Practical (asymmetric) transfer hydrogenation of ketones catalyzed by manganese with (chiral) diamines ligands

Article abstract of DOI:10.1016/j.catcom.2017.10.028

The reduction of ketones with 2-propanol as reductant was achieved using an in-situ generated catalytic system based on manganese pentacarbonyl bromide, as metal precursor, and ethylenediamine as ligand. The reaction proceeds in high yield at 80 °C, in 3 h, with 0.5 mol% of catalyst. In the presence of chiral (1R,2R)-N,N′-dimethyl-1,2-diphenylethane-1,2-diamine, as the ligand, sterically hindered alcohols were produced with enantiomeric excess up to 90%.

Full text of DOI:10.1016/j.catcom.2017.10.028

Accepted Manuscript
Practical (asymmetric) transfer hydrogenation of ketones
catalyzed by manganese with (chiral) diamines ligands
Ding Wang, Antoine Bruneau-Voisine, Jean-Baptiste Sortais
PII:
DOI:
Reference:
S1566-7367(17)30447-8
doi:10.1016/j.catcom.2017.10.028
CATCOM 5239
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12 October 2017
30 October 2017
Please cite this article as: Ding Wang, Antoine Bruneau-Voisine, Jean-Baptiste Sortais ,
Practical (asymmetric) transfer hydrogenation of ketones catalyzed by manganese with
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ACCEPTED MANUSCRIPT
Practical (Asymmetric) TransferHydrogenation of Ketones catalyzed by manganese with (chiral)
diamines ligands
a,b,c
Ding Wang,a§ Antoine Bruneau-Voisine,a,b§ Jean-Baptiste Sortais
*
a
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1,
Team Organometallics: Materials and Catalysis, 263 avenue du Général Leclerc, 35042
Rennes Cedex, France.
b
LCC-CNRS, Université de Toulouse, INPT, UPS, 205 route de Narbonne 31077 Toulouse
Cedex 4, France.
c Institut Universitaire de France, 1 rue Descartes, 75231 Paris Cedex 05, France.
§ equal contributions
Corresponding author: jean-baptiste.sortais@lcc-toulouse.fr

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Abstract
The reduction of ketones with 2-propanol as reductant was achieved using an in-situ
generated catalytic system based on manganese pentacarbonyl bromide, as metal precursor,
and ethylenediamine as ligand. The reaction proceeds in high yield at 80 °C, in 3h, with 0.5
mol% of catalyst. In the presence of chiral (1R,2R)-N,N′-Dimethyl-1,2-diphenylethane-1,2-
diamine, as the ligand, sterically hindered alcohols were produced with enantiomeric excess
up to 90%.
Keywords
Manganese, reduction, asymmetric hydrogen transfer, ketones, chiral diamines, chiral alcohol,
ethylenediamine, (1R,2R)-N,N′-Dimethyl-1,2-diphenylethane-1,2-diamine
Graphical abstract
Highlights
 In-situ generated catalytic system based on manganese pentacarbonyl bromide
and ethylenediamine promotes the reduction of ketones with low catalytic loading
 With (1R,2R)-N,N′-Dimethyl-1,2-diphenylethane-1,2-diamine as chiral ligand,
asymmetric reduction of ketones was achieved with enantioselectivity up to 90%
ee.
 Phosphine-free bidendate aliphatic diamines as ligand for hydrogen transfer
reaction with manganese
Acknowledgements
We thank the Centre National de la Recherche Scientifique (CNRS), the Université de Rennes
1, INCREASE FR-CNRS 3707, la Fondation Rennes 1 (grant to D.W.), the Institut
Universitaire de France (IUF) and the Agence National de la Recherche (ANR agency,
program JCJC ANR-15-CE07-0001 “Ferracycles”).

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Funding: This work was supported by the Agence National de la Recherche (ANR agency,
program JCJC ANR-15-CE07-0001 “Ferracycles”), l’Université de Rennes 1, the Institut
Universitaire de France (IUF) and the Centre National de la Recherche Scientifique (CNRS).
Introduction
Homogeneous catalysis plays an important role in the development of modern
environmentally friendly and atom-economical chemistry. While noble transition metal
complexes still remain the prominent actors in this area, the search for new alternatives based
on their more abundant, inexpensive first row congeners clearly becomes one of the emerging
trends of the present century.[1] Compared to iron,[2] manganese-based catalysis has
remained in the shadow in spite of the natural abundance of this metal, third most abundant
transition metal in the Earth’s crust after iron and titanium, and its biocompatibility.[3]
The rise of manganese catalyzed reduction reactions started recently after the initial work of
Beller[4] in hydrogenation and Milstein in hydrogen auto-transfer reaction.[5] The potential
of manganese catalysts in such redox reactions was exemplified with various type of
tridendate ligands, mainly phosphorus and nitrogen atoms.[6-19] Interestingly, in the case of
hydrogen transfer reaction, using isopropanol as hydrogen donor, Beller has shown that
tridentate nitrogen ligand, namely di(picolyl)amine, could promote the reduction of ketones,
at 70°C, in 24 h, with a ratio substrate:catalyst of 100:1.[20] Asymmetric reduction of ketones
with manganese is far less developed and the two first example were reported by Clarke[21]
and Kirchner[22], using related chiral ferrocenyl based tridentate PNN or PNP’ ligands.
In general, tridentate ligands were used in manganese catalyzed reduction, except in one
recent case in which bidentate amino-phosphine ligand was efficient for the hydrogenation of
esters.[23] In the meantime, most of the ligands used to date, except the dipicolylamine, were
phosphine-based ligands. Following our previous contributions on manganese catalyzed
hydrosilylation [24-26], hydrogenation and hydrogen borrowing reactions [15, 27, 28], we
were looking for simple, sustainable and practical catalytic systems to promote hydrogen
transfer reactions. We found that well-defined nitrogen-based bidendate manganese catalysts,
featuring a picolylamine ligand, were highly efficient for the reduction of ketones and
aldehydes by hydrogen transfer reactions.[29] Inspired by the breakthrough of Noyori,
introducing chiral diamines as ligands in ruthenium catalyzed asymmetric reduction of
ketones,[30, 31] we envisioned that simple diamines could be suitable for manganese-

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catalyzed reduction of ketones using isopropanol as the hydrogen donor, and that eventually
asymmetric reduction of ketones could be achieved with chiral diamines.
In the present contribution, we demonstrate that diamines, as simple as ethylenediamine, can
promote hydrogen transfer reaction with manganese, and that the catalytic system can be
generated in-situ. Besides, we have extended the reactivity to asymmetric hydrogen transfer
reaction, with ee up to 90%, employing symmetrical chiral diamines as ligands.
Experimental
Representative procedure for transfer hydrogenation reaction of acetophenone: To a
solution of acetophenone (58 μL, 0.5 mmol) in 2-propanol (0.5 mL) was added a stock
solution of manganese pentacarbonyl bromide (0.5 mL, 0.005 mol.L-1; 2.7 mg, 0.010 mmol,
in 2 mL 2-propanol) followed, in this order, by a stock solution of ethylenediamine (0.5 mL,
0.005 mol.L-1; 1.0 μL, 0.0125 mmol, in 2.5 mL 2-propanol ) and tBuOK (0.5 mL, 0.010
mol.L-1; 2.4 mg, 0.020 mmol, in 2 mL 2-propanol). The reaction mixture was stirred for 3
hours at 80°C in an oil bath. The solution was then filtered through a small pad of silica (2 cm
in a Pasteur pipette). The silica was washed with ethyl acetate. The filtrate was evaporated
1
and the conversion was determined by H NMR. The crude residue was then purified by
column chromatography (SiO2, mixture of petroleum ether/ethyl acetate or dietyl ether as
eluent.
Enantiomeric excesses were determined by GC analyses performed on GC-2014 (Shimadzu)
2010 apparatus equipped with Supelco beta-DEX 120 column (30 m x 0.25 mm). The
determination of the absolute configuration was done by comparison with (S)-alcohol
obtained by kinetic resolution of racemic alcohols with Novozym 435 (Candida Antarctica
Lipase B) and by comparison of the retention times with the literature.[32-34]
Results and Discussion
To start our investigation, based our optimized conditions for well-defined picolylamine
manganese complexes,[29] we have screened a series of diamines as ligands (0.5 mol%),
using Mn(CO)5Br as metal precursor (0.5 mol%) and tBuOK as the base (1 mol%) for the
reduction of acetophenone at 80 °C in 1 h. The results are summarized in Scheme 1. First,
several amines were found inactive for this transformation, demonstrating that the base-
catalyzed reaction was limited under these conditions.[35] Second, the reduction of

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acetophenone proceeded well with in-situ generated catalysts based on aminomethylpyridine
ligand L1, as a full conversion of acetophenone into 1-phenylethanol was observed after 1 h.
N-methylaminomethylpyridine ligand L2, featuring one NH moieties, led also to a full
conversion in 1 h but N,N-dimethylaminomethylpyridine L3 was almost inactive. These
results are in line with those obtained previously with well-defined complexes based on
picolylamine ligands.[29] Due to the simplicity of the system, we then explored different
parameters to optimize the design of the ligand. Aromatic amines, such as 2-amino-pyridine
L4, 1,8-diaminonaphtalene L5 and 1,2-diaminobenzene L6, did not promote the hydrogen
transfer. 2,2’-bipyidine L7 was completely inactive.[11] The length of the linker in between
the pyridinyl unit and the amine moieties was also found to be crucial as 2-pyridin-2-
ylethanamine L8 was inactive, as L4. Interestingly, benzimidazolyl analogue of L1, namely
1H-benzimidazole-2-methanamine L9, gave
a
good conversion (76%), but 2-
aminomethylthiophene L10 was inactive. In order to develop the simplest and the less
expensive catalytic system as possible, we have tested the simplest diamine, namely,
ethylenediamine L11: to our delight, a very encouraging conversion was obtained under
standard conditions (65%). Several diamines were also tested: the presence of at least two NH
moieties was found to be crucial to detect some activity (L11, L12 versus L13, L14). The
presence of a tosyl group on one nitrogen atom inhibited the reduction, probably due to a slow
coordination of the ligand to the manganese precursor. An ethylene bridge, leading to a five-
membered metallacycle, was more favorable than a propylene one (L16, L17, L18) (65 %
conversion with L11 versus 25% with L16). Finally, racemic ligand L20-rac, (±)-trans-1,2-
diaminocyclohexane, gave moderate (22%) conversion, opening the gate to asymmetric
reduction of acetophenone (vide infra).
Taking in account both the simplicity and the low cost of ethylenediamine L11 compared to
2-aminomethylpyridine L1, the scope of the reaction was then explored using L11 as ligand
(0.5 mol%), Mn(CO)5Br (0.5 mol%) and tBuOK as base (1 mol%) in isopropanol at 80 °C for
3 h (Scheme 2). In most cases, ketones were fully reduced, and the corresponding alcohols
were isolated in high yields. Increasing the length and the branching of the alkyl chains from
methyl (a1) to tertbutyl (a5) has little influence on the reaction. On the opposite, for ortho-
substituted acetophenones (b6-b9 and b15), a higher catalyst loading (1 mol%) was required
to afford the alcohol in quantitative yield.

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Scheme 1: Screening of bidentate nitrogen based ligands for the reduction of acetophenone in
the presence of Mn(CO)5Br and tBuOK in 2-propanol.a [a Typical conditions : acetophenone
a1 (2 mmol), 2-propanol (8 mL). Conversions were determined by 1H NMR.]

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Scheme 2: Generality of the reduction of ketones with the in-situ prepared Manganese-
ethylenediamine catalytic system.a [a Typical conditions: Ketone (0.5 mmol), 2-propanol (2
1
b
mL). Conversion determined by H NMR, isolated yield given in parentheses. Mn(CO)5Br (1
c
mol%), ethylenediamine (1 mol%), tBuOK (2 mol%), 80 °C, 3 h. Mn(CO)5Br (1 mol%),
ethylenediamine (1 mol%), tBuOK (2 mol%), 80 °C, 6 h.]

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Encouraged by these results, especially by the activity of L20-rac, we submitted a series of
commercial chiral diamines featuring an ethylenediamine motif for the reduction of
acetophenone (Scheme 3, Table 1) using one equivalent of ligand (1 mol%) per Mn(CO)5Br
(1 mol%) and two equivalents of tBuOK (2 mol%) at 80 °C for 3 h.
With (1R, 2R)-(+)-1,2-diphenyl-1,2-ethanediamine (DPEN) L21, a promising enantiomeric
excess of 36 % was obtained (entry 1). Using (1R, 2R)-(-)-1,2-diaminocyclohexane L22,
under the same conditions, the selectivity increased to 43% ee (entry 2). The enantiomeric

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excess of the product dropped to 38% after 24 h of reaction (entry 3), probably due to
racemization of the product under hydrogen transfer conditions. The activity dramatically
decreased if the reaction was performed at 30 °C (entry 4). N-tosyl substituted ligand L23
displayed no activity, as L15, even if a preactivation step at 100 °C in toluene was
accomplished (entries 5-6). Disappointingly, more sterically demanding diamine L24 or less
bulky (1S,2S)-trans-1,2-cyclopentanediamine L25 gave both a lower activity and selectivity
(entries 7-8). (1S,2S)-1,2-di-1-naphthyl-ethylenediamine L26, as the achiral aniline
derivatives L4-L6, gave almost no conversion and no enantiomeric excess (entry 9).
Gratifyingly, N,N’-dimethylated ligands L27 and L28 displayed a significant higher
selectivity than their analogues L21 and L22 (64% and 52% ee respectively, entries 10-11),
(1R, 2R)-(+)-N,N’-dimethyl-1,2-diphenyl-1,2-ethane diamine L27 giving the highest ee.
Scheme 3: Chiral diamines screened for the asymmetric reduction of ketones.
Table 1. Asymmetric reduction of acetophenone with chiral diamines ligands and
Mn(CO)5Bra
Entry
Ligand
L21
Temp. (oC) Time (h) eeb (%)
Conv.c (%)
> 97
1
2
80
80
3
3
36 (S)
43 (S)
L22
87

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3
L22
L22
L23
L23d
L24e
L25e
L26
L27
L28
80
30
80
80
80
80
80
80
80
24
24
3
38 (S)
42 (S)
0
> 97
8
4
5
0
6
3
46 (S)
16 (R)
0
4
7
3
7
8
3
16
13
95
94
9
3
6 (S)
64 (S)
52 (R)
10
3
11
3
a
Typical conditions : To a solution of acetophenone in 2-propanol were added in this order
b
the diamine (1 mol%), Mn(CO)5Br (1 mol%) and finally tBuOK (2 mol%). Enantiomeric
c
1
d
excess values were determined by chiral GC. Conversions were determined by H NMR.
Preactivation step was operated: Mn(CO)5Br (0.02 mmol) and L23 (0.02 mmol) were stirred
in refluxing toluene (1 mL) for 1 hour, then 2-propanol (8 mL), acetophenone (2 mmol) and
e
base (0.04 mmol) were added. Commercial L24.2 HCl and L25. 2HCl were first neutralized
with tBuOK (5 mol%) in 2-propanol for 30 min prior to reaction.
Based on the promising enantioselectivity obtained with L27 for the reduction of
acetophenone, we probed the scope of the reaction with several aromatic ketones (Scheme 4),
under the optimized conditions. In most cases, good to excellent conversions were obtained in
3 h. Increasing the substitution on the methyl group of the acetophenone has a beneficial
impact on the enantioselectivity, as 2,2-dimethyl-1-phenyl-1-propanol b’5 was obtained with
86% ee from pivalophenone a5. The selectivity could even be improved further to 90% ee by
lowering the temperature to 50 °C. On the other hand, in the case of ortho-substituted
acetophenone, the substitution on the aromatic ring has also a positive effect on the
enantioselectivity, leading to moderate to good ee up to 80% for b’6 and 84 % for b’15. In the
case of both electron donating (a10, a11) and electron withdrawing (a12, a13) substituents at
the para-position, the selectivity was lower than for the reduction of acetephenone a1, with ee
ranging from 30% to 46%

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Scheme 4: Scope of the asymmetric reduction of ketones catalyzed by (1R, 2R)-(+)-N,N’-
dimethyl-1,2-diphenyl-1,2-ethane diamine L27 and Mn(CO)5Br.a [a Typical conditions : To a
solution of ketone in 2-propanol were added in this order the diamine (1 mol%), Mn(CO)5Br
1
(1 mol%) and finally tBuOK (2 mol%). Conversion determined by H NMR, ee determined
b
by chiral GC given in parentheses. Each reaction has been repeated at least twice. 50 °C, 24
h.]
Conclusions
We have developed a very simple and efficient catalytic system based on manganese
pentacarbonyl bromide and ethylenediamine for the reduction of ketones by hydrogen transfer

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using isopropanol as the donor. The low cost of both metal precursor and ligand, associated
with the in-situ generation of the catalytic active species, make this system economically
attractive as a sustainable alternative to sodium borohydride for the reduction of ketones.
More importantly, the reactivity has been extended to asymmetric reaction of sterically
hindered ketones with ee up to 90% using (1R,2R)-N,N′-Dimethyl-1,2-diphenylethane-1,2-
diamine as chiral ligand. This first approach demonstrated that simple bidendate, phosphine-
free ligand, can be used with manganese to promote enantioselective reactions with good
selectivity. Further optimization of the design of the ligand to reach very high level of
selectivity is currently under investigation in our laboratory.
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Highlights
 Manganese pentacarbonyl bromide and ethylenediamine promotes hydrogen
transfer
 Asymmetric reduction of ketones was achieved with enantioselectivity up to 90%
ee
 Phosphine-free aliphatic diamines as ligand for transfer hydrogenation with
manganese