Hydrogen acceptor- and base-free N-formylation of nitriles and amines using methanol as C1 source

Article abstract of DOI:10.1002/adsc.201400982

An N-formylation method using methanol as the C₁ source without a stoichiometric amount of activating reagent is described. Nitriles as well as amines can be directly used as substrates. The reaction is catalyzed by an N-heterocyclic carbene coordinated ruthenium(II) dihydride complex, which mediates methanol dehydrogenation, nitrile reduction, and C-N bond formation without any external base, hydrogen acceptor, or oxidant.

Full text of DOI:10.1002/adsc.201400982

UPDATES
DOI: 10.1002/adsc.201400982
Hydrogen Acceptor- and Base-Free N-Formylation of Nitriles and
Amines using Methanol as C1 Source
Byungjoon Kanga,b and Soon Hyeok Honga,b,*
a
Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151-747, Republic of Korea
Fax : (+82)-2-889-1568; phone: (+82)-2-880-6655; e-mail: soonhong@snu.ac.kr
Korea Carbon Capture Sequestration R&D Center (KCRC), Daejeon 305-303, Republic of Korea
b
Received: October 13, 2014; Revised: November 27, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400982.
Abstract: An N-formylation method using metha-
nol as the C1 source without a stoichiometric
amount of activating reagent is described. Nitriles
as well as amines can be directly used as substrates.
The reaction is catalyzed by an N-heterocyclic car-
bene coordinated ruthenium(II) dihydride complex,
which mediates methanol dehydrogenation, nitrile
namic demands of the dehydrogenation reaction of
methanol.[9] Recently, Beller[10] and Grꢂtzmacher[11]
reported the dehydrogenation of methanol in water
to CO2 and H2. The reaction in aqueous media was
necessary to compensate the thermodynamically
uphill methanol dehydrogenation.[12] Without energet-
ic compensation strategies such as using hydrogen ac-
ceptors, it is still challenging to use methanol dehy-
drogenation in organic synthesis. Only a few examples
are reported where methanol is used as the C1 source
À
reduction, and C N bond formation without any
external base, hydrogen acceptor, or oxidant.
in coupling reactions, and most of them are limited to
C C bond formation.
Formamide is a key functional group that serves
a fundamental role in protein biosynthesis and post-
translational regulation steps.[14] Because of its high
biological activity, the formamide moiety is included
Keywords: formylation; homogeneous catalysis; N-
heterocyclic carbenes; ruthenium
[13]
À
With the growing global interest in a sustainable soci- in various pharmaceuticals such as Leucovarin, For-
ety and in environmental issues, atom economy and moterol, and Orlistat. It is also used as a versatile in-
safety have become major topics in organic synthe- termediate in organic synthesis, especially as a precur-
sis.[1] Progress in homogeneous catalysis facilitates the sor to isocyanides and formamidines.
replacement of classical chemical reagents with the
The classical formamide synthetic strategy requires
so-called ꢀgreener alternativesꢁ which are harmless, the presence of the corresponding amine and an
abundant, and renewable.[2] From this point of view, excess amount of ꢀformylating reagentꢁ – chloral,
methanol is an ideal green chemical reagent, especial- phenyl formate, or formic acid – which are environ-
ly as a C1 feedstock.[3] It is the simplest form of alco- mentally hazardous and have limited utility (Sche-
hol, with mild toxicity and a well-known safety pro- me 1a).[15,19c] Using methanol as a ꢀgreen formylating
file.[4] The worldwide methanol production capacity sourceꢁ is a promising strategy, but reported examples
reaches about 100 million metric tons per year,[5] suffer from the need for harsh oxidative conditions,
while biomass conversion[6] and CO2 reduction long reaction times, and limited substrate scope.[16]
chemistry[7] will further create promising ways of uni- Glorius and co-workers recently reported the N-for-
versal methanol provision. In organic synthesis, meth- mylation of an amine using methanol with an excess
anol has so far been considered a versatile solvent amount of styrene (3 equiv.) as the hydrogen accept-
and a moderate nucleophile. However, its utilization or, catalyzed by a Ru complex generated in situ, with
as a C1 building block under mild conditions has been a 12 h induction time, from a mixture of Ru(cod)(2-
explored to a much lesser extent.
methylallyl)2, ICyHCl, and KO-t-Bu at 1258C
The transition metal-catalyzed dehydrogenative al- (Scheme 1b).[17] Soon after Gloriusꢁs pioneering work,
cohol activation strategy offers a new pathway for al- Asao and co-workers reported the same N-formyla-
cohol transformations.[8] However, this kind of activa- tion using O2 as an oxidant on nanoporous Au cata-
tion requires harsher reaction conditions when ap- lysts (Scheme 1b).[18]
plied to methanol, because of the higher thermody-
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Byungjoon Kang and Soon Hyeok Hong
methanol activation with a nitrile reduction step in
complete redox-economy to exclude an additional ac-
tivating reagent. To our delight, the N-formylation of
an amine without any additional base or hydrogen ac-
ceptor was also achieved.
In the first step, benzonitrile was chosen as a model
substrate, and several well-known catalytic systems
for the dehydrogenative amidation of alcohols[19] were
tested (Table 1 and the Supporting Information). The
Milstein catalyst showed no activity (entry 1),[20] while
Gloriusꢁs N-formylating catalytic system[17] showed
limited activity (entry 2). N-Heterocyclic carbene
(NHC) coordinated Ru(II) complexes have been re-
ported as one of the most efficient catalysts for dehy-
drogenative amidation.[19,21] Indeed, various Ru(II)
precursors accompanied with in situ generated NHC
showed promising results (entries 3 and 4). The origi-
nal catalytic system for amide synthesis from nitrile
and alcohol gave only moderate yields (entry 4).[21b]
The product yield was highly dependent on the struc-
ture of the NHC precursor, and 1,3-diisopropylimida-
zolium bromide was the most effective one, as previ-
ously reported (Supporting Information, Table S1).[21]
To
our
delight,
when
the
well-defined
Scheme 1. N-Formamide synthetic strategies.
RuH2(CO)(PPh3)2(IiPr) (1) was used, 4a was formed
in 50% yield even at 908C (entry 5). Catalyst 1 not
only worked under neutral conditions, but also de-
Herein, we report the first synthesis of a formamide creased reaction time and temperature were possible,
from a nitrile and methanol under base- and hydro- by eliminating the induction period for catalyst gener-
gen acceptor-free conditions (Scheme 1c). Replacing ation. Further optimization of the amount of metha-
the amine with a nitrile not only increases the atom nol significantly increased the yield (entry 6). Finally,
economy and step economy of formamide synthesis, use of an increased catalyst loading (10 mol%) leads
but also countervails the thermodynamic demand of to formation of 4a in 87% yield within 3 h (entry 7).
Table 1. Catalyst screening.[a]
Entry
Catalytic system
Solvent (Temp.)
Time [h]
Yield [%][b]
1
2
3
4
Milstein catalyst (5%)[c]
toluene (1108C)
toluene (1108C)
toluene (1108C)
toluene (1108C)
benzene (908C)
benzene (908C)
benzene (908C)
24
36[e]
48
48
24
24
3
0
8
Glorius system[d]
RuCl2(PPh3)3 (10%), NHC precursor (10%),[f] NaH (20%)
RuH2(CO)(PPh3)3 (10%), NHC precursor (10%),[f] NaH (20%)
RuH2(CO)(PPh3)2(IiPr) (1) (5%)
RuH2(CO)(PPh3)2(IiPr) (1) (5%)
RuH2(CO)(PPh3)2(IiPr) (1) (10%)
36
46
50
82
87
5
6[g]
7[g]
[a]
Reaction conditions: 2a (0.25 mmol, 1 equiv.), methanol (6 equiv.), catalytic system, solvent (0.3 mL).
Determined by GC using dodecane as the internal standard.
[b]
[c]
Milstein
catalyst=carbonylhydrido[6-(di-tert-butylphosphinomethylene)-2-(N,N-diethylaminomethyl)-1,6-dihydropyri-
ACHTUNGTRENNUNG
[d]
[e]
[f]
[Ru(cod)(2-methylallyl)2] (5 mol%), 1,3-dicyclohexylimidazolium chloride (10 mol%), and KO-t-Bu (12.5 mol%).
12 h induction time and 24 h reaction.
1,3-Diisopropylimidazolium bromide.
12 equiv. of methanol were used.
[g]
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Hydrogen Acceptor- and Base-Free N-Formylation of Nitriles and Amines
Table 2. N-Formamide synthesis from nitriles and methACTHNUTRGNEUNG
anol.[a]
Entry
Nitrile
Time
[h]
Product
Yield
[%][b]
1
2
3
4
2a
2b
2c
2d
3
5
5
5
4a
4b
4c
4d
87
81
96
91
5
2e
5
4e
97
6
7
8
9
2f
2g
2h
2i
5
5
5
5
4f
4g
4h
4i
82
89
87
80
10
2j
5
4j
94
11[c]
12[c]
2k
2l
10
10
4k
4l
78
81
13[c]
2m
10
4m
81
14[c]
15[c]
2n
2o
10
10
4n
4o
72
68
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Table 2. (Continued)
Entry
Nitrile
Time
[h]
Product
Yield
[%][b]
16[c]
17[c]
2p
2q
10
10
4p
4q
43
71
60
18[c]
2r
2s
10
24
4r
4s-1
85[c]
84[d]
19
24
4s-2
[a]
Reaction conditions: nitrile (0.25 mmol, 1 equiv.), methanol (12 equiv.), 1 (10 mol%), benzene (0.3 mL), 908C.
Isolated yield.
20 equiv. of methanol was used.
Reaction conditions: 2s (0.25 mmol), sodium formate (0.4 mmol), formic acid (0.3 mL), 358C, 24 h.
[b]
[c]
[d]
Notably, when using 1, none of external reagents such
In classical N-formylation, the nitrile is an inert
as the base, hydrogen acceptor, external oxidant, and functional group. When 2s was subjected to the
stabilizing ligand are required, and there is no induc- common N-formylation conditions, selective N-formy-
tion time.
lation of the secondary amine occurred.[22] However,
With the optimized conditions in hand, some readi- when catalyst 1 was introduced in the reaction, the se-
ly available nitriles were transformed into the corre- lective formylation of the nitrile group of 2s proceed-
sponding formamides in good to excellent yields ed in preference to the secondary aniline group in
(Table 2). Benzonitrile derivatives worked smoothly, 85% yield, thus showing inverted selectivity in com-
regardless of electronic and steric properties (en- parison to the traditional N-formylation reaction
tries 1–10). The sterically congested ortho-tolunitrile (entry 19).
showed a slightly decreased reactivity than meta-tolu-
Next, we performed an isotope labelling study, in
nitrile (entries 2 and 3). Electron-rich benzonitriles order to obtain mechanistic insight (Scheme 2). The
had higher activity (entries 4 and 5), while electron- expected deuterium incorporation at the a-carbon of
deficient nitriles gave slightly diminished yields. It is formamide was observed, proving that the hydrogen
À
encouraging that the Ar X bond is unaffected in the generated from CD3OD is involved in the nitrile re-
developed reaction conditions and does not give any duction. Interestingly, a significant amount of H/D ex-
side product (entries 6–8). Nitriles having electron- change (66%) was detected at the b-carbon of forma-
withdrawing substituents such as a trifluoromethyl mide. When independently prepared formamide 4l
group and 1-cyanonaphthalene also exhibited good was treated with CD3OD under the same conditions,
reactivity (entries 9 and 10). The formylation of ali-
phatic nitriles, which are less susceptible to reduction
than aryl nitriles, also proceeded smoothly albeit re-
quiring longer reaction times and an increased
amount of methanol. Linear and branched alkyl cya-
nides were transformed into the corresponding forma-
mides in good yields (entries 11–13). The nitriles with
a cycloalkane ring gave good to fair yields (en-
tries 14–16). The nitriles with a bulky adamantyl
group or a furan ring also reacted well under the reac-
tion conditions (entries 17 and 18).
Scheme 2. Deuterium labelling study.
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Hydrogen Acceptor- and Base-Free N-Formylation of Nitriles and Amines
Scheme 3. Proposed mechanism.
Table 3. N-Formamide synthesis from nitrile and methACTHNUTRGNEUNG
anol.[a]
Entry
Nitrile
Product
Yield
[%][b]
1
2
3
3l
4l
84
96
56
3d
3g
4d
4g
4
5
3k
3t
4k
4t
83
82
6
7
3u
3v
4u
4v
>99
88
8
3w
3x
3y
4w
4x
4y
80
66
71
9
10
11[c]
3z (>98% ee)
4z (>98% ee)
95
[a]
Reaction conditions: amine (0.25 mmol, 1 equiv.), methanol (20 equiv.), 1 (10 mol%), toluene (0.3 mL), 1108C.
Isolated yield.
No epimerization was observed when analyzed with GC accompanied with chiral column.
[b]
[c]
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Byungjoon Kang and Soon Hyeok Hong
volatiles were removed under vacuum. Purification of the
crude product was performed by flash chromatography to
afford the corresponding product.
no deuterium incorporation to the b-position of 4l
was observed. It has been reported that an sp C H
3
À
bond adjacent to a cyano group can be activated by
transition
metal
complexes,[23]
including
RuH2(PPh3)4.[24] Indeed, fast H/D exchange between
the a-position of 2l and the hydroxy deuterium of
CD3OD was observed by H NMR spectroscopy in
the very early stages of the reaction.
1
Acknowledgements
We thank Kunsoon Kim from our group for the help with
catalyst synthesis. This work was supported by the National
Research Foundation of Korea funded by the Korean Gov-
Based on these results, a plausible mechanism is
proposed (Scheme 3). First, hydrogen transfer mediat-
ed by dihydridoruthenium[25] occurs, reducing the ni-
trile to the corresponding amine with simultaneous
generation of formaldehyde. The generated amine un-
dergoes fast coupling with formaldehyde to produce
the hemiaminal intermediate, which is further dehy-
drogenated to the product. The mechanism is further
supported by the fact that the catalyst can formylate
the amine with either methanol or paraformaldehyde
(Supporting Information, Scheme S1).
Inspired by the mechanistic insight, we investigated
the formamidation of amine with methanol in the ab-
sence of any base or hydrogen acceptor (Table 3).[17–20]
The N-formylation of aliphatic and benzylic amines
proceeded smoothly, giving moderate to excellent
yields, with 20 equiv. of methanol in 24 h (entries 1–
5). Secondary amine 3u gave 4u in an excellent yield
(entry 6). Delightfully, amines with heterocycles such
as tetrahydroisoquinoline, 1,3-benzodioxole, thio-
phene, and pyridine were well tolerated in our cata-
lytic system (entries 7–10). In addition, the chirality of
the a-position of the amine (3z) was retained
(entry 11). Employing aniline as a reactant was unsuc-
cessful like other reports on formylation of amines
using methanol,[17,18] presumably due to its low nucle-
ophilicity.
ernment
(NRF-2014R1A2A1A11050028;
NRF-
2014M1A8A1049347, Korea CCS R&D Center; NRF-
2014R1A5A1011165, Center for New Directions in Organic
Synthesis).
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8 Hydrogen Acceptor- and Base-Free N-Formylation of
Nitriles and Amines using Methanol as C1 Source
Adv. Synth. Catal. 2015, 357, 1 – 8
Byungjoon Kang, Soon Hyeok Hong*
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