Manganese and rhenium-catalyzed selective reduction of esters to aldehydes with hydrosilanes

Article abstract of DOI:10.1039/d0cc03580g

The selective reduction of esters to aldehydes, via the formation of stable alkyl silyl acetals, was, for the first time, achieved with both manganese, -Mn2(CO)10- and rhenium -Re2(CO)10- catalysts in the presence of triethylsilane as reductant. These two methods provide a direct access to a large variety of aliphatic and aromatic alkyl silyl acetals (30 examples) and to the corresponding aldehydes (13 examples) upon hydrolysis. The reactions proceeded in excellent yields and high selectivity at room temperature under photo-irradiation conditions (LED, 365 nm, 40 W, 9 h).

Full text of DOI:10.1039/d0cc03580g

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DOI: 10.1039/D0CC03580G
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Manganese and Rhenium-catalyzed Selective Reduction of Esters
to Aldehydes with Hydrosilanes
Duo Wei, a,b† Ruqaya Buhaibeh, b† Yves Canacb and Jean-Baptiste Sortais*b,c
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The selective reduction of esters to aldehydes, via the formation of esters to silyl acetals at 50 °C with 2.5 equiv. of 1,1,3,3-
stable alkyl silyl acetals, was, for the first time, achieved with both tetramethyldisiloxane (TMDS), the acetals being then easily
manganese, –Mn2(CO)10– and rhenium –Re2(CO)10– catalysts in the converted to aldehydes after hydrolysis.7
presence of triethylsilane as reductant. These two methods provide In homogeneous catalysis, a limited number of systems capable
a direct access to a large variety of aliphatic and aromatic alkyl silyl of catalyzing the hydrosilylation of esters into aldehydes have
acetals (30 examples) and to the corresponding aldehydes (13 been described. The first example, was reported by Piers and
examples) upon hydrolysis. The reactions proceeded in excellent coll., involving the organocatalyst B(C6F5)3 and Ph3SiH as
yields and high selectivity at room temperature under photo- reducing agent.8 A few examples were also described with
irradiation conditions (LED, 365 nm, 40 W, 9 h).
noble metals such as palladium, 9 ruthenium10 and iridium.11 On
the other hand, only two catalysts involving Earth abundant
metals were developed to date: a system based on cobalt-
described by Michon and coll.12 and another involving iron
described by our group.13
Manganese, which is also a 3d metal standing as the third most
abundant transition metal after iron and titanium, is attractive
for the design of sustainable homogeneous catalysts.14 Lately,
the use of manganese in (transfer)hydrogenation reactions of
various unsaturated compounds has grown exponentially15
including the reduction of esters to alcohols.16 Meanwhile,
manganese has also been proven to be effective in the
hydrosilylation of carbonyl and carboxylic acid derivatives.17 In
particular, it has been shown that esters could be selectively
reduced to alcohols18 or to ethers.19
However, to the best of our knowledge, the hydrosilylation of
esters into aldehydes remains unknown to date with
manganese while only an example was described with
rhenium.20 In the present contribution, we report thus the first
effective Mn catalyzed reduction of esters to alkyl silyl acetals
which can then be conveniently hydrolyzed to corresponding
aldehydes. In addition, following our recent study on the
rhenium-catalyzed reduction of carboxylic acids to aldehydes,21
the activity of the related rhenium complex Re2(CO)10 is
evaluated in this process and compared with that observed with
its lighter congener Mn2(CO)10.
Functional group interconversion reactions are fundamental
processes in synthetic chemistry. In this respect, the direct
conversion of carboxylic acid esters to aldehydes represents a
major but recurring challenge in organic synthesis. Indeed, due
to the higher reactivity of aldehydes with respect to their ester
precursors towards nucleophilic addition of hydride species, the
undesired formation of alcohols resulting from over-reduction
of aldehydes is generally difficult to avoid. Stoichoimetric
reducing reagents involving bulky substituents,1 such as
diisobutylaluminum hydride (DIBALH),2 have been widely
employed, usually at low temperature but these reagents prove
to be difficult to handle in both laboratorial and industrial
scales, because of their dangerous nature. Therefore, the
development of safer or/and greener catalytic processes is
highly preferable and of primary interest.
In the field of heterogeneous catalysis, a few systems based on
3
4
γ-Al2O3 Y2O3 , Mn/Al5 were developed for the direct
,
hydrogenation of esters into aldehydes. However high reaction
temperatures (260 – 420 °C) were generally required. As an
alternative, catalytic reductions using hydrosilanes as a hydride
source, i.e. via hydrosilylation, are more attractive from both
selectivity and safety points of view.6 For example, Motoyama
and coll. reported Pd/C as catalyst for the hydrosilylation of
a.Dr. D. Wei, Univ Rennes, CNRS, ISCR – UMR 6226, F-35000, Rennes, France.
b.Dr. D. Wei, R. Buhaibeh, Dr. Y. Canac, Prof. Dr. J.-B. Sortais, LCC-CNRS, Université
de Toulouse, CNRS, UPS, Toulouse, France, E-mail: jean-baptiste.sortais@lcc-
toulouse.fr
c. Prof. Dr. J.-B. Sortais, Institut Universitaire de France, 1 rue Descartes, F-75231
Paris Cedex 05, France.
Scheme 1. Catalytic selective reduction of carboxylic esters to aldehydes.
† These authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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Based on our previous studies on the hydrosilylation of after only 1h but the selectivity 2a
Journal Name
3a dropped toV8ie5w:A1rt5icl(eTOanblinlee
:
carboxylic acid derivatives,13, 21-22 we firstly reacted methyl 2- S1, entry18). In the absence of any liDgOhtI: 1o0r.10u3n9d/De0rCCth0e35rm80aGl
naphthylacetate 1a with Et3SiH (4 equiv.) in the presence of conditions10 (100 oC), no conversion of 1a was detected after 6
Mn2(CO)10 (5.0 mol%) under irradiation (LED, 365 nm, 4*10 W) h (entries 8 and 9), demonstrating that the photo irradiation is
in toluene at room temperature (Table 1 .
).23 To our delight, essential to reduce methyl 2-naphthylacetate 1a
within 3 h, 1a was converted to the corresponding alkyl silyl Having optimized the reduction of 1a with Mn2(CO)10 , we then
acetal 2a obtained as a major product in 92% conversion and investigated the catalytic efficiency of the related complex
82% selectivity, while only 18% of the undesired silyl ether 3a Re2(CO)10, applying the optimized conditions, albeit using a
was formed simultaneously due to over reduction (entry 1). lower loading of catalyst (0.5 mol%) as in the case of carboxylic
Lowering the amount of silane from 4 to 1.1 equiv. induced a acids.21 1a was thus quasi-quantitatively converted (96%) and
decrease of the conversion (from 92% to 60%) but enhanced the corresponding acetal 2a was obtained in good yield with
significantly the selectivity toward the desired product 2a high selectivity (>95%, entry 10, more details in S.I. table S2).
(entries 2-4). With only 1.1 equiv. of Et3SiH, in 9 h, 2a was “On−Off” experiments (see S.I. Figure S1 (Mn) and S2 (Re))
obtained in 89% NMR yield with an excellent selectivity (90% confirmed that continuous irradiation is also mandatory for
conversion, ratio 2a
:
3a over >95: <5, entry 6).
both reductions to proceed.20 In addition, the presence of
TEMPO inhibited the reaction with both metals. (See S.I. for
complementary experiments and discussion).23
Table 1. Optimization of the parameters for the reduction of methyl 2-naphthylacetate
1a[a]
With the optimized conditions in hand (Table 1): Method
A
(Mn2(CO)10, 5.0 mol%, entry 6) or method (Re2(CO)10,
B
0.5 mol%, entry 10), 1.1 equiv. of Et3SiH, toluene, room
temperature, 9 h, photo irradiation (365 nm, 40W), we then
explored the scope of this transformation (Table 2, and S.I. for
limitations). Noteworthy, since the two methods generally give
similar results, we will detail below only those obtained with
Et3SiH
[equiv.]
Conv. of 1a
Selectivity
Entry
Time [h]
[%][b]
2a : 3a [%][b]
method
A. The results observed with method B will only be
1
2
3
4
5
4
3
2
1.1
1.1
1.1
2
2
2
1.1
3
3
3
3
6
9
6
6
6
9
92
82
73
60
85
90
56
<1
<1
96
82: 18
>95: <5
>95: <5
>95: <5
>95: <5
>95: <5
>95: <5
-
mentioned, if there is a significant difference between the two
metals. Methyl 2-naphthylacetate 1a, 1-naphthylacetate 1c and
2-phenylacetate 1e were readily converted into the
corresponding alkyl silyl acetals 2a, 2c and 2e in 71-82% isolated
yields. In general, ethyl esters were found to be more reactive
than their methylated analogues, as demonstrated with the
6
7[c]
8[d]
9[e]
10[f]
quantitative reduction of esters 1b
corresponding acetals 2b 2d and 2f obtained in high yields (94-
99%). p-, m-, o-Methyl substituted 2-phenylacetates 1g 1h and
, 1d and 1f into the
,
-
>95: <5
,
1i were reduced in reasonable yields (59-83%). Increasing the
steric hindrance at the phenyl ring barely affects the efficiency
of this reaction, as illustrated with the ester 2j featuring a
mesityl group formed in 77% yield. Methyl 2-phenylacetate 1k
bearing a p-methoxy substituent and its ethyl analogue 1l were
smoothly converted into the corresponding alkyl silyl acetals 2k
and 2l isolated in 87% and 97%, respectively. From esters
[a] General conditions: In a Schlenk tube, Mn2(CO)10 (4.9 mg, 5.0 mol%), toluene
(0.5 mL), Et3SiH, and 1a (50 mg, 0.25 mmol) were added in that order, then stirred
under irradiation (LED 365 nm, 40W) at r.t. (c.a. 30 °C); [b] Conversion of 1a and
yields of 2a and 3a detected by 1H NMR; [c] irradiation (400-800 nm, 30 W); [d] in
the dark; [e] at 100 oC; [f] Re2(CO)10 (0.5 mol%)
As in the case of carboxylic acids, 21-22 the nature of the silane
was found to be crucial for the selectivity of the reaction (See
S.I. Table S1, entries 8-13). Indeed, the use of the secondary
silane Et2SiH2 led to partial conversion of 1a (41%) with the
formation of a mixture of products 2a and 3a in a ratio 49: 51.
On the contrary, Ph2SiH2, PhSiH3 and TMDS reversed the
selectivity of the reaction and 3a was detected as the sole
product. With other tertiary silanes such as Ph3SiH and
MePh2SiH, no reaction was observed.
bearing halogen atoms (1m-1p), the corresponding products
2m 2p were obtained in moderate to excellent yields (68-99%).
-
It must be noted that the acetal 2n decomposed into the
corresponding aldehyde 4h during its purification on silica gel
(See also Table 3, entry 8). While Mn2(CO)10 afforded product
2o in 59% yield, no conversion of the ester 1o exhibiting a p-
bromo substituent was observed with Re2(CO)10, in line with the
results obtained for the reduction of carboxylic acids.21.
However, the reaction is tolerant to an electron-withdrawing
group such as a p-trifluoromethyl substituent yielding the
product 2p in 75% yield. Increasing the steric hindrance at the
α-position of the ester decreased the reactivity, as observed
with the methyl 2-phenylbutanoate 1q converted into 2q in 68%
yield in the presence of 4 equiv. Et3SiH. The reactions between
Et3SiH and methyl/ethyl/benzyl 3-phenylpropanoate substrates
Then a series of control experiments were performed. Under
visible light irradiation (LED, 400-800 nm, 30 W) using 2 equiv.
of Et3SiH, 56% conversion of 1a was observed, with a ratio of
>95: <5 for products 2a: 3a (entry 7). Replacing the UV-LED
devices by a Rayonnet RPR100 apparatus (350 nm) had little
influence on both reactivity and selectivity (Table S1, entry 17).
Noteworthy, under the same conditions, the use of a medium
pressure UV mercury lamp (150 W) led to a 86% conversion
1r-1t afforded the corresponding acetals 2r-2t in 88%, 99% and
2 | J. Name., 2012, 00, 1-3
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Table 2. Scope of the catalyzed reduction of carboxylic esters 1 to alkyl silyl acetals 2[a]
Table 3. Scope of the reduction of carboxylic esters 1 to aldehydes 4.[a]
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DOI: 10.1039/D0CC03580G
[a] General conditions: ester (0.5 mmol), Et3SiH (88 µL, 0.55 mmol), Mn2(CO)10 (9.8
mg, 5.0 mol%, method A) or Re2(CO)10 (1.6 mg, 0.5 mol%, method B), r.t., toluene
(1.0 mL), irradiation (LED 395 nm, 45W), 9 h; then hydrolysis (THF/HCl 1 N), 4 h.
Conversions of 1 detected by 1H NMR and isolated yields of 4 in parentheses; [b]
4.67 mmol (1 gram) scale; [c] Isolated as solid trioxane derivatives, see S.I.; [d]
1.0.mmol scale, toluene (1.0 mL), [e] NMR yield determined with internal standard.
[a] General conditions: ester (0.5 mmol), Et3SiH (88 µL, 0.55 mmol), Mn2(CO)10 (9.8
mg, 5.0 mol%, method A) or Re2(CO)10 (1.6 mg, 0.5 mol%, method B), r.t., toluene
(1.0 mL), irradiation (LED 395 nm, 45W), 9 h; Conversion of 1 detected by 1H NMR
and isolated yields of 2 in parentheses; [b] 1.0 mmol scale, toluene (1.0 mL); [c]
2.2 equiv. Et3SiH; [d] 4.0 equiv. Et3SiH; [e] Mn2(CO)10 (10.0 mol%); [f] Re2(CO)10 (1.0
mol%).
95% yields with Mn2(CO)10. With Re2(CO)10 slightly lower
conversions were observed for 2z and 2aa (75% and 90%,
respectively). Methyl 4-chlorobenzoate 1ab was reduced with a
conversion of 37% and 80%, by using Mn and Re based-
catalysts, respectively. Heteroaromatic substrates such as
99% yields, respectively.
Esters bearing aliphatic chains like methyl decanoate 1u, ethyl
acetate 1v and butyl formate 1w gave full conversion affording
methyl (or ethyl) furan-2-carboxylate 1ac
(1ad) can be
the corresponding products 2u (method B), 2v and 2w in 96%,
transformed into 2ac 2ad) in 40% (96%) isolated yield.
(
99% and 99% yields, respectively. Dimethyl tridecanedioate 1x
was proved to be a suitable substrate since diacetal 2x was
formed in 92% isolated yield with 2.2 equiv. of Et3SiH and
Re2(CO)10 (1.0 mol%). The internal C=C bond in methyl oleate 1y
was also tolerated, as the acetal 2y was produced in 56% yield
with the C=C bond remaining intact.24 On the opposite, when
methyl 5-hexynoate was engaged as substrate, even in the
presence of 2 equiv. of Et3SiH, the hydrosilylation took place
only at the terminal triple bond in line with the results reported
by Wang and coll.25 Good isolated yields were generally
obtained from benzoate derivatives: methyl and ethyl benzoate
In order to directly obtain the aldehyde products from the
esters, we then performed an one-pot synthesis consisting in
carrying out the hydrosilylation of the esters followed by the
acidic hydrolysis of the acetals formed into aldehydes. The
general scope of the present reaction is presented on Table
Overall, the ester substrates were readily converted under
standard conditions. For instance, the 2-(2-
3.
naphthalenyl)acetaldehyde 4a was isolated in 93% yield, with
Mn2(CO)10 as catalyst. Furthermore, from ethyl 2-(1-
naphthalenyl)acetate 1d, we have demonstrated the synthetic
utility of this methodology in the preparation of aldehyde in
gram scale, as evidenced with the corresponding aldehyde 4b
produced in 75% yield after purification by bulb to bulb
(1z, 1z’) and ethyl 4-methoxybenzoate 2aa were thus
transformed into the acetals 2z, 2z’ and 2aa in 99%, 75% and
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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11 a) C. Cheng and M. Brookhart, Angew. Chem. IVnietw. EAdrti.c,le2O0n1lin2e,
51, 9422-9424; b) Y. Corre, V. Rysak, DF.OCI:a1p0.e1t0,3J9./-DP0.CDCju03k5ic8,0FG.
distillation. In addition, 2-phenylacetaldehyde 4c and its
derivatives bearing methyl- 4d, 4e, methoxy- 4f, fluoro- 4g,
Agbossou-Niedercorn and C. Michon, Chem. Eur. J., 2016, 22
,
chloro- 4h and trifluoromethyl- 4i groups were isolated in 61-
93% yields. 3-Phenylpropanal 4j, decanal 4k, tridecandial 4l and
benzaldehyde 4m could also be prepared in over 80% yields.
In conclusion, the first Mn-catalyzed hydrosilylation of esters
into corresponding silylacetals was carried out under mild
conditions with excellent yield and high chemoselectivity. In
addition, an alternative Re-based catalyst was considered
showing comparable results for the same transformation. The
two simple catalytic systems are based on commercially
available Mn2(CO)10 (5.0 mol%) or Re2(CO)10 (0.5 mol%)
complexes in the presence of a stoichiometric amount of Et3SiH
(1.1 equiv.) as an inexpensive silane source. With both catalysts,
at room temperature under irradiation at 365 nm (LED, 4*10W),
a large variety of carboxylic esters was thus reduced in
moderate to good yields to the corresponding protected
aldehydes without noticeable formation of silylethers arising
from over-reduction. Upon hydrolysis, aromatic and aliphatic
aldehydes, including di-aldehydes, were easily produced and
isolated in good yields. For future developments in this
competitive field, the two metallic systems reported here will
have to be envisaged in a complementary manner, the catalytic
loading 10 times lower used with rhenium having to be opposed
with the lower price of manganese.
14036-14041.
12 V. Rysak, A. Descamps-Mandine, P. Simon, F. Blanchard, L.
Burylo, M. Trentesaux, M. Vandewalle, V. Collière, F.
Agbossou-Niedercorn and C. Michon, Catal. Sci. Technol.,
2018, 8, 3504-3512.
13 H. Li, L. C. Misal Castro, J. Zheng, T. Roisnel, V. Dorcet, J.-B.
Sortais and C. Darcel, Angew. Chem. Int. Ed., 2013, 52, 8045-
8049.
14 a) D. A. Valyaev, G. Lavigne and N. Lugan, Coord. Chem. Rev.,
2016, 308, 191-235; b) W. Liu and L. Ackermann, ACS Catal.,
2016, 6, 3743-3752; c) Y. Hu, B. Zhou and C. Wang, Acc. Chem.
Res., 2018, 51, 816-827.
15 F. Kallmeier and R. Kempe, Angew. Chem. Int. Ed., 2018, 57
,
46-60.
16 a) S. Elangovan, M. Garbe, H. Jiao, A. Spannenberg, K. Junge
and M. Beller, Angew. Chem. Int. Ed., 2016, 55, 15364-15368;
b) N. A. Espinosa-Jalapa, A. Nerush, L. J. W. Shimon, G. Leitus,
L. Avram, Y. Ben-David and D. Milstein, Chem. Eur. J., 2017,
23, 5934-5938; c) R. van Putten, E. A. Uslamin, M. Garbe, C.
Liu, A. Gonzalez-de-Castro, M. Lutz, K. Junge, E. J. M. Hensen,
M. Beller, L. Lefort and E. A. Pidko, Angew. Chem. Int. Ed.,
2017, 56, 7531-7534; d) M. B. Widegren and M. L. Clarke, Org.
Lett., 2018, 20, 2654-2658.
17 a) R. J. Trovitch, Acc. Chem. Res., 2017, 50, 2842-2852; b) X.
Yang and C. Wang, Chem. Asian J., 2018, 13, 2307-2315; c) B.
Royo, Adv. Organomet. Chem., 2019, 72, 59-102.
18 a) O. Martínez-Ferraté, B. Chatterjee, C. Werlé and W. Leitner,
Catal. Sci. Technol., 2019,
9, 6370-6378; b) T. K.
Mukhopadhyay, C. Ghosh, M. Flores, T. L. Groy and R. J.
Trovitch, Organometallics, 2017, 36, 3477-3483; c) T. K.
Mukhopadhyay, M. Flores, T. L. Groy and R. J. Trovitch, J. Am.
Chem. Soc., 2014, 136, 882-885; d) C. M. Kelly, R. McDonald,
O. L. Sydora, M. Stradiotto and L. Turculet, Angew. Chem. Int.
Ed., 2017, 56, 15901-15904.
Conflicts of interest
There are no conflicts to declare.
19 Z. Mao, B. T. Gregg and A. R. Cutler, J. Am. Chem. Soc., 1995,
117, 10139-10140.
Notes and references
1
a) L. I. Zakharkin, V. V. Gavrilenko, D. N. Maslin and I. M. 20 Fan and coll. already reported that Re carbonyl complexes
Khorlina, Tetrahedron Lett., 1963,
4
, 2087-2090; b) P. M.
such as Re(CO)5Cl and Re2(CO)10 catalyses the hydrosilylation
of ethyl acetate to the corresponding silyl ether under
photochemical activation (200 - 800 nm). Acetaldehyde was
identified as the intermediate. See: C. K. Toh, Y. N. Sum, W. K.
Fong, S. G. Ang and W. Y. Fan, Organometallics 2012, 31,
3880-3887.
Weissman and H. C. Brown, J. Org. Chem., 1966, 31, 283-287;
c) M. S. Kim, Y. M. Choi and D. K. An, Tetrahedron Lett., 2007,
48, 5061-5064; d) M. Masayoshi and M. Teruaki, Chem. Lett.,
1975,
4
, 215-218; e) J. S. Cha and S. S. Kwon, J. Org. Chem.,
1987, 52, 5486-5487; f) N. M. Yoon, J. H. Ahn, D. K. An and Y.
S. Shon, J. Org. Chem., 1993, 58, 1941-1944.
L. I. Zakharkin and I. M. Khorlina, Tetrahedron Lett., 1962,
619-620.
21 D. Wei, R. Buhaibeh, Y. Canac and J.-B. Sortais, Org. Lett.,
2019, 21, 7713-7716.
22 a) J. Zheng, S. Chevance, C. Darcel and J.-B. Sortais, Chem.
Commun., 2013, 49, 10010-10012; b) L. C. Misal Castro, H. Li,
J.-B. Sortais and C. Darcel, Chem. Commun., 2012, 48, 10514-
10516.
2
3,
3
4
5
A. Feinstein and E. K. Fields, U.S. Patent 3,935,265, 1976.
S. T. King and E. J. Strojny, J. Catal., 1982, 76, 274-284.
a) A. Chen, H. Xu, W. Hua, W. Shen, Y. Yue and Z. Gao, Top.
Catal., 2005, 35, 177-185; b) H.-L. Xu, W. Shen and Y.-T. Yang, 23 a) M.-A. Tehfe, J. Lalevée, D. Gigmes and J. P. Fouassier, J.
Chin. J. Chem., 2001, 19, 647-651; c) C. Pan, G. Chen, W. Shen
and H. Xu, Catal. Commun., 2009, 10, 1718-1721; d) A. Chen,
H. Xu, Y. Yue, W. Hua, W. Shen and Z. Gao, Appl Catal A: Gen,
2004, 274, 101-109.
D. Addis, S. Das, K. Junge and M. Beller, Angew. Chem. Int. Ed.,
2011, 50, 6004-6011.
Polym. Sci., Part A: Polym. Chem., 2010, 48, 1830-1837; b) M.
S. Wrighton and D. S. Ginley, J. Am. Chem. Soc., 1975, 97
2065-2072; c) D. M. Allen, A. Cox, T. J. Kemp, Q. Sultana and
R. B. Pitts, J. Chem. Soc., Dalton Trans., 1976, DOI:
10.1039/DT9760001189, 1189-1193; d) S. A. Hallock and A.
Wojcicki, J. Organomet. Chem., 1973, 54, C27-C29.
,
6
7
8
S. Hosokawa, M. Toya, A. Noda, M. Morita, T. Ogawa and Y. 24 a) X. Yang and C. Wang, Chin. J. Chem., 2018, 36, 1047-1051;
Motoyama, ChemistrySelect, 2018,
3
, 2958-2961.
b) S. L. Pratt and R. A. Faltynek, J. Organomet. Chem., 1983,
258, C5-C8; c) H. S. Hilal, M. Abu-Eid, M. Al-Subu and S. Khalaf,
J. Mol. Catal., 1987, 39, 1-11; d) H. S. Hilal, M. A. Suleiman, W.
J. Jondi, S. Khalaf and M. M. Masoud, J. Mol. Catal. A: Chem.,
1999, 144, 47-59.
a) D. J. Parks and W. E. Piers, J. Am. Chem. Soc., 1996, 118
,
9440-9441; b) D. J. Parks, J. M. Blackwell and W. E. Piers, J.
Org. Chem., 2000, 65, 3090-3098.
J. Nakanishi, H. Tatamidani, Y. Fukumoto and N. Chatani,
Synlett, 2006, DOI: 10.1055/s-2006-939058, 869-872.
9
25 X. Yang and C. Wang, Angew. Chem. Int. Ed., 2018, 57, 923-
928.
10 M. Igarashi, R. Mizuno and T. Fuchikami, Tetrahedron Lett.,
2001, 42, 2149-2151.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CC03580G
Mn
or
2(CO)10 (5.0 mol%)
Re
SiEt
3
hydrolysis
O
O
O
2(CO)10 (0.5 mol%)
Et3SiH
+
irradiation (LED 365 nm)
room temperature
R
OR'
R
OR'
R
1.1 equiv.
30 examples
R = alkyl, aryl,
heteroaromatic
R' = Me, Et, Bn
The selective reduction of carboxylic esters into silyl alkyl acetals promoted by manganese and
rhenium catalysts provides facile access to aldehydes upon hydrolysis.