Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate

Article abstract of DOI:10.1002/chem.202100849

Performing carbonylation without the use of carbon monoxide for high-value-added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO₂ hydrogenation, the protocols represent indirect approaches for chemical valorization of CO₂.

Full text of DOI:10.1002/chem.202100849

Accepted Article
Accepted Article
Title: Selective production of linear aldehydes and alcohols from
alkenes using formic acid as syngas surrogate
Authors: Junjun Chen, Kaimin Hua, Xiaofang Liu, Yuchao Deng, Baiyin
Wei, Hui Wang, and Yuhan Sun
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To be cited as: Chem. Eur. J. 10.1002/chem.202100849
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10.1002/chem.202100849
Chemistry - A European Journal
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Selective Production of Linear Aldehydes and Alcohols from
Alkenes using Formic Acid as Syngas Surrogate
Junjun Chen+,[a,b] Kaimin Hua+,[a,b] Xiaofang Liu,* [a] Yuchao Deng,[a,c] Baiyin Wei,[a,c] Hui Wang* [a] and
Yuhan Sun [a,c,d]
[a]
J. Chen, K. Hua, X. Liu, Y. Deng, B. Wei, Prof. H. Wang, Prof. Y. Sun
CAS Key Laboratory of Low-carbon Conversion Science and Engineering
Shanghai Advanced Research Institute, Chinese Academy of Sciences
Shanghai 201210, P. R. China
E-mail: liuxiaofang@sari.ac.cn, wanghh@sari.ac.cn
J. Chen, K. Hua
University of Chinese Academy of Science
Beijing 100049 (P. R. China)
Y. Deng, B. Wei, Prof. Y. Sun
Shanghai Tech University
Shanghai 201210 (P. R. China)
Prof. Y. Sun
Shanghai Institute of Clean Technology
Shanghai, 201620, P. R. China.
These authors contribute equally to this work
[b]
[c]
[d]
[+]
Supporting information for this article is given via a link at the end of the document.
[9]
Abstract: Performing carbonylation without the use of carbon
monoxide for high-value-added products is an attractive yet
challenging topic in sustainable chemistry. Herein, effective methods
for producing linear aldehydes or alcohols selectively with formic acid
as both carbon monoxide and hydrogen source have been described.
Linear-selective hydroformylation of alkenes proceeds smoothly with
up to 88% yield and > 30 regioselectivity in the presence of single Rh
catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru
catalysts accomplish efficient and regioselective hydroxymethylation
in one pot. The present processes utilizing formic acid as syngas
surrogate operate simply under mild condition, which opens a
sustainable way for production of linear aldehydes and alcohols
without the need for gas cylinders and autoclaves. As formic acid can
be readily produced via CO2 hydrogenation, the protocols represent
indirect approaches for chemical valorization of CO2.
which is readily produced by catalytic hydrogenation of CO2 or
oxidation of biomass. [10] Clearly, formic acid is able to decompose
and generate CO by dehydration[11] and/or H2 via catalyst,
rendering it a feasible replacement for syngas (or single CO gas).
For example, formic acid could be used as an in situ source of CO
in the hydrocarboxylation and alkoxycarbonylation of alkenes. [13]
Recently, an effective hydroformylation of alkenes using formic
acid in the presence of 5 mol% Pd catalyst to form linear
By contrast, the more
challenging regioselective hydroxymethylation of alkenes with
[12]
[14]
aldehydes has been described.
[15]
formic acid to produce linear alcohols remains elusive.
Obviously, to achieve such a transformation, the linear-selective
hydroformylation of alkenes with HCOOH as both C1 and
hydrogen source has to be combined with the efficient (transfer)
hydrogenation of aldehydes in one process.
Herein, we report an operationally safe and highly efficient
strategy for selective hydroformylation and hydroxymethylation of
alkenes utilizing formic acid as both C1 and hydrogen source. In
the presence of single rhodium catalyst (as low as 0.1 mol%),
various alkenes are effectively converted to linear aldehydes in
up to 88% yield and n/i > 30 regioselectivity. Notably, the
admixture of Rh/Ru dual system can accomplish efficient
production of linear alcohols (up to 87% yield and n/i > 20) by a
simple one-pot process.
Introduction
Carbonylation especially hydroformylation of alkenes are among
the most important industrially homogeneous catalytic
transformations. Nowadays, aliphatic alkenes are converted on a
million-ton scale by hydroformylation into the primary products
linear aldehydes, [1] and further on into linear alcohols, [2]which are
used as major components of plasticizers, detergents, solvents
etc. However, the processes suffer from the handling of toxic and
flammable syngas under high pressure and forcing reaction
conditions.
Results and Discussion
Hydroformylation/hydroxymethylation of alkenes catalyzed
by single Rh and dual Rh/Ru system
To overcome these problems, substantial attention has been
paid to the development of carbonylation reactions with syngas
We initially carried out the selective hydroformylation of 1-decene
[3]
[4]
[4a, 5]
surrogates,
such as formic acid,
formaldehyde,
o
with formic acid at 90 C in NMP (1-methyl-2-pyrrolidinone) with
[6]
[7]
diboron/silacarboxylic acid/H2O, CO2/hydrosilane, and even
0.5 mol% Rh(acac)(CO)2 as a catalyst precursor and acetic
anhydride (Ac2O) as a dehydrant. Screening of various phosphine
[3b, 8]
CO2/H2.
Among these, formic acid is probably the most
convenient syngas surrogate as a nontoxic, renewable liquid
1
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10.1002/chem.202100849
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ligands showed that the nature of the ligand markedly affected the
reaction performance especially regioselectivity (Table 1 and
Table S1, detailed products distribution can be found in Table S6).
With simple PPh3, acceptable yield of C1-elongated aldehyde
could be obtained albeit with poor linear selectivity (Table 1, entry
1). The regular bidentate ligands including dppb, dppe and dppf
moderately improved the regioselectivity (entries 2-4). Another
bidentate ligand Biphephos, well known for efficient regioselective
hydroformylation of alkenes with syngas, afforded unsatisfactory
aldehyde yield and regioselectivity (entry 5), which was ascribed
to its susceptibility towards acid (formic acid in the present case).
By contrast, Xantphos gave decent yield of linear aldehyde and
regioselectivity (49% and n/i = 9.8, entry 6). Moderate yield and
regioselectivity of linear aldehyde were achieved in the presence
of Nixantphos ligand with identical xanthene structure (entry 7).
The nice performance especially linearity for Xantphos-type
ligands could be attributed to their rigid backbone, large bite angle
and strong acid resistance. [16]
Table 1. hydroformylation/hydroxymethylation of alkenes to linear
[a]
aldehydes or alcohols selectively
Encouraged by this result, additional reaction parameters were
further investigated with Xantphos as the ligand. Screening of
rhodium precursor (Table S2, Supporting Information) and its
dosage (Figure S1) showed 0.5 mol% Rh(acac)(CO)2 was best
and as low as 0.1 mol% Rh could give modest yield coupled with
intact linearity. Increasing the ratio of the ligand to Rh from 2 to 6
markedly improved the linearity (Table S3). No reaction occurred
in the absence of an anhydride, which was necessary for the
decomposition of formic acid to CO. Other than acetic anhydride,
trifluoroacetic anhydride and benzoic anhydride could also be
used (Table S4). Raising the amount of formic acid to 6 equiv.
would somewhat boost the aldehyde yield (Figure S2). In addition,
the effects of reaction temperature were evaluated, which
Yield[b] [%]
Entry
Ru cat.
L
Solvent
2a
2a’
3a
3a’
1
2
-
PPh3
L1
L2
L3
L4
L5
L6
L5
L5
L5
L5
L5
L5
L5
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
MeCN
CYH
NMP
NMP
NMP
NMP
22
30
2
trace
-
71
42
19
14
49
26
71
83
81
1
25
trace
trace
6
trace
trace
trace
trace
trace
trace
trace
trace
trace
5
3
-
16
4
-
8
5
-
2
trace
7
6
-
5
3
o
indicated 90 C was optimal, as lower temperature suppressed
7
-
trace
20
catalytic activity while higher one led to undesired isomerization
of alkenes (Figure S3). From a plot of conversion/yield versus
reaction time, we observed that yield increased with reaction time,
and reached a plateau after 16 h (Figure S4). Through above
optimization, the yield of linear aldehyde and regioselectivity
could be improved to 71% and >30, respectively (entry 8). It was
worth noting that further hydrogenated products undecanol
(3a+3a’) held an unignorable proportion in most cases. The
solvent was found to be an important factor for the competition
between hydroformylation and hydroxymethylation. When the
reactions were carried out in acetonitrile (MeCN) or cyclohexane
(CYH), the formation of alcohols was suppressed below 5%,
coupled with improved chemo- and regioselectivity of linear
aldehyde 2a (over 80% yield and 40 n/i ratio, entries 9 and 10).
As shown in Table S5, there seemed to be a roughly positive
correlation between alcohol yield and electron donatability of
solvents.
Having established the efficient aldehyde synthesis from alkene
and formic acid, the more challenging regioselective
hydroxymethylation with formic acid to produce linear alcohols in
one pot was explored. We became interested in the admixture of
two catalysts, as each catalyst operates one reaction with high
efficiency without disturbing the other reaction. The additional
catalyst should be relatively inert in the hydroformylation step
compared to the rapid hydroformylation by Rh. Possible side
reactions like hydrogenation of 1-decene to decane or
isomerization to 2-decenes should be suppressed. Ruthenium-
based catalysts were therefore selected for aldehyde-selective
(transfer) hydrogenation. Among the Ru catalysts we examined,
8[c]
9[c]
10[c]
11[d]
12[d]
13[d]
14[d]
-
2
-
2
4
-
2
4
Shvo’s cat.
Ru(acac)3
RuCl3
trace
trace
2
87
1
87
6
34
1
52
3
RuCl2(PPh3)3
trace
80
4
[a]. Reaction condition: 1-decene (1.0 mmol), Rh(acac)(CO)2 (0.5 mol%),
Rh:L=1:2, solvent (4.0 mL), HCOOH (4 equiv.), Ac2O (2 equiv.), 90 ºC , 12 h;
[b]. Yields were determined by GC analysis using isooctane as internal
standard; [c]. Rh:L=1:6, 6 equiv. HCOOH, 3 equiv. Ac2O, 24 h; [d]. Rh:L=1:6,
9 equiv. HCOOH, 3 equiv. Ac2O, 1.25 mol% [Ru], 24 h.
the use of Shvo’s complex gave the best result (linear alcohol
87%, n/i = 17.4) with additional 3 equiv. HCOOH. Other Ru
catalysts also work, delivering comparable or moderate yield and
linearity (entries 11-14). The universality of Ru catalysts was
different from that under syngas atmosphere, [17] which might be
attributed to low local concentration of CO in the present system.
In a word, a high-yielding synthesis of linear alcohol (87%) by the
reaction of a terminal olefin with formic acid has been achieved
using Rh/Ru dual catalysts in one pot.
2
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Substrate scope
[b]. The yields of linear aldehydes were determined by GC analysis using
isooctane as internal standard; [c]. With 4 mL acetonitrile; [d]. With 1.0 mol%
Rh(acac)(CO)2.
With the optimized reaction conditions in hand, we investigated
the hydroformylation of other alkenes with formic acid (Table 2).
Aliphatic terminal alkenes 1a-1e demonstrated similar reactivity
profiles irrespective of the length of the carbon chain, affording
the corresponding linear aldehydes 2a-2e in good to excellent
yield (73%-88%) and regioselectivity (>30). Remarkably, ester
group was well tolerated for 1f. It’s gratifying that cyclic alkene
norbornene 1g was quantitatively transformed into aldehyde 2g.
Moreover, aryl alkenes styrene 1h was also converted into linear
aldehyde in good yield (60%), albeit with reduced regioselectivity
(71/29), which might be due to the stability of the benzylic Rh-
species. [14a, 18] By contrast, the hydroformylation of phenylbutene
1i and allylbenzene derivative 1j furnished the corresponding
aldehydes 2i and 2j in excellent yield and high regioselectivity.
Notably, the ether group in 1j was retained in the transformation.
In addition, this protocol was compatiable with hydroxyl group (1k),
showing good compatibility of functional groups. However, the
present catalytic system was not very suitable for internal alkenes
with only 15% linear aldehyde yield for 2-octene 1l. Similarly, the
hydroformylation of 1,1-disubstituted alkene 1m gave very poor
yield of aldehyde 2m, which was due to its large steric hindrance.
Furthermore, we explored the utility of the hydroxymethylation
of alkenes with formic acid by using Rh/Ru dual system (Table 3).
Aliphatic terminal alkenes 1a-1e provided the linear alcohols 3a-
3e in good to excellent yields and high regioselectivity (59%-87%,
n/i=11.5-24). The reaction also proceeded smoothly with alkene
1f with ester group. Furthermore, cycloalkene norbornene 1g was
effective substrate for the hydroxymethylation process, giving
alcohol 3g in 98% yield. Compared with hydroformylation process,
the hydroxymethylation of styrene 1h halved the yield of alcohols,
coupled with more undesired hydrogenation of alkene due to the
strong hydrogenation ability of Ru towards aryl alkenes. Besides,
the hydroxymethylation can be extended to phenylbutene 1i and
allylbenzene derivative 1j, albeit with lower regioselectivity which
might be attributed to mild interference of Ru towards the
hydroformylation step. In a word, by introducing Shvo’s catalyst,
equal or moderately inferior yield and regioselectivity of linear
alcohols compared to those of linear aldehydes could be obtained.
Table 2. Rh-catalyzed hydroformylation of alkenes[a].
Table 3. Rh/Ru-catalyzed hydroxymethylation of alkenes[a]
.
Yield[b ][%]
Entry
1[c]
Substrate
Product
Yield[b]
(n:i)
Entry
Substrate
Product
(%)(n:i)
83 (97:3)
1
2
3
4
5
87 (96:4)
59 (97:3)
76 (96:4)
84 (96:4)
63 (92:8)
2
73 (97:3)
3
4
88 (97:3)
78 (97:3)
77 (96:4)
69 (96:4)
5
6[d]
6[c]
64 (86:14)
98 (-)
7[d]
8[d]
9
99 (-)
7[c]
60 (71:29)
84 (95:5)
83 (95:5)
8[c]
30 (71:29)
56 (90:10)
56 (90:10)
9[c]
10[d]
10[c]
11
71 (84:16)
15 (50:50)
[a]. Reaction condition: alkene (1.0 mmol), Rh(acac)(CO)2 (0.5 mol%), Shvo’s
catalyst (2.5 mol%), Rh:L=1:6, NMP (4.0 mL), HCOOH (9 equiv.), Ac2O(3
equiv.), 90 °C, 24 h; [b]. The yields of linear alcohols were determined by GC
analysis using isooctane as internal standard; [c]. Rh(acac)(CO)2 (1.0 mol%).
12d]
13
5 (100:0)
[a]. Reaction condition: alkene (1.0 mmol), Rh(acac)(CO)2 (0.5 mol%),
Rh:L=1:6, NMP (4.0 mL), HCOOH (6 equiv.), Ac2O (3 equiv.), 90 °C, 24 h;
Control experiments
3
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Several control experiments were performed to explore possible
intermediates in the hydroformylation/hydrogenation tandem
reaction (Scheme 1). When the reaction was carried out in the
100
90
80
70
60
50
40
30
20
10
0
presence of HCOOAc (generated from HCOOH and Ac2O),
[14a]
previously proposed by Shi et al. as C1 source,
trace of
aldehyde could be obtained (Scheme 1a), which excluded the
possibility of HCOOAc as C1 intermediate. Delightedly, the
reaction could proceed smoothly with 5/5 bar CO/H2, affording
excellent yield and selectivity comparable to those of bench
reaction (Scheme 1b), which proved in situ syngas from formic
acid acted as major C1 and hydrogen source. Using HCOOH
instead of H2, mediocre performance (18% aldehyde yield) was
achieved (Scheme 1c), indicating that HCOOH could also serve
as a hydrogen source in the hydroformylation step. Next, the
hydrogenation step was investigated. Experimental results
demonstrated that both formic acid and molecular hydrogen could
fulfill the function of hydrogen source (Scheme 1d and 1e). It was
worth noting that even in the CO atmosphere, 90% yield of
alcohols could be observed with Shvo’s catalyst (Scheme 1f),
which was owed to the tolerance of Shvo’s catalyst against CO
poisoning. [19]
Conv. of 1-decene
Yield of undecanal
Yield of undecanol
0
3
6
9
12
15
18
21
24
Time (h)
Figure 1. Conversion and yield of aldehyde and alcohol with respect to the
reaction time. Reaction conditions: 1-decane (1.0 mmol), Rh(acac)(CO)2 (0.5
mol%), Rh:L=1:6, Shvo’s catalyst (0.625 mol%), HCOOH (9 equiv.), Ac2O (3
equiv.), NMP (4.0 mL), 90 °C. Yields were determined by GC analysis using
isooctane as internal standard.
On the basis of these studies and previous mechanistic
[18]
investigations,
we proposed the following mechanism for
hydroformylation/hydroxymethylation of alkenes as shown in
Scheme 2. In the presence of Xantphos and in situ CO and H2
generated from formic acid, Rh precursor is converted into
hydridorhodium carbonyl complex 4. Subsequently, alkene
coordination and insertion towards 4 leads to acylrhodium
complex 5 upon CO migratory insertion. Further hydrogenolysis
of the M–acyl bond in 5 liberates the linear aldehyde 2 coupled
with regeneration of Rh catalyst. Finally, the aldehyde will
undergo (transfer) hydrogenation to afford the desired linear
alcohol 3 mediated by Ru catalyst. Rh/Ru tandem catalysis plays
an essential part in alcohol synthesis.
To identify efficient catalytic system for hydroformylation,
several important factors should be taken into consideration.
Firstly, as the control experiments has demonstrated, the
hydroformylation was conducted under low carbon monoxide
pressure (presumably lower than 10 bar), noble metals e.g. Rh,
Ru, Ir, Pt and Pd were better choice than Co, Mn or Fe, which
generally needed high operation pressure. Secondly, the present
acidic environment induced by formic acid required the ligand with
stringent acid-resistance character. For example, phosphites and
phosphoramidites which were extremely sensitive to acids should
be excluded, although they were well-known for efficient
regioselective hydroformylation of alkenes with syngas. By
contrast, phosphines characterized by three carbon atoms
surrounding the central phosphorus atom would be focused.
Scheme 1. Control experiments. The yields of linear aldehydes and
alcohols were determined by GC analysis using isooctane as internal
standard.
Time course of the hydroxymethylation
To gain further mechanistic information on this tandem reaction,
Lastly, as the ligand with rigid backbone and suitable bite angle
[1]
the
conversion/time
profile
for
Rh/Ru-mediated
favored linear hydroformylation,
bidentate ligands were
hydroxymethylation of 1-decene with formic acid was depicted in
Figure 1. More than 90% of 1-decene was gradually converted
within 8 h. In contrast, the yield of undecanal reached a maximum
after 3 h (41%) and then was reduced coupled with constant
growth of undecanol yield, which proved again the tandem
pathway via aldehyde intermediate was feasible. It should be
noted that undecanol could be observed from the very beginning
and kept up with the production of undecanal in the initial 4 h,
which implied the hydroformylation was the rate-determining step
of the present tandem reaction.
preferable. In a word, noble metal precursor in combination with
bidentate phosphine ligands proved to be the privileged catalytic
system for the present hydroformylation. The results of the ligand
screening also confirmed this in Table 1 and Table S1.
Next, the protocols for direct synthesis of linear alcohols from
alkenes with formic acid were analyzed. [2a] In comparison with
catalytic systems depending on one single metal catalyst to
perform the two different reactions, the admixture of two catalysts,
each of which operates one reaction with high efficiency without
disturbing the other reaction would be more desired. In addition,
the additional catalyst should be relatively inert in the
4
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Beller, J. Am. Chem. Soc. 2013, 135, 14306-14312; g) Y. Yuki, K. Takahashi,
Y. Tanaka, K. Nozaki, J. Am. Chem. Soc. 2013, 135, 17393-17400.
[3] Selected reviews for carbonylation with syngas surrogates: a) T. Morimoto,
K. Kakiuchi, Angew. Chem. Int. Ed. 2004, 43, 5580-5588; b) L. Wu, Q. Liu,
R. Jackstell, M. Beller, Angew. Chem. Int. Ed. 2014, 53, 6310-6320; c) D. N.
Gorbunov, M. V. Nenasheva, Y. S. Kardasheva, E. A. Karakhanov, Russ.
Chem. B. 2020, 69, 625-634.
hydroformylation step compared to the rapid hydroformylation by
Rh. Possible side reactions like alkenes hydrogenation or
isomerization should be suppressed. Rh/Ru dual catalyst system
which was efficient for tandem hydroformylation/hydrogenation
with syngas[17,19] proved to be suitable for our present system with
formic acid. Actually, the catalytic systems applied in
regioselective hydroxymethylation with syngas could be
competent alternative for that using formic acid, which thus shed
light on designing efficient single-component catalyst.
[4] Recent representative examples on carbonylation with formic acid: a) J. Cao,
Z.-J. Zheng, Z. Xu, L.-W. Xu, Coordin. Chem. Rev. 2017, 336, 43-53; b) J.
B. Peng, W. F. Wang, F. P. Wu, J. Ying, X. X. Qi, X. F. Wu, J. Catal. 2018,
368, 275-278; c) L. Wang, H. Neumann, M. Beller, Angew. Chem. Int. Ed.
2018, 57, 6910-6914; Angew. Chem. 2018, 130, 7026-7030; d) R. Yang, J.
T. Yu, S. Sun, J. Cheng, Org. Chem. Front. 2018, 5, 962-966; e) X.-D. Lang,
F. You, X. He, Y.-C. Yu, L.-N. He, Green Chem. 2019, 21, 509-514; f) W. L.
Ren, J. X. Chu, F. Sun, Y. A. Shi, Org. Lett. 2019, 21, 5967-5970; g) L. Liu,
H. Gao, S.-Q. Yang, X.-C. Chen, Y. Lu, Y. Liu, F. Xia, J. Catal. 2020, 385,
183-193; h) Z. K. Chen, L. C. Wang, X. F. Wu, Chem. Commun. 2020, 56,
6016-6030; i) R. Geitner, A. Gurinov, T. B. Huang, S. Kupfer, S. Grafe, B.
M. Weckhuysen, Angew. Chem. Int. Ed. 2021, 60,3422-3427; Angew. Chem.
2021, 133,3464-3469.
Scheme 2. Proposed mechanism for regioselective hydroformylation and
hydroxymethylation.
[5] Recent representative examples on carbonylation with formaldehyde: a) G.
Makado, T. Morimoto, Y. Sugimoto, K. Tsutsumi, N. Kagawa, K. Kakiuchi,
Adv. Synth. Catal. 2010, 352, 299-304; b) Q. Liu, K. Yuan, P.-B. Arockiam,
R. Franke, H. Doucet, R. Jackstell, M. Beller, Angew. Chem. Int. Ed. 2015,
54, 4493-4497; c) V. J. Garza, M. J. Krische, J. Am. Chem. Soc. 2016, 138,
3655-3658; d) T. Meyer, R. Konrath, P. C. J. Kamer, X. F. Wu, Asian J. Org.
Chem. 2021, 10, 245-250.
Conclusion
[6] S. K. Pedersen, H. G. Gudmundsson, D. U. Nielsen, B. S. Donslund, H. C.
D. Hammershøj, K. Daasbjerg, T. Skrydstrup, Nat. Catal. 2020, 3, 843-850.
[7] Selected examples for hydroformylation/hydroxymethylation with
CO2/hydrosilane: a) Y. Tani, K. Kuga, T. Fujihara, J. Terao, Y. Tsuji, Chem.
Commun. 2015, 51, 13020-13023; b) X.-W. Chen, L. Zhu, Y.-Y. Gui, K. Jing,
Y.-X. Jiang, Z.-Y. Bo, Y. Lan, J. Li, D.-G. Yu, J. Am. Chem. Soc. 2019, 141,
18825-18835; c) J. Qiu, S. Gao, C. Li, L. Zhang, Z. Wang, X. Wang, K. Ding,
Chem. –Eur. J. 2019, 25, 13874-13878; d) M.-Y. Wang, X. Jin, X. Wang, S.
Xia, Y. Wang, S. Huang, Y. Li, L.-N. He, X. Ma, Angew. Chem. Int. Ed. 2021,
60, 3984-3988; Angew. Chem. 2021, 133, 4030-4034.
In summary, effective hydroformylation and hydroxymethylation
protocols have been developed using HCOOH/Ac2O under mild
reaction conditions. With single Rh catalyst, a wide variety of
linear aldehydes can be obtained in good yields with high
regioselectivities. Introducing Ru into the system, the dual Rh/Ru
catalysts enable efficient conversion of alkenes to linear alcohols.
Both protocols operate simply and avoid using flammable and
toxic syngas, which represents a sustainable approach for the
preparation of value-added compounds. Considering the readily
availability of HCOOH, the present methods provide alternatives
for hydroformylation and hydroxymethylation in both industry and
laboratory.
[8] Recent representative examples on hydroformylation/hydroxymethylation
with CO2/H2: a) K. Hua, X. Liu, B. Wei, S. Zhang, H. Wang, Y. Sun, Acta
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21776296, 21905291), The National Key
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5
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Entry for the Table of Contents
Effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen
source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly in the presence of single Rh catalyst,
strikingly, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. Both protocols operate
simply and avoid using flammable and toxic syngas, which represents a sustainable approach for the preparation of value-added
compounds.
7
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