Phosphine-Free NNN-Manganese Complex Catalyzed α-Alkylation of Ketones with Primary Alcohols and Friedl?nder Quinoline Synthesis

Article abstract of DOI:10.1002/adsc.201800380

Herein, we report a very simple and inexpensive catalytic system based on Earth's abundant transition metal manganese and on a bench-stable phosphine-free NNN-pincer ligand for an atom-efficient α-alkylations of ketones with primary alcohols via hydrogen-autotransfer C?C bond formation protocol. The precatalyst could be generated in situ and could be activated by using catalytic amount of base under milder conditions. A range of ketones were efficiently diversified with a broad range of primary alcohols in good to excellent isolated yields. Remarkably, this catalyst could also be employed for the synthesis of quinoline derivatives using 2-aminobenzyl alcohol as an alkylating agent. The later reaction is highly benign producing only hydrogen and water as byproducts. (Figure presented.).

Full text of DOI:10.1002/adsc.201800380

Title: Phosphine-Free NNN-Manganese Complex Catalyzed α-
Alkylation of Ketones with Primary Alcohols and Friedländer
Quinoline Synthesis
Authors: Milan K. Barman, Akash Jana, and Biplab Maji
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800380
Link to VoR: http://dx.doi.org/10.1002/adsc.201800380

10.1002/adsc.201800380
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Phosphine-Free NNN-Manganese Complex Catalyzed -
Alkylation of Ketones with Primary Alcohols and Friedländer
Quinoline Synthesis
Milan K. Barman,a,† Akash Jana,a,† and Biplab Maji a,*
a
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246,
Nadia (India)
Email: bm@iiserkol.ac.in
These two author contributed equally for this work.
†
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. Herein, we report a very simple and inexpensive
catalytic system based on Earth’s abundant transition metal
manganese and on a bench-stable phosphine-free NNN-
pincer ligand for an atom-efficient α-alkylations of ketones
with primary alcohols via hydrogen-autotransfer C-C bond
formation protocol. The precatalyst could be generated in
situ and could be activated by using catalytic amount of
base under milder conditions. A range of ketones were
efficiently diversified with a broad range of primary
alcohols in good to excellent isolated yields. Remarkably,
this catalyst could also be employed for the synthesis of
quinoline derivatives using 2-aminobenzyl alcohol as an
alkylating agent. The later reaction is highly benign
producing only hydrogen and water as byproducts.
α-alkylation of ketones using alcohols as alkylating
agents have been reported. In contrast, only recently
the manganese catalyzed[10] such reaction has been
disclosed by the Beller group using a manganese
complex of tridendate aliphatic
[(iPr)2PCH2CH2]2NH ligand.[11]
a
Mainly, the current state-of-the-art manganese
catalysts established by the studies of Milstein,[12]
Beller,[7,11,13] Kempe,[14] Kirchner,[10f,15] Sortais,[16]
Boncella[17] and others[18] utilizes diethylamine-core
PNP ligands, pyridinyl-core PNP and PN3P ligands
and triazinyl-core PN5P ligands. However, the major
concerns of these phosphine based pincer ligands in
base-metal catalysis are not only their cost, which are
usually more expensive than the nonprecious metals
by many folds, but also the difficulties lie in their
preparations and handling under standard laboratory
conditions.
Keywords: Alkylation; Manganese catalysts; Hydrogen-
autotransfer; Friedländer reaction; NNN-pincer.
The use of borrowing-hydrogenation or hydrogen-
autotransfer strategy for the alkylations of ketones or
amines have emerged as an eco-friendly repertoire for
the construction of C-C or C-N bonds in compared to
the traditional methods.[1] Typically, this concept
involves
the
transition-metal-catalyzed
dehydrogenation of alcohols followed by the
condensation of the in situ generated aldehydes with
the ketones or the amines. Subsequently, the borrowed
hydrogen reduces the intermediates (e.g. enones or
imines) to yield the desired alkylated products and
water as a sole by-product (Scheme 1).[1b, 1c, 1g, 2]
Scheme 1. Mn-catalyzed hydrogen-autotransfer strategy
for the -alkylation of ketones with alcohols.
In search for simple, overall inexpensive and
sustainable catalytic process, our recent research
focuses on the development of an alternative, cheap,
and bench stable ligands for promoting bifunctional
catalysis. Recently, we have disclosed olefinations of
methylheteroarenes with alcohols catalyzed by a
manganese complex derived from non-innocent
hydrazone-type NNN-pincer ligand.[19] Herein, we
report on the α-alkylation of ketones under hydrogen-
autotransfer conditions using primary alcohols as
Using this strategy, the α-alkylation of ketones have
emerged as a very eco-friendly and attractive protocol
as it avoids the use of stoichiometric strong bases,
cryogenic temperature, and alkyl halides as alkylating
agents.[2a,
Several homogeneous catalysts with
3]
transition metals such as Ru,[4] Ir,[5] Pd,[6] Re[7] etc.
have already been developed for such reactions.
Recently, non-precious iron[8]- and cobalt[9]-catalyzed
1
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10.1002/adsc.201800380
Advanced Synthesis & Catalysis
alkylating agents. The Mn-complex stabilized by the
NNN-ligand mediate the reaction under low catalyst
loading and tolerate reducible functional groups such
as fluoro, chloro, bromo, and iodo despite of the
involvement of the hydrogen under the reaction
condition. The same catalyst also promote the
Friedländer annulation reactions for the green
synthesis of quinoline derivatives using 2-
aminobenzyl alcohol via acceptorless dehydrogenative
coupling where water and dihydrogen were produced
as by-products.
MS analysis of the crude mixture using bromobenzene as
standard. c) Isolated yield was given in the parenthesis. d) 2
mol% catalyst was used. e) L5 was not used. f) Base was not
used. g) Mn(CO)5Br was not used. h) From Ref 11.
To optimize the reaction conditions, preliminary
experiments were done with acetophenone 1a (1
equiv.) and benzyl alcohol 2a (1.2 equiv.) as substrates
using 2.5 mol% of an in situ generated manganese
complex and a base (20 mol%) at 120 oC under argon
atmosphere (Table 1). The Mn-complexes, derived
from 2-picolylamine L1 and di(2-picolyl)amine L2,
independently utilized for the transfer hydrogenations
of aldehydes and ketones by Sortais[16b] and Beller,[13c]
were found to be inefficient for the α-benzylation of
1a (31% and 42% yields of 3a, respectively; entries
1,2). Similarly, unsatisfactory results were obtained
when 2-hydrazinyl pyridine L3 and imine-type pincer
ligand L4 were used (entries 3,4). However, very high
catalytic activity was observed when the hydrazone-
type pincer ligand L5 derived from 2-hydrazinyl
pyridine was used (89% yield, entry 5).[20] The yield
could significantly be improved to 99% by increasing
Table 1. Optimization of the reaction conditions for the
manganese catalyzed α-alkylation of acetophenone 1a with
benzyl alcohol 2a.a)
o
the temperature to 140 C and the desired product 3a
Base
Entr
y
Liga
nd
T
Yield
[%]b)
Solvent
[oC]
was isolated in 91% yield under these conditions
(entry 6). The use of other bases were found to be
detrimental for this reaction (entries 7-9). The base and
the manganese loading could be lowered to 10 and 2
mol%, respectively without any loss of catalytic
activities (entries 10,11). Other solvents like toluene,
1,4-dioxane and t-BuOH were found to be less suitable
(entries 12-14). A series of control experiments
demonstrate the necessity of the metal precursor
Mn(CO)5Br, L5 and t-BuOK, as traces of 3a were
obtained in their absence (entries 15-17). It should be
noted that the PNP-Mn catalyst developed by the
Beller group delivered 88% of 3a under their
conditions.[11]
[mol%]
t-BuOK
(20)
t-BuOK
(20)
t-BuOK
(20)
t-BuOK
(20)
t-BuOK
(20)
t-BuOK
(20)
t-BuOLi
(20)
t-BuONa
(20)
Cs2CO3
(20)
t-BuOK
(10)
t-BuOK
(10)
t-BuOK
(10)
t-BuOK
(10)
t-BuOK
(10)
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
t-AmOH
toluene
120
120
120
120
120
140
140
140
140
140
140
140
140
120
31
42
10
29
89
1
2
L1
L2
L3
L4
L5
L5
L5
L5
L5
L5
L5
L5
L5
L5
3
4
5
99
6
(91)c)
72
73
32
99
99
67
73
68
7
Utilizing this optimized conditions (Table 1, entry 11),
we have demonstrated the scope of this Mn-catalyzed
α-alkylation reactions (see Table 2). Initially, the
reactions of different substituted ketones with benzyl
alcohol derivatives were tested. As shown in Table 2,
a series of acetophenone derivatives with electron rich
such as 4-Me (1b), and 3-OMe (1c) and electron
deficient such as 4-F (1d), and 4-Cl (1e) functional
groups were α-benzylated in 68-90% yields. However,
4-cyano- and 4-carboethoxy acetophenones (1f,g)
were found to be unsuitable coupling partner. When
methylnapthyl ketone 1h, α-tetralone 1i and methyl
thiophenyl ketone 1j were used, the desired products
were obtained in 65-82% yields. With the success with
arylmethyl ketone we have turn our attention to more
challenging alkylmethyl ketone. While mixture of
compounds were obtained when iso-propylmethyl
ketone 1k was used, tert-butylmethyl ketones 1l was
found to be suitable coupling partner delivering the
product in 64% yield.
8
9
10
11d)
12
13
14
1,4–dioxane
t-BuOH
t-BuOK
(10)
15e)
16f)
17g)
-
t-AmOH
t-AmOH
t-AmOH
140
140
140
10
–
–
L5
L5
t-BuOK
(10)
12
PNP-
Mn
Cs2CO3
(5)
18h)
t-AmOH
140
88
a) General reaction conditions: Mn(CO)5Br (2.5 μmol) and a
ligand (2.5 μmol) were stirred at 80 °C in t-AmOH (0.5 mL)
for 2 h, after which a base, acetophenone 1a (0.1 mmol), and
benzyl alcohol 2a (0.12 mmol) were added and the reaction
was heated to 120 or 140 oC for 24 h. b) Determined by GC–
The compatibility of different primary alcohols for this
Mn-catalyzed C-C bond formation reaction were then
evaluated. Consequently, structurally diverse primary
2
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10.1002/adsc.201800380
Advanced Synthesis & Catalysis
Table 2. Scope of the Mn–catalyzed α-alkylations of
1i took place when ethanol 2k was used as an
electrophile and the product 3v was isolated in
moderate 49% yield. However, no product was
observed when methanol 3w was used. Whereas, when
higher alcohol n-butanol 2m was used as an alkylating
agent the corresponding α-butylated ketones 3x-z were
isolated in 63-83% yields. Strained cyclopropyl
methanol 2n was also found to be viable coupling
partner and the product 3aa was isolated in 79% yield.
The NNN-Mn complex developed in this work also
revealed an efficient activity for the syntheses of
quinoline derivatives when 2-aminobenzyl alcohol
was used as coupling partner (Table 3). Traditionally,
the Friedlꢀnder annulation reactions[21] utilizes the
condensation reactions of 2–aminobenzaldehydes with
ketones under acidic or basic conditions and often
suffers from the issues like the limited stability of 2–
aminobenzaldehydes, self-condensations etc.[13c]
Using comparatively more stable 2–aminobenzyl
alcohols and catalytic amount of base, the acceptorless
dehydrogenative coupling allows greener synthesis of
quinolines.[10a, 10e, 10f, 14c, 21] Recently, Fe-, Co-, Ni-, and
Cu-based catalysts have been employed for such
reactions.[10d, 10e, 13c, 16b, 22]
ketones with alcohols.a)
Table 3. Scope of Mn–catalyzed Friedlꢀnder quinoline
syntheses.a)
a) Reaction conditions: Mn(CO)5Br (5 μmol) and the ligand
L5 (5 μmol) were stirred at 80 °C in t-AmOH (1.0 mL) for
2 h, after which t-BuOK (0.02 mmol), ketones 1a-l (0.2
mmol), and primary alcohols 2a-n (0.24 mmol) were added
and the reaction was heated to 140 oC for 24 h. Yields of the
isolated products were given. b) Mixture of compounds. c)
1:1 mixture of t-AmOH:EtOH (1.0 mL) was used. d) 1:1
mixture of t-AmOH:MeOH (1.0 mL) was used.
alcohols were used as alkylating agents and the results
are summarized in Table 2. Remarkable, reducible
halogen functional groups such as fluoro, chloro,
bromo and iodo at 3- or 4-position of the benzyl
alcohol were tolerated delivering the alkylated
products 3n-q in 62-96% yields. Similarly, 4-CF3-
benzyl alcohols 2g also underwent smooth α-
alkylation reaction and the product 3r was isolated in
81% yield. Pyridine, furan, and thiophen containing
heteroaromatic alcohols 2h-j were also found to be
viable coupling partners delivering the products 3s-u
in 62-83% yields. Furthermore, synthetically more
challenging aliphatic alcohols could also be used for
this strategy. For example, α-ethylation of α-tetralone
a) Reaction conditions: Mn(CO)5Br (5 μmol) and the ligand
L5 (5 μmol) were stirred at 80 °C in t-AmOH (1.0 mL) for
2 h, after which t-BuOK (0.02 mmol), the ketones 1a-p (0.2
mmol), and the amino alcohol 2o (0.24 mmol) were added
and the reaction was heated to 140 oC for 24 h. Yields of the
isolated products were given.
The manganese catalyst described in Table 1 for the
α-alkylation of ketones also displayed efficient
activities for Friedlꢀnder annulation reaction using 2–
aminobenzyl alcohol 2o. As shown in Table 3, 2-
phenylquinoline 4a was isolated in 81% yield from the
3
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10.1002/adsc.201800380
Advanced Synthesis & Catalysis
reaction of 2o and 1a (Table 3) in a comparatively
shorter reaction time than the reported examples.[9a, 9d]
A wide range of aryl ketones with different electronic
substituents also underwent smooth annulation
reactions delivering the quinolines in 40-97% yields
(Table 3). More interestingly, heteroaromatic
methylketones, such as 2-acetylthiophene 1j and 2-
acetylpyridine 1o performed well for this reaction to
yield the corresponding quinolies 4g and 4h in 76%
and 80% yields, respectively. The use of α-tetralone 1i
as coupling partner resulted in formation of 5,6-
dihydrobenzo[c]acridine 4i in 72% yield. Similarly,
fused 11H-indeno[1,2-b]quinoline 4j was obtained in
82% yield when 1-indanone 1p was used.
reaction of 2o with 1a was carried out in one chamber
and the other chamber contains α-methyl styrene and
Pd/C. The observed 70% yield of cumene conclusively
support the acceptorless liberation of dihydrogen.
A probable mechanistic cycle is proposed in
Scheme 2 based on literature reports and our
observations.[11,19,23] The manganese complex I
generated in presence of base dehydrogenate the
alcohol via an alkoxy complex II. The liberated
aldehyde 5 or the aminoaldehyde 6 then undergo aldol
condensation with the ketone to generate the α,β-
unsaturated compounds 7 and 8 with the release of one
molecule of water. The hydrogenation of 7 then yields
the desired product 3 and regenerate the catalyst. In
case of 8, it undergoes fast dehydative cyclization to
yield the quinoline product 4a. We believe that the
manganese complex III then react with one molecule
of 2o to liberate one molecule of dihydrogen and
complete the catalytic cycle.[22f]
Scheme 3. Control experiments.
In conclusion, we have demonstrated that a Mn-
complex of a bench stable NNN-pincer ligand is an
efficient catalyst for the α-alkylation of ketones with
primary alcohols in presence of catalytic amount of
base. This catalyst also showed efficient catalytic
activity for Friedlꢀnder quinoline synthesis. This is the
first example when an inexpensive phosphine-free
NNN-pincer ligand is being used for the manganese
catalyzed ketone alkylation reactions and acceptorless
dehydrogenative synthesis of quinolines.
Experimental Section
General procedure for Mn–catalyzed α-alkylation of
ketones with alcohols: In a 15 mL Schlenk tube, Mn(CO)5Br
(1.10 mg, 0.0040 mmol, 2.0 mol%) and L5 (0.9 mg, 0.004
o
mmol) were stirred at 80 C in t-AmOH (2.0 mL) for 2 h
under argon. Then t-BuOK (1.1 mg, 0.01 mmol), ketone (0.2
mmol), and corresponding primary alcohol (0.24 mmol)
were added and the tube was closed before the mixture was
o
placed in a preheated oil bath at 140 C for 24 h under Ar
atmosphere. The progress of the reaction was monitored by
TLC. Upon completion, the solvent was evaporated and the
residue was purified by column chromatography over silica
gel (100–200 mesh) with hexane/ethyl acetate mixture as
eluent.
Scheme 2. Proposed mechanism.
General procedure for Mn–catalyzed Friedlꢀnder quinoline
synthesis: In a 15 mL Schlenk tube, Mn(CO)5Br (1.1 mg,
0.0040 mmol, 2.0 mol%) and L5 (0.9 mg, 0.004 mmol) were
Previously, we and others have shown the
involvement of the dehydrogenation catalyst in the
CC-bond forming aldol condensation process.[19, 23] To
probe whether the NNN-Mn complex is also involved
in the aldol reaction we have perform the reaction of
benzaldehyde with 1a in presence and absence of the
catalyst (Scheme 3a). The observed 2.3 fold rate
acceleration is an indicative of the involvement of the
catalyst in the key CC-bond formation process.
o
stirred at 80 C in t-AmOH (2.0 mL) for 2 h under argon.
Base t-BuOK (1.1 mg, 0.01 mmol), ketone (0.2 mmol) and
2-aminobenzyl alcohol (0.24 mmol) were mixed. The
mixture was then stirred at 140 °C for 24 h under Ar
atmosphere. The progress of the reaction was monitored by
TLC. Upon completion, the solvent was evaporated and the
residue was purified by column chromatography over silica
gel (100–200 mesh) with hexane/ethyl acetate mixture as
eluent.
Then the acceptorless liberation of molecular
hydrogen was probed by performing the Pd/C
catalyzed hydrogenation of α-methyl styrene in an H-
shaped bridged tube (Scheme 3b) using the liberated
dihydrogen in the annulation reaction. In such
experiment, the manganese catalyzed annulation
Acknowledgements
The author thanks IISER Kolkata (Start-up grant) and SERB
(ECR/2016/001654) for financial support. M.K.B. thanks SERB
(PDF/2016/001952) for an NPDF fellowship. A.J. thanks CSIR for
PhD fellowship.
4
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10.1002/adsc.201800380
Advanced Synthesis & Catalysis
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10.1002/adsc.201800380
Advanced Synthesis & Catalysis
COMMUNICATION
Phosphine-Free NNN-Manganese Complex
Catalyzed -Alkylation of Ketones with Primary
Alcohols and Friedländer Quinoline Synthesis
Adv. Synth. Catal. Year, Volume, Page – Page
†
†
Milan K. Barman, Akash Jana, and Biplab Maji*
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