation
transformation, no arylation product was observed (Scheme 4),
indicated that the carbonyl group is necessary for the arylation
reaction. When 6-methyl-3,4-dihydro-2H-pyran-2-one, which
was difficult isomerization to conjugated acrylate, was examined
in the same reaction, no product was detected. Then, β-angelica
lactone was conducted in the transformation,[12] leading to the
formation of the arylation product 3b in 89% yield. The results of
1H NMR and control experiments suggesting that the arylation of
α-angelica lactone reaction proceeds through isomerization/1,4-
addition pathway.
Figure 2. Proposed Mechanism.
To further demonstrate the application of arylation reaction.
First, scaled-up experiment was conducted (10 mmol scale,
0.5% catalyst loading, Scheme 5), we found the yield was much
better (85%). Meanwhile, the product can be converted to 1,4-
diol (4) through the hydrogenation using LiAlH4. Note that 1, 4-
diol was very important intermediate for biologically active
compounds and polymers.[13] Moreover, the product 3b can also
be readily converted to γ-methoxy-carboxylate (5). Thus, the Rh-
catalyzed 1,4-addition reaction is synthetically useful because γ-
Scheme 4. Control experiments.
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10.1002/cssc.201902761
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lactone structure can be readily converted to diverse important
molecules.
concentrated. The residue was purified by flash column chromatography on
silica gel with petroleum ether/ethyl acetate as the eluent to give the products.
Scale-up Arylation of α-angelica lactone
A 250 mL chlenk tube equipped with a magnetic stirrer was charged with
Rh(C2H4)2Cl2 (20 mg, 0.05 mmol), rac-BINAP (31 mg, 0.05 mmol), and 4-
biphenylboronic acid (3.96g, 20 mmol). The tube was evacuated and
backfilled with argon for three times, and then EtOH (50 mL) was added. Then,
the α-angelica lactone (10 mmol) and NEt3 (2.88 mL, 20 mmol) was added by
syringe under argon. The reaction mixture was stirred at room temperature for
12 h. Then EtOAc and water were added and the layers were separated. The
aqueous phase was extracted with EtOAc (x2) and the combined organic
layers were dried over Na2SO4, filtered, and concentrated. The residue was
purified by flash column chromatography on silica gel with petroleum
ether/ethyl acetate as the eluent to give the product 3b.
Scheme 5. Transformation of the product 3b.
As mentioned above, AL (both α-AL and β-AL) can be
easily obtained by dehydration of LA. We tried the arylation
experience using levulinic acid (Scheme 6). First, levulinic acid
catalyzed by H3PO4, 42% of AL mixture (α-AL : β-AL ≈ 5 : 1 )
was obtained under vacuum distillation. Then, the obtained AL
mixture was used directly for the arylation reaction, 84% yield of
3b was obtained.
Transformation of the product.
A solution of lactone 3b (0.2 mmol) in dry THF (0.55 ml) was added dropwise
to a slurry of LiAlH4 (30 mg, 0.8 mmol) in dry THF (1 ml) under nitrogen at 0 °C.
The reaction mixture was stirred at 0 oC for 4 h. Then EtOAc and water were
added and the layers were separated. The aqueous phase was extracted with
EtOAc (x2) and the combined organic layers were dried over Na2SO4, filtered,
and concentrated. The residue was purified by flash column chromatography
give the product 4 (81%).
H2SO4 (1 μL) was added to a solution of lactone 3b (0.2 mmol), CH(OMe)3
(0.4 mmol) in MeOH (1 mL). The reaction mixture was stirred at 50 oC for 12
h. Then EtOAc and water were added and the layers were separated. The
aqueous phase was extracted with EtOAc (x2) and the combined organic
layers were dried over Na2SO4, filtered, and concentrated. The residue was
purified by flash column chromatography on silica gel give the product 5.
Scheme 6. Arylation reaction by using levulinic acid (LA) as starting material.
In summary, we have developed an unprecedented Rh(I)-
catalyzed 1,4-addition of organoboron to α-AL, providing the β,
γ-disubstituted-γ-butyrolactone
products
with
high
regioselectivity and enantioselectivity. Both arylboronic and
alkenylboronic acids can be applied in this transformation.
Mechanistic studies show that, first, isomerization of α-AL to β-
AL in the presence of base. Then, Rh-catalyzed 1,4-addition of
β-AL afford the products. Moreover, γ-lactone structure can be
readily converted to 1,4-diol and γ-methoxy-carboxylate. Further
efforts are still in progress in our lab, such as heterogeneous
catalysis of α-AL.
Acknowledgements
We acknowledge the support from National Key R&D Program of China
(2018YFB1501600), National Natural Science Foundation of China
(21732006, 21702200 and 51821006), Strategic Priority Research
Program of CAS (XDA21060101, XDB20000000) and the Major Program
of Development Foundation of Hefei Centre for Physical Science and
Technology (2017FXZY001). CAS President’s International Fellowship
Initiative and Fundamental Research Funds for the Central Universities
Experimental Section
Arylation of α-angelica lactone
Keywords: Biomass conversion• Angelica lactone • Arylation •
Isomerization
A 10 mL chlenk tube equipped with a magnetic stirrer was charged with
Rh(C2H4)2Cl2 (1.6 mg, 0.004 mmol), rac-BINAP (2.5 mg, 0.004 mmol), and
arylboronic or alkenylboronic acids (2.0 equiv., 0.4 mmol). The tube was
evacuated and backfilled with argon for three times, and then EtOH (1 mL)
was added. Then, the α-angelica lactone (18 μL, 0.2 mmol) and NEt3 (2.0
equiv., 0.4 mmol) was added by syringe under argon. The reaction mixture
was stirred at room temperature for 12 h. Then EtOAc and water were added
and the layers were separated. The aqueous phase was extracted with EtOAc
(x2) and the combined organic layers were dried over Na2SO4, filtered, and
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10.1002/cssc.201902761
ChemSusChem
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Kai-Feng Zhuo, Shang-Hai Yu, Tian-Jun
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Regioselective β-Arylation of α-
Angelica Lactone via Isomerization
/Addition under Mild Conditions
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The conversion of biomass-based platform molecules into various high-value
chemicals greatly promote the utilization of renewable biomass resources. Herein, we
reported an example of Rh-catalyzed β-arylation of α-angelica lactone under mild
reaction conditions, providing the γ-lactone structure products with high
regioselectivity. Moreover, the obtained γ-lactone products can be readily converted to
high-valuable products, such as 1, 4-diol and γ- methoxy-carboxylate.
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