DMAP Mediated Efficient Construction of Functionalized Chromenes through One-Pot Reaction of para-Quinone Methides with Allenoates

Article abstract of DOI:10.1002/ejoc.202100112

A novel DMAP-mediated Rauhut-Currier/oxa-Michael addition cascade reaction of hydroxylphenyl-substituted para-quinone methide with allenoate was reported for the first time. A series of functionalized chromenes were successfully obtained with moderate to

Full text of DOI:10.1002/ejoc.202100112

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DMAP Mediated Efficient Construction of Functionalized
Chromenes through One-Pot Reaction of para-Quinone
Methides with Allenoates
[a]
[b]
[b]
[a, c]
Zefeng Song, Yuping Jia, Daizhou Zhang, and De Wang*
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A novel DMAP-mediated Rauhut-Currier/oxa-Michael addition
cascade reaction of hydroxylphenyl-substituted para-quinone
methide with allenoate was reported for the first time. A series
of functionalized chromenes were successfully obtained with
moderate to good yields under this one-pot cascade reaction.
The chromene products could be easily transformed into
different derivatives and a plausible mechanism was proposed
to elucidate this novel reaction.
Introduction
workers reported the first domino reaction of ortho-hydrox-
yphenyl-substituted p-QMs with isatin derived alkenes for
construction of spiro-chromans. Fan and co-workers realized
[8]
Chromenes and their derivative chromans are important motifs
widely existing in numerous natural products as well as
pharmaceutically relevant compounds. Several examples of
these bioactive molecules are illustrated in Figure 1. For
example, ormeloxifene (A) is a readily available drug molecule
the synthesis of dihydrocoumarin derivatives via phosphine-
[1]
[9]
catalyzed intramolecular Rauhut-Currier reaction. Two more
examples for preparation of functional chroman derivatives
were achieved with ortho-hydroxyphenyl-substituted p-QMs
[2]
[10]
which target estrogen receptor modulator. Crolibulin (B) is
and azlactons by phosphoric acid catalysis.
Recently, two
known as anticancer compound and has remarkable properties
groups reported cycloaddition of para-quinone methide deriva-
[3]
as apoptosis inducer for anaplastic thyroid cancer treatment.
Compounds C–D exhibit potential anti-osteoporotic and anti-
tives with activated alkynones or ynals, constructing functional-
[11]
ized chromenes independently (Scheme 1a).
Despite the
[4]
neoplastic activities. Different strategies aiming at construc-
reported impressive achievements, the development of novel
strategies for construction of chromene is still challenging and
meaningful. It was noticed that allenoates had been applied as
useful synthons in catalytic Rauhut-Currier reaction with p-QMs
enabled by base or Lewis base catalysts, where diarylmethane
with allene motifs compounds were synthesized efficiently
[5]
tion of such skeletons have been developed in recent years.
Nevertheless, as the increasing requirement of these type of
molecules in medicine and pharmacy, a direct and valuable
strategy for efficient synthesis of chromene framework, espe-
cially for the functionalized ones, is highly demanded.
[12]
para-Quinone methides (p-QMs) were considered as power-
ful precursor for construction of 1,1-diarylmethane compounds
(Scheme 1b). Encouraged by these pioneer works disclosed
by Mohanan’s, Chandra’s and Tang’s group independently, we
hypothesis that it might undergoes a cascade reaction to form
heterocyclic scaffold with an orth-nucleophilic site existence. As
a part of our ongoing investigations on the organocatalyzed
[6]
in recent years. To be noticed, the installation of a suitable
nucleophilic site on terminal aryl group could make the p-QMs
into double functionalization substrates, and a set of seminal
works based on these ortho-hydroxyphenyl-substituted p-QMs
have been presented for the synthesis of chromene related
[13]
methodology of p-QMs, hereby, we reported a Lewis base
serving as effective catalyst in a one-pot domino reaction of the
ortho-hydroxyphenyl-substituted p-QMs with allenoates, com-
bining Rauhut-Currier reaction and hetero-Michael addition
together to provide an effective synthetic protocol for the
preparation of biologically interesting chromenes (Scheme 1c).
[7]
structures with various catalytic strategies. Enders and co-
[
a] Z. Song, Prof. Dr. D. Wang
Molecular Synthesis Center, Key Laboratory of Marine Drugs, Ministry of
Education, School of Medicine and Pharmacy, Ocean University of China &
Laboratory for Marine Drugs and Bioproducts and Open Studio for
Druggability Research of Marine Natural Products, Pilot NLMST,
Qingdao, China
Results and Discussion
[
b] Y. Jia, D. Zhang
Shandong Academy of Pharmaceutical Sciences,
Jinan, Shandong, China
Initial examinations use ortho-hydroxyphenyl-substituted p-QM
1
a and allenoate 2a as model substrates in the presence of
[c] Prof. Dr. D. Wang
different Lewis base (PPh , DABCO and DMAP) to evaluate our
3
State Key Laboratory of Chemical Oncogenomics, Key Laboratory of
Chemical Genomics,
Peking University Shenzhen Graduate School,
Shenzhen, 518055 Guangdong, China
E-mail: wangde@ouc.edu.cn
hypothesis. Unfortunately, the desired product was not
detected under the catalytic reaction conditions (Scheme 2,
eq. 1), probably due to the affection of the hydroxyl moiety’s
acidity. To our delight, when TBS protected compound p-QM
1b applied with DMAP as catalyst in toluene at room temper-
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/ejoc.202100112
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Scheme 1. Reaction design with Allenoate and p-QMs.
Figure 1. Natural products and pharmaceuticals containing chroman skeleton.
ature, the reaction proceeded well to afford desired product 3
in 39% yield (Scheme 2, eq. 2). A chromene product 4a was
successfully formed after treating with tetra-n-butyl aminonium
fluoride (TBAF). Realized that compound 3 was not stable
enough during the purification, we then tried to explore the
reaction in a one-pot procedure without isolating the inter-
mediate product to overcome this shortage. As expected, the
yield of product 4a was enhanced to 68% (Scheme 2, eq. 3).
Encouraged by the initial results, we turned our attention to
optimize the reaction conditions with p-QM 1c and allenoate
best solvent in the reaction, giving the desired product 4b in
74% yield (Table 1, entry 8). The other solvents such as toluene,
o-xylene, DCM, THF, MTBE, 1,4-dioxane or CH CN failed to
3
improve the efficiency (52-69%). A slight decreased yield was
observed when using 30 mol% DMAP catalyst, but a 10 mol%
catalyst loading in the one-pot reaction is still proceeded good
to generate product 4b in 75% yield (Table 1, entries 11–12).
Lowering the reaction temperature to 0°C, the yield decreased
dramatically to 57% (Table 1, entry 13). However, it was also
found the efficacy of the reaction could not be improved by
further increasing the temperature (Table 1, entry 14). More-
over, the reaction could already proceed smoothly within
2 hours under standard catalytic conditions to generate product
4b in 75% yield (Table 1, entry 15).
2
a as model substrates, the results are summarized in Table 1.
In the presence of different Lewis base catalysts, the corre-
sponding product 4b was generated in 63% yield under the
DMAP catalysis, while the other catalysis options only gave
trace product (Table 1, entries 1–3). We further optimized the
reaction conditions by screening of different solvents (Table 1,
Having the optimal reaction conditions identified, the
generality of the two steps in one-pot cascade reaction was
examined using various p-QMs 1 and allenic esters 2. The
entries 4–10). It was revealed that ethyl ether (Et O) was the
2
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Scheme 2. Hydroxyl-p-QM involved in Rauhut-Currier reactions.
[a]
Table 1. Optimization of the reaction conditions.
[b]
Entry
cat.
x (loading)
Solvent
T [°C]
t [h]
Yield [%]
[
c]
1
2
3
4
5
6
7
8
9
1
PPh
3
20
20
20
20
20
20
20
20
20
20
30
10
10
10
10
toluene
toluene
toluene
o-xylene
DCM
THF
MTBE
25
25
25
25
25
25
25
25
25
25
25
25
0
8
8
trace
trace
63
52
61
56
62
74
64
69
72
75
57
74
75
[c]
DABCO
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
DMAP
12
12
12
12
12
12
12
12
12
12
12
12
2
Et
1,4-dioxane
CH CN
Et O
2
O
0
3
11
2
1
1
1
2
3
4
Et
Et
Et
2
2
2
O
O
O
40
25
15
2
Et O
[a] The reactions were performed with 1c (0.1 mmol), 2a (0.12 mmol) and catalyst in solvent (1.0 mL); [b] Isolated yield; [c] Decomposed, only trace product.
1
1
results are summarized in Table 2. All reactions proceeded
smoothly to give the corresponding products 4 in moderate to
good yields. In details, p-QMs 1b–1m bearing electron-neutral
(R =H), electron-donating (R =OMe, Me) or electron-withdraw-
ing (R =F, Cl, Br) groups on the aryl ring underwent this
domino reaction process to afford chromene products 4a–4h
1
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[a]
Table 2. Substrate scope of the one-pot reaction.
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[a] All reaction carried out with 1 (0.1 mmol), 2 (0.12 mmol) and DMAP (0.01 mmol) in Et
2
O (1.0 mL) at room temperature for 2 hours; then TBAF (1 M in THF,
0
.1 mmol) for 1 hour.
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in 68–82% yield. The structure of 4e has been determined by
unfortunately became decomposed and no correspondent
dihydroquinone product was detected (Scheme 3, eq. 4).
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[14]
X-ray diffraction and the ORTEP drawing is shown in Table 2.
t
Multi-substituted groups (even bulky group di- Bu ) were
At last, we turn our attention to explore the enantioselective
control of this Lewis base-catalyzed reaction (Scheme 4). We
first applied p-QM 9 and allenoate 2a as model substrates to
investigate the Rauhut-Currier reaction stereoselectivity control.
After screening several different chiral phosphines and chiral
tertiary amines which were widely used in asymmetric synthesis
of allenoates transformation (see SI for details), it was found
2
tolerated in the reaction, the corresponding products 4i–4k
were produced in slightly decreased yields (51–62%). To be
noticed, steric hindrance naphthyl is also suitable for the
reaction, where product 4l was obtained in 49% yield
correspondingly. Moderate yields (52–58%) were obtained with
tert-butyl buta-2,3-dienoate 2b or phenyl buta-2,3-dienoate 2c
as substrates. Moreover, γ-substituted allenoate (2d) was also
compatible in the reaction to generate the corresponding 4o in
[16]
that cinchonine derived β-ICD was the most efficient catalyst
in the reaction, product 10 was obtained in 34% yield along
with 70% ee (Scheme 4, eq. 1). Then, we tried to complete the
one-pot chromene construction with β-ICD as catalyst. Unfortu-
nately, product 3 was not detected under the optimal catalytic
conditions because of the steric affection of substrate 1a
(Scheme 4, eq. 2).
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8% yield, the low efficiency is probably due to the proton shift
[15]
from terminal methyl group of allenoate 2d.
To evaluate the robustness and practical utility of this one-
pot cascade reaction, an enlarge reaction of 1c with 2a was run
under the optimal reaction conditions. As shown in Scheme 3,
the desired chromene product 4b was obtained in 71% yield.
Moreover, several transformations and applications of 4b have
been explored to show the utility of this methodology
A plausible mechanism was illustrated on basis of our
[17]
experiments and previous reports (Scheme 5). The reaction
was initiated by the nucleophilic attack of DMAP at the β-
carbon of allenoate 2 to generate the zwitterionic intermediate
A, which coexist with intermediate B via allyl equilibrium. An α-
attack of A to substrate 1 followed by aromatication generate
C. Sequentially, a proton shift and regenerated tertiary amine
catalyst to give the product 3. Then the de-protection of sillyl
group by TBAF and the in-situ generated nucleophilic species
undergo oxa-Michael addition to form intermediate E. Finally,
intermediate E go through protonation and double bond
isomerization to produce the desired chromene product 4.
(Scheme 3). The ester group was easily transfer to hydroxymeth-
yl product 5 in high yield with the chromene skeleton
maintenance. The hydroxyl of phenol was easily protected by
methyl group to give product 6 in 87% yield under mild
conditions. Moreover, the product 4b could be transferred to a
chromene acid 7 in 96% yield via heterogeneous Pd/C hydro-
genation (Scheme 3, eq. 1–3). An amino-substituted p-QM 8
was also investigated in the reaction, but the reaction
Scheme 3. Scale-up and transformation experiments.
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Scheme 4. Asymmetric allenylation.
Scheme 5. Proposed mechanism.
Experimental Section
Conclusion
General Procedure: p-QMs 1 (1.0 eq.), DMAP (0.1 eq.) and anhydrous
Et O (0.1 M) were added to an oven dried Schlenk tube, then
In summary, we have established a novel and efficient method
to access functionalized chromene by using hydroxyl p-QMs
and allenoates with moderate to good yields (up to 82%) in
mild conditions. Different substituted groups were tolerated in
this methodology and a set of transformations were furnished
to exhibit the potential utility. A Rauhut-Currier and oxa-Michael
cascade progress enabled by DMAP and TBAF organocatalysts
in one-pot progress was proposed as the mechanism of the
reaction. The methodology provides a new route to the
construction of chromene related compounds. Further applica-
tions of this method for biologically active compounds and its
asymmetric synthesis are ongoing in our lab.
2
allenotes 2 (1.2 eq.) was added and the reaction mixture were
stirred at room temperature for 2 hours. Then, TBAF (1.0 M in THF,
1.0 equiv) were added directly in one-pot and the mixture were
stirred for another 1 h. Then water (2 mL) was added to the reaction
mixture and extracted with ethyl ether (3 mL*2). The organic layer
was dried over with anhydrous Na SO and filtered. The solvent was
removed under reduced pressure and the residue were purified by
column chromatography on silica gel (PE:EA=20:1, R =0.3–0.5),
affording the corresponding products 4.
2
4
f
Benzyl4-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-methyl-4H-chro-
mene-3-carboxylate (4a). Compound 4a (33 mg, 68% yield) was
obtained as a white solid following the general procedure from 1b
(0.1 mmol, 43 mg) and 2a (0.12 mmol, 21 mg). R =0.5 (PE:EA=
f
1
20:1); H NMR (400 MHz, CDCl
) δ 7.30–7.27 (m, 3H), 7.14–7.12 (m,
3
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4
H), 7.02–7.00 (m, 2H), 6.98 (s, 2H), 5.12 (d, J=1.2 Hz, 2H), 5.03 (s,
2015, 7, 1524–1526; c) P. Chauhan, U. Kaya, D. Enders, Adv. Synth. Catal.
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Front. 2020, 7, 1743–1778.
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13
2
1
H), 4.98 (s, 1H), 2.51 (s, 3H), 1.34 (s, 18H); C NMR (100 MHz, CDCl3)
δ 167.1, 161.0, 152.3, 149.5, 137.2, 136.4, 135.5, 129.0, 128.4, 127.7,
127.4, 127.2, 125.6, 124.5, 124.0, 116.0, 106.3, 65.8, 41.0, 34.2, 30.2,
19.5; IR ν 3635, 2958, 1712, 1643, 1596, 1493, 1209, 1062, 821,
[
8] K. Zhao, Y. Zhi, T. Shu, A. Valkonen, K. Rissanen, D. Enders, Angew.
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Chem. 2018, 83, 364–373.
À 1
+
+
6
5
96 cm ; m.p. 148–149°C; HRMS calcd. for C H O Na [M+Na] :
32
36
4
07.2511, found: 507.2506.
Supporting Information (see footnote on the first page of this
article): Spectroscopic data of the compounds shown in Tables and
Schemes, the detailed descriptions of experimental procedures and
the crystal structure of 4e (CCDC 2044635).
[
[11] a) G.-J. Mei, S.-L. Xu, W.-Q. Zheng, C.-Y. Bian, F. Shi, J. Org. Chem. 2018,
1
1
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1
1
1
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83, 1414–1421; During preparation of this manuscript, a similar work
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We thank the Fundamental Research Funds for the Central
Universities in China (202041003, 861801013177, 841912005 and
8
for financial support. The project was partially funded by National
Science and Technology Major Project of China (No.
2
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crystallographic data for this paper. These data are provided free of
charge by the joint Cambridge Crystallographic Data Centre and
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42064004) and NSFC (No. 81991522, U1706213 and 81973232)
018ZX09735-004), Youth Innovation Plan of Shandong Province
(
(
2019KJM004) and Jinan municipal government fund
2019GXRC039).
[
Conflict of Interest
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Keywords: Allenaotes · Chromenes · One-pot reaction · para-
Quinone methides · Tertiary amine
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Manuscript received: January 28, 2021
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