1-Arylvinyl formats: A New CO Source and Ketone Source in Carbonylative Synthesis of Chalcone Derivatives

Article abstract of DOI:10.1002/cctc.201900011

1-Arylvinyl formates as a kind of new CO surrogate have been explored for the first time. Most of the known CO precursors usually produce undesired residuals, which have to be removed. In this strategy, after CO release, the in situ generated acetophenones from 1-arylvinyl formates can be successfully applied as a good ketone source in the synthesis of chalcones with benzaldehydes via a palladium-catalyzed reductive carbonylation reaction. A variety of chalcones were isolated in satisfactory to good yields with good substrates compatibilities under mild conditions.

Full text of DOI:10.1002/cctc.201900011

Accepted Article
Title: 1-Arylvinyl formats: A New CO Source and Ketone Source in
Carbonylative Synthesis of Chalcone Derivatives
Authors: Xiao-Feng Wu, ming lai, xinxin qi, Jin-Bao Peng, Jun Ying,
and Min-Jie Zhu
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To be cited as: ChemCatChem 10.1002/cctc.201900011
Link to VoR: http://dx.doi.org/10.1002/cctc.201900011
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10.1002/cctc.201900011
ChemCatChem
COMMUNICATION
1-Arylvinyl formats: A New CO Source and Ketone Source in
Carbonylative Synthesis of Chalcone Derivatives
Xinxin Qi,[a] Ming Lai,[a] Min-Jie Zhu,[a] Jin-Bao Peng,[a] Jun Ying,[a] Xiao-Feng Wu*[a,b]
Abstract: 1-Arylvinyl formates as a kind of new CO surrogate have
been explored for the first time. Most of the known CO precursors
usually produce undesired residuals, which have to be removed. In
this strategy, after CO release, the in situ generated acetophenones
from 1-arylvinyl formates can be successfully applied as a good
ketone source in the synthesis of chalcones with benzaldehydes via
a palladium-catalyzed reductive carbonylation reaction. A variety of
chalcones were isolated in satisfactory to good yields with good
substrates compatibilities under mild conditions.
CO pressure have become a powerful strategy for the synthesis
of chalcones and their analogs.[13] In our continuous efforts on
the development of new CO surrogates, we recently reported a
series of palladium-catalyzed carbonylation reaction with formic
acid as the CO source.[14] However, with acetic anhydrides as
activator, the in situ generated acetic acid need excess amount
of base to neutralize. Considering both the synthetic interest for
chalcones and the investigation of new CO precursors,
compound 1-phenylvinyl formate came into our mind. It would
release CO and acetophenone under base condition. The in situ
formed CO could react with iodobenzene via a reductive
carbonylation reaction to give benzaldehyde, followed by an
aldol condensation with residual acetophenone to afford
chalcone product (Scheme 1). With this idea in mind, we
describe here a palladium-catalyzed reductive carbonylation
reaction for the synthesis of chalcones and their derivatives from
aryl iodides with 1-arylvinyl formates as both CO source and
ketone source.
Since the pioneering work of Heck and co-workers in 1974,[1]
palladium-catalyzed carbonylative transformations have drawn
continuously attentions for their widely application in the
synthesis of numerous congeners of carbonyl compounds.[2] As
a fundamental C1 source, carbon monoxide (CO) gas is cheap
and easily available, it has been widely utilized in palladium-
catalyzed carbonylative transformations, especially in industrial
scales. However, gaseous CO is odorless, toxic, and requires
high pressure-resistant equipment. All of these characters of CO
gas restrict its utilization on a laboratory scale. Therefore, many
efforts have been put in alternative methods with CO gas-free
conditions, and various CO surrogates have been development
in recent years, such as metal carbonyl complexes,[3] oxalyl
chlorides,[4] paraformaldehyde,[5] formates,[6] formamides,[7]
benzene-1,3,5-triyl triformate (TFBen),[8] and others.[9] However,
the known CO precursors have several disadvantages, including
harsh reaction conditions, (sub)stoichiometric metal wastes or
other unneeded residuals, and so on. In this sense, the
searching for new CO sources without byproducts affecting
under mild reaction conditions are still highly in demand.
Scheme 1. Proposed method for carbonylative synthesis of
chalcone with 1-phenylvinyl formate as the new designed CO
surrogate.
Table 1. Screening of reaction conditions.a
Chalcones and their derivatives represent a valuable class
of natural products, which display a wide spectrum of biological
activities.[10] They also serve as very important synthons for
heterocycle preparation. Due to their versatile bioactive
properties and promising application for the investigation of new
drugs, research on chalcones and their derivatives have drawn
continuously attention.[11] Traditional synthetic methods for
chalcones mainly rely on Claisen-Schmidt condensation reaction
of aromatic aldehydes with acetophenones under strong basic
conditions.[12] And in recent years, palladium-catalyzed
carbonylative heck-type coupling reaction between aryl
triflates/halides with diverse vinyl-containing compounds under
Yield
Entry
Ligand
Base
Solvent
(%)b
33
22
23
61
36
17
19
16
0
1
2
PCy3
PPh3
BuPAd2
L1
DBU
DBU
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
THF
3
DBU
4
DBU
5
Xantphos
DPPB
DPPPE
DPPF
L1
DBU
6
DBU
7
DBU
8
DBU
[a]
[b]
Dr. X. Qi, M. Lai, M.-J. Zhu, Dr. J.-B. Peng, Dr. J. Ying, Prof. Dr. X.-
F. Wu
Department of Chemistry, Zhejiang Sci-Tech University
Xiasha Campus, Hangzhou 310018, People’s Republic of China.
E-mail: xiao-feng.wu@catalysis.de
9
Et3N
10
11
12
13
14
15
L1
DiPEA
DABCO
NaHMDS
Cs2CO3
KOH
0
L1
0
L1
0
Leibniz-Institut für Katalyse e.V. an der Universität Rostock
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
L1
0
L1
0
Supporting information for this article is given via a link at the end of
the document.
L1
DBU
43
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10.1002/cctc.201900011
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COMMUNICATION
16
17
18
19
20c
L1
L1
L1
L1
L1
DBU
DBU
DBU
DBU
DBU
CH3CN
DMF
49
32
18
45
65
Table 2. Substrates scope on aryl iodides.a
DMSO
Toluene
1,4-dioxane
aReaction conditions: iodobenzene (0.5 mmol), 1-phenylvinyl
formate (1.5 mmol), catalyst (3 mol%), ligand (3 or 6 mol%), base
b
(2.0 mmol), Et3SiH (1.0 mmol), solvent (2 mL), 80 °C, 24 h. Yield
were determined by GC with dodecane as an internal standard.
cMgSO4 (1.0 mmol). L1: 2-(diphenylphosphino)biphenyl.
Initially, iodobenzene was used as model substrate,
Pd(OAc)2 as catalyst, PCy3 as ligand, Et3SiH as hydrogen
source, DBU as base, 1-phenylvinyl formats as both CO and
ketone source, in 1,4-dioxane at 80°C. Fortunately, 33% yield of
the desired product was obtained (Table 1, entry 1). Encouraged
by this result, various mono- and bidentate phosphine ligands
were
studied,
involving
PPh3,
BuPAu2.
L1
[2-
(diphenylphosphino)biphenyl], Xantphos, DPPB, DPPPE, and
DPPF (Table 1, entries 2-8). 61% yield was obtained with L1 as
the ligand (Table 1, entry 4). It was noteworthy that the base
played a very important role in this reaction, no product could be
observed with Et3N, DiPEA, DABCO, NaHMDS, Cs2CO3, or
KOH as the base (Table 1, entries 9-14). Furthermore,
screening of different solvents proven 1,4-dioxane to be the best
solvent for the transformation (Table 1, entries 15-19).
Remarkably, a slightly higher yield can be achieved when
MgSO4 was used as an additive (Table1, entry 20). Here, the
role of MgSO4 is to absorb the water generated from aldol
condensation between acetophenone and benzaldehyde.
With the optimized reaction conditions in hands, we went
on our study on substrates scope and the results were
summarized in Table 2. Aryl iodides with electron-donating
groups, involving methyl, ethyl, t-butyl, methoxy and dimethyl-
substitute groups are tolerated well to give the corresponding
chalcone products in good yields (3aa-3ka). Notably, those
substrates bearing ortho- and para-substitute afforded the target
products in higher yields compared with meta-substituted
starting materials, which might due to the electronic effect (3ga,
and 3ia vs. 3ha). Aryl iodides with chloro and fluoro groups
could smoothly produce the final products in 55% and 68%
yields as well (3la-3an). Notably, aryl iodides bearing both
methyl and fluoro groups were also worked well to provide the
corresponding chalcone in moderate yield (3oa). Furthermore,
substrates with 1-biphenyl, 1- and 2-naphthalene moieties were
examined; the desired chalcone products were obtained in good
yields (3pa-3ra). We also tested heterocycles such as 3-
thiophene, 5-benzodioxole, and 6-iodoquinoline groups; the
desired products were isolated in 50%, 52%, and 58% yields,
respectively (3sa-3ua).
aReaction conditions: aryl iodides (0.5 mmol), 1-phenylvinyl formate
(1.5 mmol), Pd(OAc)2 (3 mol%), L1 (6 mol%), DBU (2.0 mmol),
Et3SiH (1.0 mmol), MgSO4 (1.0 mmol), 1,4-dioxane (2 mL), 80 °C, 24
h, isolated yield. b60 °C.
Furthermore, the substrates scope of 1-arylvinyl formats have
been investigated (Table 3). 1-Arylvinyl formats with methyl, t-
butyl, fluoro, and chloro groups worked well to produce the
chalcone derivatives in moderate to good yields (3ab-3ae).
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Table 3. Substrate scopes on 1-arylvinyl formats.a
In conclusion, 1-arylvinyl formats as a kind of new CO
precursors have been prepared and applied. As both promising
CO source and ketone source, 1-arylvinyl formates have been
successfully utilized in the synthesis of chalcone derivatives
through a palladium-catalyzed reductive carbonylation reaction
with aryl iodides for the first time. A series of aryl iodides were
tolerated well to provide the final chalcone products in moderate
to high yields under mild reaction conditions. The further
applications of this kind of CO surrogate are under progress.
Experimental Section
Under nitrogen, Pd(OAc)2 (3 mol%), L1 ([1,1'-biphenyl]-2-
yldiphenyl phosphine) (6 mol%) and MgSO4 (1.0 mmol) were
added to a 15 mL tube. Then iodobenzene (0.5 mmol), 1-
arylvinyl formate (1.5 mmol), Et3SiH (1.0 mmol) and DBU (2.0
mmol) were added by syringe. The tube was sealed and the
reaction mixture was stirred at 60-80 oC for 24 h. After the
reaction was completed, the reaction mixture was concentrated
by rotary evaporation. The crude mixture was purified by silica
gel column chromatography (PE/EA = 50/1) to provide the
desired pure products.
aReaction conditions: iodobenzene (0.5 mmol), 1-arylvinyl formates
(1.5 mmol), Pd(OAc)2 (3 mol%), L1 (6 mol%), DBU (2.0 mmol),
Et3SiH (1.0 mmol), MgSO4 (1.0 mmol), 1,4-dioxane (2 mL), 80 °C, 24
h, isolated yield.
Based on the above results, a plausible reaction mechanism
is proposed (Scheme 2). First, arylpalladium complex was
formed from the oxidative addition of Pd0Ln with aryl iodide.
Subsequently, benzoylpalladium intermediate will be formed
after the coordination and insertion of CO (in situ generated from
1-arylvinyl formates) to the arylpalladium complex, which will
finally eliminate aromatic aldehydes in the presence of Et3SiH.
Furthermore, an aldol condensation between produced aromatic
aldehydes and acetophenones (in situ generated from 1-
arylvinyl formates) in the presence of DBU, affording the final
chalcone products.
Acknowledgements
The authors thank the financial supports from NSFC
(21772177, 21602201). X.-F. Wu appreciates the general
supports from Professors Matthias Beller and Armin Börner
in LIKAT.
Keywords: CO surrogate • 1-arylvinyl formates • chalcones •
palladium catalyst • reductive carbonylation
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Xinxin Qi, Ming Lai, Min-Jie Zhu, Jin-Bao
Peng, Jun Ying, Xiao-Feng Wu*
Page No. – Page No.
1-Arylvinyl formats: A New CO
Source and Ketone Source in
Carbonylative Synthesis of Chalcone
Derivatives
1-Arylvinyl formates as a kind of efficient and convenient CO surrogates have been
explored for the first time. In this strategy, after CO release, the in situ generated
acetophenones from 1-arylvinyl formates could be successfully applied as a good
ketone source in the synthesis of chalcones with benzaldehydes via a palladium-
catalyzed reductive carbonylation reaction. A variety of chalcones were isolated in
moderate to excellent yields with good substrates compatibilities under mild
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