Manganese-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as a Sustainable C1 Building Block

Article abstract of DOI:10.1021/jacs.7b05253

This study represents the first example of a manganese-catalyzed environmentally benign, practical three-component aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes in combination with amines and MeOH as a C1 source. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps which give rise to selective C-C and C-N bond formations, thereby releasing hydrogen and water. A well-defined hydride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way, and a total of 28 different aminomethylated products were synthesized and isolated yields of up to 91%. In a preliminary study, a related Fe(II) PNP pincer complex was shown to catalyze the methylation of 2-naphtol rather than its aminomethylation displaying again the divergent behavior of isoelectronic Mn(I) and Fe(II) PNP pincer systems.

Full text of DOI:10.1021/jacs.7b05253

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Communication
Manganese-Catalyzed Aminomethylation of Aromatic Com-
pounds with Methanol as Sustainable C1 Building Block
Matthias Mastalir, Ernst Pittenauer, Günter Allmaier, and Karl Kirchner
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 19 Jun 2017
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Manganese-Catalyzed Aminomethylation of Aromatic Com-
pounds with Methanol as Sustainable C1 Building Block
Matthias Mastalir,† Ernst Pittenauer,‡ Günter Allmaier,‡ Karl Kirchner*,†
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† Institute of Applied Synthetic Chemistry and ‡ Institute of Chemical Technologies and Analytics, Vienna University of
Technology, Getreidemarkt 9, Aꢀ1060 Wien, Austria.
ABSTRACT: This study represents the first example of a manganeseꢀcatalyzed environmentally benign, and practical threeꢀcomponent
aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes in combiꢀ
nation with amines and MeOH as C1 source. These reactions proceed with high atomꢀefficiency via a sequence of dehydrogenation and
condensation steps which give rise to selective CꢀC and CꢀN bond formations, thereby releasing hydrogen and water. A wellꢀdefined hyꢀ
dride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way and a total of 28 difꢀ
ferent aminomethylated products were synthesized and isolated yields of up to 91 %. In a preliminary study, a related Fe(II) PNP pincer
complex was shown to catalyze the methylation of 2ꢀnaphtol rather than its aminomethylation displaying again the divergent behavior of
isoelectronic Mn(I) and Fe(II) PNP pincer systems.
During the past decade, the acceptorless dehydrogenation
(AD) of alcohols,1 an oxidantꢀfree, atomꢀeconomical approach to
yield carbonyl compounds, has emerged as powerful tool for the
benign construction of valuable complex organic molecules. Alꢀ
cohols are sustainable and abundant building blocks as they are
readily available by a variety of industrial processes and can be
obtained renewably via fermentation or catalytic conversion of
lignocellulosic biomass.2,3 Ketones and aldehydes generated in
situ can be converted into other useful organic materials such as
amines, imines, amides, or heterocycles. In the course of these
transformations only dihydrogen and water as nontoxic byprodꢀ
ucts are generated. Due to the significance of CꢀC and CꢀN bond
forming reactions, in recent years several efficient homogeneous
catalysts based on nonꢀprecious, inexpensive, earth abundant metꢀ
als like Mn,4,5,6,7 Fe,8,9,10 Co11,12,13 or Ni14 have been developed
which are highly active for AD of alcohols as well as in the oppoꢀ
site reaction, i.e. the hydrogenation of carbonyl compounds. In
particular AD reactions catalyzed by Mn(I) pincer complexes beꢀ
came a very important research topic, after seminal reports in
2016 by the groups of Milstein,5a,b Beller,5f,g and us5d,e on deꢀ
hydrogenative coupling reactions of alcohols and amines to
yield imines, αꢀalkylation of ketones with primary alcohols, and
multicomponent reactions to form heterocycles such as quinolines
and pyrimidines. Within the following months a remarkable
number of intriguing developments in catalytic transformations
with Mn pincer complexes has been achieved. The group of
Kempe5c and our group5d,e reported the dehydrogenative couꢀ
pling of alcohols with amines and amidines to form pyrimꢀ
idines. Beller et al. described the Mnꢀcatalyzed dehydrogenaꢀ
tion of MeOH,5h and the Milstein group described the N-
Inspired by these rapidly growing developments in Mn(I) caꢀ
talysis, we describe here an efficient threeꢀcomponent amiꢀ
nomethylation of activated aromatic and hetero aromatic comꢀ
pounds with MeOH as key feedstock (Scheme 1). A Ruꢀcatalyzed
aminomethylation of phenol derivatives utilizing MeOH as C1
source was recently described by Kim and Hong (Scheme 1).15
Surprisingly, when 2ꢀnaphthol was employed instead of phenol,
only methylation was observed.
Scheme 1. Catalytic aminomethylations of aromatic com-
pounds utilizing amines and MeOH as C1 source.
formylation of amines with MeOH 5m
Gauvin et al described an
.
First, the reaction conditions were optimized for the three
component reaction of 2ꢀnaphtol, piperidine and MeOH (in a
1:1.1:1.3 ratio) as model system in toluene (4 mL) in the presence
acceptorless dehydrogenative coupling of alcohols to esters,5j and
the group of Darcel and Sortais reported the monoꢀNꢀmethylation
of anilines with MeOH.5k
of 1.3 equiv KO
tBu and 4 mol% [Mn] at 130 °C (Table 1). The
1
products were analyzed by H and 13C{1H} NMR and identified
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by comparison with authentic samples. In general, isolated yields
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after purification by column chromatography are reported. Under
these reactions conditions 1ꢀ(piperidinꢀ1ꢀylꢀmethyl)naphthaleneꢀ
2ꢀol (1) was selectively formed in 86 % isolated yield (Table 1,
entry 1). Shorter reaction times led to a drop in yield (Table 1,
entry 2), while longer reaction time did not lead to an improveꢀ
ment of the yield (Table 1, entry 3). Lowering the temperature to
3
5
4
6
5 (92 %)
7 (84 %)
6 (85 %)
o
110 C resulted in low yields (Table 1, entry 5). Likewise, also
lowering of the catalyst loading (2 mol %) led to a reduced yield
(Table 1, entry 4). When the reaction was performed in the abꢀ
sence of amine, dimerization of 2ꢀnaphtol through a bridging
methylene group took place to give 1,1'ꢀmethylenedinaphthaleneꢀ
2ꢀol (2) in 63 % isolated yield (Table 1, entry 6).
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8 (49 %)
Table 1. Optimization of the reaction conditions for the
aminomethylation of aromatic compounds.a,b
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8
9 (60 %)
10 (78 %)
12 (78 %)
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11 (81 %)
entrya
base
T
[°C]
time
[h]
yieldb
1 [%]
yieldb
2 [%]
11
13
1
2
tBuOK
tBuOK
tBuOK
tBuOK
tBuOK
tBuOK
130
130
130
130
110
130
130
16
8
86
72
87
78
37
(81 %)
14 (87 %)
16 (82 %)
3
24
16
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16
13
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14
16
4c
5
15 (61 %)
6d
63
7
traces
17 (77 %)
OH
a Reaction conditions: 1.3 mmol MeOH, 1.0 mmol 2ꢀnaphthol, 1.1 mmol
piperidine, 1.3 mmol tBuOK, 4 mL toluene, 130 °C. b Isolated yields. c 2
mol % [Mn]. d In the absence of amine.
18 (68 %)
20 (64 %)
Cl
N
17
18
Table 2. Aminomethylation of aromatic compounds with
MeOH and amines catalyzed by [Mn].a,b
Cl
19 (55 %)
19c
20c
21 (43 %)
22 (44 %)
24 (52 %)
entry
1
product
entry
2
product
21
22
23 (75 %)
3 (72 %)
4 (91 %)
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and dimerized compounds 1 and 2, respectively, as minor prodꢀ
ucts (Table 3, entry 1). In the absence of amine, was the major
product (54 % yield), with being formed in only 17 % yield.
Table 3, entry 2). In the absence of KO Bu no products were
obtained at all. If the reaction is performed in the presence of
0.2 equiv of piperidine, the major product is the methylated 2ꢀ
naphtol 31, with only 13 % of dimerized product (Table 3, entry
4). The yield of 31 could be further increased to 75 %, if the
temperature is raised to 140 oC (Table 3, entry 5).
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2
1
23
24
(
t
26 (81 %)
28 (74 %)
25 (74 %)
27 (64 %)
25d
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28
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Table3. Optimization of the reaction conditions for the
methylation of 2-naphthol.a,b
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29 (76 %)
30 (59 %)
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a
Reaction conditions: 1.3 mmol MeOH, 1.0 mmol substrate, 1.1 mmol
amine, 1.3 mmol tBuOK, 4 mol % [Mn], 4 mL toluene, 130 °C. b Isolated
yields. c 2.2 mmol MeOH, 1.0 mmol substrate, 2.2 mmol amine, 2.6 mmol
tBuOK, 7 mol % [Mn], 4 mL toluene. d Imidazole as Nꢀnucleophile.
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entrya
base
amine
yieldb
yieldb
yieldb
29 [%]
1 [%]
2 [%]
1
2
tBuOK
tBuOK
piperidine
48
17
28
17
54
Having established the optimal reaction conditions, this methꢀ
odology was applied to other aromatic and heteroaromatic comꢀ
pounds in combination with different amines and MeOH (Table
2). 2ꢀNaphtol (Table 2, entries 1ꢀ6), 1ꢀnaphtol (Table 2, entry 7),
phenols (Table 2, entries 8ꢀ17), 3ꢀhydroxypyridine (Table 2, enꢀ
tries 18ꢀ20), carbazole (Table 2, entry 21), indole (Table 2, entry
22), 1ꢀmethylindole (Table 2, entries 23 and 24) and 3ꢀ
methoxythiophene (Table 2, entries 26ꢀ28) were treated with diꢀ
ethylamine, benzylamine, methylbenzylamine, piperidine, pyrolꢀ
lidine, morpholine, imidazole and 1.3 equiv of MeOH to afford
the corresponding aminomethylated products in good to high isoꢀ
lated yields. Methylation was not observed in any of the investiꢀ
gated cases, as observed by Kim and Hong15 when 2ꢀnaphthol was
employed instead of phenol. 2ꢀNaphtol affords selectively the reꢀ
spective 1ꢀaminomethylated products (Table 2, entries 1ꢀ6), while
1ꢀnaphtol yields the 2ꢀaminomethylated compound (entry 7).
Phenols, depending on the substitution pattern, yield selectively
either 2ꢀ orꢀ4ꢀaminometylated products (Table 2, entries 8ꢀ17).
The reaction of 3ꢀhydroxypyridine with 1 or 2 equiv of benzylaꢀ
mine and MeOH resulted in the formation of 6ꢀ
(dibenzylaminomethyl)pyridinꢀ3ꢀol and 2,6ꢀbis(dibenzylaminoꢀ
methyl)pyridinꢀ3ꢀol, respectively (Table 2, entries 18 and 20).
With carbazole and indole aminomethylation occurred at the niꢀ
trogen site rather than at a Cꢀposition yielding 1ꢀ(pyrrolidinꢀ1ꢀylꢀ
methyl)ꢀ1Hꢀindole and 9ꢀ(piperidinꢀ1ꢀylmethyl)ꢀ9Hꢀcarbazole
(Table 2, entries 21 and 22). The reaction of 1ꢀmethylindole with
imidazole resulted in dimerization rather than aminomethylation
to give bis(1ꢀmethylꢀ1Hꢀindoleꢀ3ꢀyl)methane (Table 2, entry 25).
3ꢀMethoxythiophenes afforded selectively 2ꢀaminomethylated
products (Table 2, entries 26ꢀ28).
3
piperidine
piperidine
piperidine
traces
67
traces
traces
traces
traces
14
4c
tBuOK
tBuOK
5c,d
75
13
a Reaction conditions: 1.3 mmol MeOH, 1.0 mmol 2ꢀnaphthol, 1.1 mmol
amine, 1.3 mmol tBuOK, 4 mol % [Fe], 4 mL toluene, 130 °C. b Isolated
yields.c 0.2 mmol amine. d 140 °C.
In conclusion, this study represents the first example of a
manganeseꢀcatalyzed environmentally benign, and practical threeꢀ
component aminomethylation of aromatic compounds including
naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes
in combination with amines and MeOH as C1 source. These reacꢀ
tions proceed with high atomꢀefficiency via a sequence of dehyꢀ
drogenation and condensation steps which give rise to selective Cꢀ
C and CꢀN bond formations, thereby releasing hydrogen and waꢀ
ter. Moreover, in a preliminary study a related Fe(II) PNP pincer
complex was shown to catalyze the methylation of 2ꢀnaphtol raꢀ
ther than its aminomethylation underlining again the divergent
reactivity of isoelectronic Mn(I) and Fe(II) PNP pincer systems.
As described recently,5d both Mn and Fe catalysts are able to form
coordinatively unsaturated intermediates upon deprotonation of
the PNP ligand (bifunctional behavior). The important difference
is that Mn contains two, Fe only one inert CO coꢀligand, but Fe
additionally contains a hydride ligand which can participate in the
catalytic reaction. Accordingly, the Mn catalyst is able to perform
only dehydrogenation reactions, while the Fe system (in analogy
to many Ru systems) is capable of performing both dehydrogenaꢀ
tions and hydrogenations (via an insertion mechanism). This study
demonstrates that base metal catalysts begin to challenge precious
metal catalysts and may contribute to a further advancement of
wasteꢀfree sustainable base metal catalysis.
Since the isoelectronic Mn(I) and Fe(II) PNP pincer complexꢀ
es [Mn] and [Fe], respectively, exhibited divergent reactivities in
the dehydrogenative coupling of alcohols with amines,5d we
also studied the three component reaction of 2ꢀnaphtol, piperidine
and MeOH with 4 mol% [Fe] as catalyst (Table 3). In contrast to
the Mnꢀcatalyzed reaction under identical reaction conditions, the
methylated product 1ꢀmethylnaphthaleneꢀ2ꢀol (31) was formed as
major product (48 % yield), together with the aminomethylated
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Supporting Information
The supporting information is available free of charge on the ACS
1
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Publications website at DOI: xxxxx
1
Synthetic procedures, H, 13C{1H} and 19F{1H} NMR spectra of
all organic products (PDF).
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Glatz, M.; Pittenauer, E.; Allmaier, G.; Kirchner, K. J. Am. Chem.
AUTHOR INFORMATION
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Sortais, J.ꢀB.; Junge, K.; Darcel C.; Beller, M. Nat. Commun. 2016, 7,
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AndérezꢀFernández, M.; Vogt, L. K.; Fischer, S.; Zhou, W.; Jiao, H.;
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Roisnel, T.; Darcel, C.; Sortais, J.ꢀB. J. Catal. 2017, 347, 57ꢀ62. (k)
Nguyen, D. H.; Trivelli, X.; Capet, F.; Paul, J.ꢀF.; Dumeignil, F.;
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Corresponding Author
* Eꢀmail for K.K.: karl.kirchner@tuwien.ac.at
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ORCID
Matthias Mastalir: 0000ꢀ0002ꢀ8969ꢀ7902
Ernst Pittenauer: 0000ꢀ0002ꢀ8409ꢀ802X
Günter Allmaier: 0000ꢀ0002ꢀ1438ꢀ9462
Karl Kirchner: 0000ꢀ0003ꢀ0872ꢀ6159
Notes
Chakraborty, S.; Gellrich, U.; Diskinꢀꢀ Posner, Y.;
7261ꢀ7265. (m)
Leitus, G.;
The authors declare no competing financial interest.
Avram, L.; Milstein, D. Angew. Chem., Int. Ed. 2017
56, 4229ꢀ4233.
,
ACKNOWLEDGMENT
MM and KK gratefully acknowledge the Financial support by the
Austrian Science Fund (FWF) (Project No. P29584ꢀN28).
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