A Strategy for Accessing Aldehydes via Palladium-Catalyzed C?O/C?N Bond Cleavage in the Presence of Hydrosilanes

Article abstract of DOI:10.1002/adsc.202000794

We report the catalytic reduction of both active esters and amides by selective C(acyl)?X (X=O, N) cleavage to access aldehyde functionality via a palladium-catalyzed strategy. Reactions are promoted by hydrosilanes as reducing reagents with good to excellent yields and with excellent chemoselectivity for C(acyl)?N and C(acyl)?O bond cleavage. Carboxylic acid C(acyl)?O bonds are activated by 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) to form triazine ester intermediates, which further react with hydrosilanes to yield aldehydes in one-pot two-step procedures. We demonstrate that C(acyl)?O cleavage/formylation offers higher yields and broader substrate scopes compared with C(acyl)?N cleavage under the same reaction conditions.

Full text of DOI:10.1002/adsc.202000794

Title: A Strategy for Accessing Aldehydes via Palladium-Catalyzed C-
O/C-N Bond Cleavage in the Presence of Hydrosilanes
Authors: Zhanyu He, Zijia Wang, Junxiang Ru, Yulin Wang, Tingting
Liu, and Zhuo Zeng
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000794
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10.1002/adsc.202000794
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
A Strategy for Accessing Aldehydes via Palladium-Catalyzed C-
O/C-N Bond Cleavage in the Presence of Hydrosilanes
Zhanyu He,a† Zijia Wang,a† Junxiang Ru,a Yulin Wang,a Tingting Liu,a,* Zhuo Zengab,*
a School of Chemistry, South China Normal University, Guangzhou 510006, People’s Republic of China
Fax:(+86)-20-3931-0187 E-mail: liutt5@163.com; zhuoz@scun.edu.cn;
† These authors contributed equally to this work.
b
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science,
345 Lingling Road, Shanghai 200032, China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete
if
not
appropriate))
Abstract. We report the catalytic reduction of both active
esters and amides by selective C(acyl)–X (X = O, N)
cleavage to access aldehyde functionality via a palladium-
catalyzed strategy. Reactions are promoted by
hydrosilanes as reducing reagents with good to excellent
yields and with excellent chemoselectivity for C(acyl)–N
and C(acyl)–O bond cleavage. Carboxylic acid C(acyl)–O
bonds are activated by 2-chloro-4,6-dimethoxy-1,3,5-
triazine (CDMT) to form triazine ester intermediates,
which further react with hydrosilanes to yield aldehydes in
one-pot two-step procedures. We demonstrate that
C(acyl)–O cleavage/formylation offers higher yields and
broader substrate scopes compared with C(acyl)–N
cleavage under the same reaction conditions.
aldehydes in moderate yields with the isolation of the
corresponding alcohols as overreduction byproducts.
To obtain aldehydes efficiently, carboxylic acids are
first converted into highly reactive derivatives such as
acyl chlorides[6], then further converted to aldehydes
with high chemoselectivity. Rosenmund reduction has
been the general method for the transformation of
acyl chlorides into aldehydes (Scheme 1a)[7].
In recent decades, transition-metal-catalyzed
reactions have engendered a central transformation in
organic synthesis[8]. Recently, tremendous progress
has been made on the selective C-O/C-N bond
cleavage of active esters/amides. The Garg[9],
Keywords: C-O/C-N bond cleavage; Hydrosilanes;
Palladium-catalyzed; Reduction; Aldehydes;
Szostak[10]
,
Rueping[11]
,
Yamaguchi[12]
,
Shi[13]
,
Huang[14] and Zou[15] groups have reported many
works in this field, providing a powerful strategy to
obtain target molecules in organic synthesis. These
activated esters/ amides can be converted from
carboxylic acids directly and used in transition-metal-
catalysis, which indicates that they can provide a new
protocol for the synthesis of aldehydes.
Aldehydes play an important role in constructing
different kinds of organic molecules, and they have a
wide range of applications in pharmaceuticals,
agrochemicals, and perfumes as vital intermediates[1].
A simple and efficient approach to aldehydes
preparations remains
a
challenge in organic
chemistry[2], and the classic methods used to prepare
aldehydes mainly include the oxidation of primary
alcohols or the reduction of carboxylic acids and their
derivatives[3]. The Oxidation of primary alcohols
requires careful handling to avoid overoxidation and
the creation of carboxylic acid byproducts. In the case
of carboxylic acid derivatives, there are two possible
reduction products: an aldehyde and an alcohol.
Carboxylic acids or their derivatives can be reduced
in a variety of ways, and aluminum-H, boron-H, and
H2 are the most powerful reductants[4]. Compared
with hydrosilanes, these traditional reagents are
flammable and unstable due to their pyrophoric
nature[5]. Furthermore, the process produces
To the best of our knowledge, the one-pot
conversion process of carboxylic acids to aldehydes
has been well developed. In 1998, the Yamamoto
group[16] first reported a catalytically hydrogenated
approach to obtain aldehydes from carboxylic acids in
the presence of Piv2O. They carried out the reduction
under 30 bar of flammable hydrogen. Later, Professor
Gooßen[17] modified the catalyst system to conduct a
reaction under 5 bar of hydrogen. In 1999, the Taddei
group[18] first reduced triazine esters to aldehydes
from carboxylic acids in the presence of 5 bar of
hydrogen, but an overreduced alcohol byproduct was
obtained (Scheme 1b). In 2013, the Tsuji group
1
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10.1002/adsc.202000794
Advanced Synthesis & Catalysis
developed
a
palladium-catalyzed reduction of step procedure in our previous report. We anticipate
carboxylic acids to corresponding aldehydes in the the use of this one-pot procedure to investigate the
presence of hydrosilanes (Scheme 1c)[19]. These reduction of carboxylic acids to aldehydes by C-O
exceptional works provided
a
straightforward bond cleavage. The proposed C-O/formylation was
approach for the efficient synthesis of aldehydes from first surveyed in a model reaction between benzoic
carboxylic acids. Despite the significant progress that acid and hydrosilanes. The catalysts, ligands, solvents,
has been achieved in the reduction of carboxylic acids, temperature, and hydrosilanes, were systematically
limits remain, such as the production of overreduced screened in this reaction, and their data are
alcohol, longer reaction times, and the presence of summarized in Table 1. Initially, we attempted to
explosively flammable hydrogen.
achieve this transformation in the presence of a 5
mol% Pd(PPh3)4 catalyst, resulting in corresponding
aldehydes in 78% yield (Table 1, Entry 1). After
several experiments in different catalyst systems
(Table 1, Entries 2-9), we found that the ligand is
essential and influences the yield; PPh3 was found to
be
the
most
efficient
ligand,
(PCy3),
(dppb),
whereas
1,4-
tri(cyclohexyl)phosphine
bis(diphenylphosphino)butane
bis(diphenylphosphino)ferrocene
1,1'-
2-
(dppf),
(dicyclohexylphosphino)-3,6-dimethoxy-2'-4'-6'-tri-i-
propyl-1,1'-biphenyl (Brettphos), and 4,5-
bis(diphenylphosphino)-9,9-dimethylxanthene
(Xantphos) delivered the product in low yields. With
this condition in hand, we selected the Pd(PPh3)2Cl2
as the catalyst system.
Furthermore, the solvents were also screened with
toluene being the best choice (Table 1, Entries 10-13).
Based on the above conditions, the reaction
temperature was further optimized. Surprisingly, the
target compound could be obtained in good yield at
80 °C (Table 1, Entries 14-15).
In addition, decreasing the amount of Pd(PPh3)2Cl2
resulted in a significant decrease in yield while
increasing the catalyst loading from 3 mol% to 8
mol% did not obviously affect the yield. (Table 1,
Entries 16-18). Finally, we compared various
hydrosilanes and found that Ph(CH3)2SiH gave the
best result (Table 1, Entries 18-21).
Scheme 1. Reduction of carboxylic acids and derivatives
Our group has a continuing interest in C-O/C-N
bond cleavage by metal catalysis[20], as carboxylic
acids/amides can now be used in several important
transformations, including Suzuki-Miyaura couplings,
C–H functionalization, and transamidation. Here, we
hypothesize that triazine ester or N-acylsaccharins can
be utilized in the synthesis of aldehydes by highly
chemoselective C(acyl)–X (X=O, N) cleavage.
(Scheme 1d). The characteristics of our study
include: (a) proof of a general and facilitating path for
the formylation of carboxylic acids; (b) a simple
catalytic system for the direct reduction of a wide
range of carboxylic acids via C(acyl)–X (X=O, N)
cleavage; and (c) utilization of a mild reductant
instead of flammable hydrogen to avoid overreduced
alcohol and provide a gram-scale reaction in the
laboratory.
Based on these experiments, the optimized reaction
conditions were set as 5 mol% Pd(PPh3)2Cl2,
Ph(CH3)2SiH (1.5 equiv) in toluene at 80 °C for 6 h.
Table 1. Optimization studies for the reduction of
carboxylic acids[a]
Entry Catalyst(mol%)
Ligand
none
none
none
PCy3
Solvent Yield[b]
1
2
3
4
Pd(PPh3)4 (5)
Pd2(dba)3 (5)
PdCl2 (5)
toluene
toluene
toluene
toluene
78
<5
<5
50
Triazine esters were synthesized efficiently from
carboxylic acids in high yield, and then further
transformed to aryl ketones through a one-pot two-
PdCl2 (5)
2
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10.1002/adsc.202000794
Advanced Synthesis & Catalysis
5
6
7
8
9
10
11
12
13
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
dppb
dppf
brettphos toluene
Xantphos toluene
toluene
toluene
<5
<5
62
29
85
27
30
71
75
56
78
81
85
37
<5
<5
<5
(1.5 equiv) in toluene at 80 °C for 6 h (Scheme 2).
Benzoic acid 1a was employed as a substrate and
resulted in the highest yield (3a, 85%). To investigate
electronic factors, Ph(CH3)2SiH (2a) was used as a
reducing reagent. Several carboxylic acids with
electron-donating groups in para-positions reacted
with 2a to provide corresponding aldehydes in good
yields (3b-3f). Electron-withdrawing substrates
containing trifluoromethyl, aldehyde, ester, and cyano
groups were well tolerated in this protocol and
provided the desired products in 64%, 96%, 88%, and
75% yields respectively (3g-3j). In addition, steric
hindrance on the carboxylic acid (3d) was also
tolerated. The halide substituents F (1k), Cl (1l), and
Br (1m) were tolerated in this reaction and afforded
the desired products in medium yield. In addition,
alkenyl (1n) and heteroaromatic acid (1o)
demonstrated good reactivity and provided the
corresponding products in 81% and 61% yields (3n,
PdCl2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
none
none
none
none
none
none
none
none
none
none
none
none
none
toluene
DMSO
DMF
dioxane
CH3CN
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
14[c] Pd(PPh3)2Cl2 (5)
15[d] Pd(PPh3)2Cl2 (5)
16
17
Pd(PPh3)2Cl2 (3)
Pd(PPh3)2Cl2 (8)
18[e] Pd(PPh3)2Cl2 (5)
19[f]
Pd(PPh3)2Cl2 (5)
20[g] Pd(PPh3)2Cl2 (5)
21[h] Pd(PPh3)2Cl2 (5)
[a]Reactions were conducted on 0.3 mmol 1a and 1 mL solvent
at 80 °C using 0.45 mmol of hydrosilane in the presence of 5
mol% catalysis, for 6 h.
[b]Yield was determined by using GC.
[c]At 70 °C. [d]At 90 °C.
3o).
Other
carboxylic
acids
including
[e]Using 0.45 mmol Et3SiH as the reductant.
[f]Using 0.45 mmol Ph2CH3SiH as the reductant.
[g]Using 0.45 mmol Ph3SiH as the reductant.
[h]Using 0.45 mmol Ph2SiH2 as the reductant.
NMM= 4-Methylmorpholine.
primary/secondary/tertiary alkyl acids (1p-1t) were
all well tolerated and obtained excellent yields.
To explore the yield-determining step, the phenyl
and p-methoxyphenyl triazine esters were isolated and
purified. These triazine esters were reacted with
hydrosilanes directly (Scheme 3). Considering the
yield of aldehydes, the subsequent silane reduction
step was the yield-determining step in this reaction.
dba= dibenzylideneacetone
Scheme 3. Investigation of yield-determining step
Fortunately, the present reaction is amenable to
being scaled-up to a gram-scale using methyl 4-
formylbenzoate and Ph(CH3)2SiH as substrates, and
90% yield was achieved.
[a]Reactions were conducted on 0.3 mmol 1 and 1 mL
toluene at 80 °C using 0.45 mmol of Ph(CH3)2SiH in the
presence of 5 mol% of Pd(PPh3)2Cl2, for 6 h.
[a]Gram scale reaction (in 10 mmol), see the SI for details.
Scheme 4. Scale-up of the one-pot reaction[a]
[b]GC yield was given because a product with a low boiling
point was considerably lost during the isolation process.
Scheme 2. Scope of carboxylic acids in the one-pot
synthesis of aldehydes[a]
To demonstrate the availability of this mild
reduction method, we accomplished the synthesis of
2,6-dichlorobenzaldehyde oxime, an important
pharmaceutical intermediate for the manufacture of
diclofenac sodium and dichlobenil[21]. The traditional
Under optimized reaction conditions, we explored
the functional-group tolerance of carboxylic acids in
the case of 5 mol% Pd(PPh3)2Cl2 and Ph(CH3)2SiH
starting
from
1-chloro-2-methyl-3-nitrobenzene
3
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10.1002/adsc.202000794
Advanced Synthesis & Catalysis
involves chlorination, hydrolysis, and deuteration[22]
.
Our method utilizes carboxylic acids as the starting
material to obtain the target molecule with a one-pot
procedure in 46% yield. This example emphasizes the
potential synthetic utility of the method and this green
and convenient method is suitable for industrial
applications.
Scheme 7. The reduction of N-acylsaccharins
Next, we optimized the reaction conditions. After
several experiments for extensive optimization (see SI
for optimization details), we identified conditions to
achieve the reduction of N-acylsaccharins. The
aldehyde products were obtained in the highest yield
with 5 mol% Pd(PPh3)Cl2 catalyst, Ph(CH3)2SiH (1.5
equiv) in toluene at 80 °C for 4 h. Other Pd(II)
precatalysts, ligands, solvents, and hydrosilanes were
screened (see SI) and provided aldehydes in lower
yields. As shown in the SI, Ph(CH3)2SiH obtains a
better yield than other hydrosilanes. Additionally, the
reaction using toluene as a solvent had a higher yield
than THF, CH3CN, DMF, and DMSO.
Scheme 5. Synthesis of 2,6-dichlorobenzaldehyde oxime
A step-wise reaction was then investigated by
adding all components at one time. 4-
(methoxycarbonyl)benzoic acid, as a representative
example, was reacted with CDMT, NMM,
Ph(CH3)2SiH in the presence of Pd catalyst at 80 °C
for 7 h in one-pot. The corresponding aldehydes were
obtained in 89% yield (Scheme 6).
The high reactivity of the developed reaction
system was emphasized in this transformation, as
electron-neutral (5a, 5b, 5c, 5d, 5e, 5f, 5g), electron-
rich (5h and 5i) and electron-deficient (5j, 5k, 5l)
substrates were all tolerated (Scheme 8). In an effort
to synthesize alkenyl, heteroaryl, and alkyl
substituents (5m, 5n, 5o, 5p), the target molecules
were obtained in 40-58% yield. N-acylsaccharins will
be developed as new intermediate reducing carboxylic
acids to generate a variety of aldehydes.
Scheme 6. One-pot procedure for synthesis of methyl 4-
formylbenzoate
We then turned our attention to the reduction of the
active amide. The electronic-destabilization of the N-
C(O) bond in active amide enables a synthetically
appealing catalytic reduction by C-N acyl cleavage[23]
.
In 2013, Manabe’s group[24] reported the palladium-
catalyzed reduction of N-benzoylsaccharin with
Et3SiH via Pd/dppb catalyzed in the presence of
Na2CO3 (1 equiv) in DMF at 60 °C for 15 h to give
benzaldehyde in 64% yield (Scheme 7a). It is
regrettable that they only elucidated the mechanism
by this reaction and only one example was reported.
Inspired by Manabe’s work, we considered that the
easily prepared and stable N-acylsaccharins[25] can be
harnessed as electrophile coupling partners with
hydrosilanes in palladium-catalyzed reduction
reactions (Scheme 7b).
[a] Reactions were conducted on a 0.3 mmol 4 and 1 mL
toluene at 80 °C using 0.45 mmol of Ph(CH3)2SiH in the
presence of 5 mol% of Pd(PPh3)2Cl2, for 4 h.
4
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10.1002/adsc.202000794
Advanced Synthesis & Catalysis
[b] GC yield was given because a product with a low boiling
point was considerably lost during the isolation process.
Scheme 8. Scope of aldehydes in the reduction of N-
acylsaccharins[a]
A plausible mechanism for the catalytic reaction is
shown in Scheme 10. First, we employ active esters
as a model to discuss the mechanism. Carboxylic
acids and CDMT provide triazine esters. As shown in
the scheme, Pd(II) is reduced to Pd(0), and
Furthermore, comparative experiments were
carried out under the optimized reduction condition
for a range of electronically and sterically different
amides were carried out (Scheme 9). N-Boc (4r) and
N-Ts (4s) were not suitable for this protocol. The
reduction of twisted cyclic imides (4t and 4u) was
completely unreactive. The experimental data shows
the unique activity of N-acylsaccharins (4a) in this
transformation. An electron-withdrawing sulfonyl
moiety and distortion of the amide bond might result
in ground-state destabilization of N-acylsaccharins,
which could explain its high reactivity in this
1
intermediate A was detected by H NMR. Then, the
oxidative addition takes place at the C-O bond of the
triazine ester to afford an acylpalladium (II) complex.
Following transmetallation, complex (III) is
generated under the reaction of hydrosilanes.
Intermediate
B
was detected by 29Si NMR
measurements of the resulting reaction mixture
(δ=1.13 ppm, without 1H decoupling, s) Then,
reductive elimination occurred to form aldehydes and
regenerate the Pd(0) species. Next, the reduction of N-
acylsaccharins to aldehydes proceeds through a
similar mechanism as triazine ester.
reaction[20d, 26]
.
In summary, we have developed a palladium-
catalyzed approach for the reduction of triazine
esters/N-acylsaccharins to aldehydes via C-O/C-N
bond cleavage. This new approach offers an easy
method and practical routine for the synthesis of
aldehydes in the laboratory to avoid explosively
flammable hydrogen as an H-source. Remarkably, the
transformation was achieved under a simple catalyst
system and a short reaction time. The high functional
group tolerance allows the production of a variety of
aldehydes in moderate to good yields. Notably,
primary, secondary, and tertiary alkyl carboxylic
acids were also well tolerated. Overall, this reaction
performed well at the gram scale, which indicates its
potential applicability in batch processes.
Scheme 9. Control reaction
Experimental Section
General Procedure for the synthesis of aldehydes
by C-O bond cleavage
A sealed tube equipped with a stir bar was charged
with 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT)
(0.3 mmol), carboxylic acids (0.3 mmol), and 4-
methylmorpholine (0.3 mmol) stirring in toluene (1
mL) at room temperature for 1 h. After reaction
completion monitored by TLC, the flask was charged
with Pd(PPh3)2Cl2 (5 mol%) and Ph(CH3)2SiH (0.45
mmol). The mixture was stirred and heated at 80 °C
for 6 h. After cooling to room temperature, the
mixture was purified by silica gel column
chromatography (petroleum ether or hexane/EtOAc =
50:1 or 20:1) to afford aldehydes and calculate the
yields. Because some aldehydes have low boiling
points, their reaction mixture was analyzed by GC
directly and the yield was determined using
cyclohexane, decane or dodecane as an internal
standard.
General Procedure for the synthesis of aldehydes
by C-N bond cleavage
Scheme 10. A plausible mechanism for the catalyst
reaction
5
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10.1002/adsc.202000794
Advanced Synthesis & Catalysis
A sealed tube equipped with a stir bar was charged
with Ph(CH3)2SiH (0.45 mmol), N-acylsaccharins (0.3
mmol., Pd(PPh3)2Cl2 (5 mol%) and toluene (1 mL).
The reaction mixture was placed in an oil bath and
stirred for 4 h at 80 °C. After cooling to room
temperature, the mixture was purified by silica gel
column chromatography (petroleum ether or
hexane/EtOAc = 50:1 or 20:1) to afford aldehydes
and calculate the yields. Because some aldehydes
have low boiling points, their reaction mixture was
analyzed by GC directly and the yield was determined
using cyclohexane, decane or dodecane as an internal
standard.
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Acknowledgments
The authors gratefully acknowledge the support of
Science and Technology Planning Project of
Guangdong Province (2017A010103017), National
Natural Science Foundation of China (51703069,
21272080), Special Innovation Projects of Common
Universities in Guangdong Province (20178S0182).
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UPDATE
A Strategy for Accessing Aldehydes via Palladium-
Catalyzed C-O/C-N Bond Cleavage in the Presence
of Hydrosilanes
Adv. Synth. Catal. Year, Volume, Page – Page
Zhanyu He,a† Zijia Wang,a† Junxiang Ru,a Yulin
Wang,a Tingting Liu,a,* Zhuo Zengab,*
8
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