Aminocarbonylation of Aryl Halides to Produce Primary Amides by Using NH4HCO3 Dually as Ammonia Surrogate and Base

Article abstract of DOI:10.1002/cctc.201700893

An efficient and clean protocol was developed for rapid production of primary aromatic amides by aminocarbonylation with NH₄HCO₃. Without addition of auxiliary base, the use of solid and cheap NH₄HCO₃ dually as ammonia surrogate and base not only promoted aminocarbonylation over subsequent dehydration and hydrolysis of amides owing to its weak basicity, and it also made the reaction manipulation clean and simplified without the presence of stinky NH₃ or organic amines. The Xantphos ligand with relatively intensive π-acceptor character (¹J_31P–77Se=758 Hz) and wide natural bite angle (β_n=111°) was found to be indispensable for the high efficiency of this reaction.

Full text of DOI:10.1002/cctc.201700893

Accepted Article
Title: Aminocarbonylation of aryl halides to produce primary amides
using NH4HCO3 dually as ammonia surrogate and base
Authors: Ye Liu, Dong-Liang Wang, Huan Liu, Da Yang, Peng Wang,
and Yong Lu
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10.1002/cctc.201700893
ChemCatChem
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Aminocarbonylation of aryl halides to produce primary amides
using NH4HCO3 dually as ammonia surrogate and base
Dong-Liang Wang [a], Huan Liu [a], Da Yang [a], Peng Wang [a], Yong Lu [a] and Ye Liu*[a]
Abstract: The efficient and clean protocol was developed for rapid
production of primary aromatic amides via aminocarbonylation with
NH4HCO3. Without addition of auxiliary base, the uses of solid and
cheap NH4HCO3 dually as ammonia surrogate and base not only
facilitated aminocarbonylation against subsequent dehydration and
hydrolysis of amides due to its weak basicity, but also made the
reaction manipulation clean and simplified without presence of stinky
22], formamide,[23–25] ammonium carbamate[26,27], NH4Cl[28], and
hydroxylamine (derivatives)[8,29] were applied instead of gaseous
NH3. On the other hand, in aminocarbonylation of aryl halides, the
auxiliary strong bases[16] such as N,N-diisopropylethylamine
(DIPEA)[28], 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)[29], or 1,4-
diazabicyclo[2.2.2]octane (DABCO)[8] etc. were unexceptionally
required as the acid scavengers, which not only prevented the
utilization of this methodology for the preparation of alkali-
sensitive targeted structures, but also resulted in the universally
NH3 or organic amines. Xantphos ligand with relatively intensive -
77
acceptor character (1J31 Se = 758 Hz) and wide natural bite angle (n
P-
= 111 o) was found indispensable for the high efficiency of this reaction. observed side reactions such as dehydration[25] and hydrolysis of
amides[30,31]. An efficient and clean protocol to produce primary
amides without using gaseous NH3 and the additional strong
bases is thereby an urgent need but still a challenge in green
organic synthesis.
Introduction
In this work, a solid ammonia surrogate of NH4HCO3 was firstly
used in aminocarbonylation of aryl halides, which served a dual
compounds in organic and bioorganic chemistry due to their wide
role as the ammonia surrogate to afford aromatic primary amides
Primary aromatic and heteroaromatic amides are important
applicationsin organic synthesis, detergents, lubricants,
and as the base to scavenge the acid of hydrogen halide (HX).
pharmaceuticals as well as agrochemicals.[1,2] The transformation
The use of cheap and solid NH4HCO3 not only made the reaction
of carbonyl compounds (such as aldehydes, ketones) or activated
manipulation simplified and inodorous, but also facilitated the
carboxylic acid derivatives is an important method for the
formation of primary amides against the subsequent dehydration
synthesis of amides. For example, the Beckmann rearrangement
is to convert ketoximes (RR’C=NOH) into the corresponding
amides (RCONHR’) under the acidic condition.[3–5] However,
or hydrolysis due to the mild basicity of NH4HCO3. On the other
hand, it has been commonly known that the phosphine ligands
play indispensable roles in promoting aminocarbonylation of aryl
aldoximes (RCH=NOH) susceptibly gives the corresponding
halides[16]. Then a series of diphosphines were screened in
nitriles (RCN) via dehydration rather than primary amides
aminocarbonylation of aryl halides by using NH4HCO3 dually as
(RCONH2). Hence, the synthesis of primary amides from
the ammonia surrogate and base. The ligand of Xantphos based
aldoximes is very difficult and exclusive reagents have to be used
for the transformation.[6] In addition, primary aromatic amides are
on a rigid xanthene backbone was found to give the highest
efficiency for this reaction due to its unique -acceptor ability and
also synthesized by the reaction of activated carboxylic acid
wide natural bite angle of 111 o. To our knowledge, Xantphos-
derivatives (such as acryl chlorides, anhydrides, or esters) with
based Pd-catalyzed aminocarbonylation of aryl halides with
NH4HCO3 into primary amides free of auxiliary base has not been
reported to date.
ammonia[7,8]
,
hydration of benzonitriles[9,10]
,
oxidation of
benzylamines[11] or benzyl alcohols[12]
.
Comparatively, aminocarbonylation of aryl halides with
primary/secondary amines and carbon monoxide catalyzed by
Pd-complexes has become an attractive route for the synthesis of
secondary/tertiary amides since it was firstly reported by Heck in
1974[13]. Recently, a novel copper-catalyzed aminocarbonylation
reaction of alkanes with amines[14] and a C–C bond cleavage/C–
N bond formation reaction were also developed to synthesize
amides.[15] Anyway, the preparation of aromatic primary amides
relatively received less attention[16]. In order to obtain primary
amides, the stinky and gaseous NH3 was required as an ammonia
surrogate.[17,18] And there will be difficulties in handling two kinds
of toxic gases (CO and NH3) in one reaction vessel. To avoid this
Results and Discussion
Initially the influence of different ligands on the catalytic
performance of PdCl2(CH3CN)2 was investigated in the model
reaction of aminocarbonylation of iodobenzene with NH4HCO3
(Table 1). By applying PdCl2(CH3CN)2 (0.5 mol%) and the
different ligands (0.5 mol%), the reaction of iodobenzene (2 mmol)
with two equivalents NH4HCO3 was carried out under CO
o
pressure of 1.0 MPa at 120 C for 1 h respectively (Table 1). It
was noted that, without involvement any auxiliary base, only the
diphosphines of Xantphos and Nixantphos led to the desired
benzamide with acceptable yields (Entries 4 and 5). However, the
incorporated N-atom in Nixantphos serving as an additional N-
donor ligand could interfere the catalytic performance of the Pd-
[19–
problem, various of ammonia surrogates such as NH(SiMe3)2
[a]
D.-L. Wang, H. Liu, D. Yang, P. Wang, Prof. Y. Lu, and Prof. Y. Liu
Shanghai Key Laboratory of Green Chemistry and Chemical
Processes, School of Chemistry & Molecular Engineering, East China
Normal University.
3663 North Zhongshan Road, 200062 Shanghai, China.
Corresponding author‘s email: yliu@chem.ecnu.edu.cn
1
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Table 1 Pd-catalyzed aminocarbonylation of iodobenzene for synthesis of benzamide under different conditions.[a]
Entry
1
Ligand
NH2-source
Base
Temp. (oC)
120
Time (h)
Conv. (%)[b]
Sel. (%)[b]
100
--
BINAP
NH4HCO3 (2.0 eq.)
NH4HCO3 (2.0 eq.)
NH4HCO3 (2.0 eq.)
NH4HCO3 (2.0 eq.)
NH4HCO3 (2.0 eq.)
NH4HCO3 (2.0 eq.)
NH4HCO3 (2.0 eq.)
NH4HCO3 (2.5 eq.)
NH4HCO3 (2.5 eq.)
NH4HCO3 (2.5 eq.)
NH4HCO3 (2.5 eq.)
NH3 (0.2 MPa)
--
1
1
1
1
1
2
3
2
2
2
2
2
2
2
2
2
10
--
2
Dppf
--
120
3
Dppp
--
120
--
--
4
Nixantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
L1
--
120
54
69
77
78
95
96
72
55
96
99
99
99
46
100
100
100
100
100
100
100
100
100
40
5
--
120
6
--
120
7
--
120
8
--
120
9
--
130
10
11[c]
12
13[d]
14[e]
15[e]
16
--
110
--
120
--
120
Aqueous NH3 (2.5 eq.)
NH4HCO3 (1.0 eq.)
NH4HCO3 (1.0 eq.)
NH4HCO3 (2.5 eq.)
--
120
K2CO3 (1.5 eq.)
KOH (1.5 eq.)
--
120
67
120
54
120
100
[a] PhI (2 mmol), PdCl2(CH3CN)2 (0.01 mmol), ligand (0.01 mmol), P/Pd =2/1 (molar ratio), CO (1.0 MPa), solvent CH3CN (4 mL); [b] Determined by GC calibrated
with the commercial sample of benzamide;[c] 0.5 MPa of CO; [d] Benzoic acid was found as only by-product due to the hydrolysis of benzamide; [e] Triphenyltriazine
was found as only by-product due to trimerization of benzamide, which was confirmed by GC-Mass and 1H NMR analyses.
complex, resulting in the decreased transformation rate in spite of
its highly structural similarity to Xantphos (Entry 4 vs 5). The other
tested diphosphines barely resulted in the product at all (Entries
1-3). Therefore, we chose Xantphos for the further condition
optimization.
and inexpensive NH4HCO3 indeed behaved dually as NH3 source
and acid scavenger to afford the amide with advantages of easy
manipulation and odourless working environment. In addition, the
negative effect from CO2 and H2O (derived from the
decomposition of NH4HCO3) was not observable herein. Under
the same reaction conditions (Xantphos as a ligand, 120 oC, 2 h),
the use of ammonia water (30%, 2.5 eq.) in place of NH4HCO3
resulted in abundant formation of benzoic acid due to serious
hydrolysis of benzamide (Entry 13).
Increasing the reaction time from 1 h to 2 h could improve
benzamide yield up to 77% (Entry 6). However, a further
prolonged reaction time to 3 h led to a similar yield (Entry 7). After
evaluating the reaction at 110 oC, 120 oC and 130 oC respectively
with involvement of 2.5 equivalents of NH4HCO3 (Entries 8-10),
o
the temperature of 120 C was proven to be the best choice to
correspond to 95% yield of benzamide (Entry 8), which was
competitive to the result obtained over gaseous NH3 (Entry 12).
Comparatively, the reduced pressure of CO down to 0.5 MPa was
detrimental to the formation of benzamide with the decreased
yield of 55% (Entry 11 vs 8). These results indicated that the solid
2
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Table 2 Comparison of catalytic performance of Pd-catalyst for aminocarbonylation of PhI with NH4HCO3, [a] 1J31 Se of the diphosphine-selenide, and natural bite
77
P-
angle of the diphosphines.
77
Entry
Ligand
Dppf
Conv. (%)[b]
Natural bite angle (n, o) [c]
1J 31 Se (Hz) [d]
P-
1
2
3
--
91
736
722
758
Dppp
--
96
Xantphos
69
111
[a] PhI (2 mmol), PdCl2(CH3CN)2 (0.01 mmol), ligand (0.01 mmol), P/Pd =2/1 (molar ratio), NH4HCO3 4 mmol, CO (1.0 MPa), solvent CH3CN (4 mL), 120 oC;
77
[b] Determined by GC calibrated with the commercial sample of benzamide; [c] Natural biting angle (n) was taken from Ref. 33; [d] 1J 31 Se was detected in this
P-
work.
It was worth to be noted that, although water also existed while
NH4HCO3 was used as the ammonia source, the much weaker
basicity of NH4HCO3 in comparison to that of ammonia water
completely inhibited the hydrolysis of benzamide (Entries 8 vs 13).
When K2CO3 or KOH was added as an auxiliary base, a unique
and thermaldynamically stable by-product of triphenyltriazine was
found due to trimerization of benzamides under strong alkali
condition (Entries 14 and 15). It was also found that when the
chelating coordination mode of Xantphos as a bidentate ligand
was destroyed, its promoting effect on catalytic performance of
Pd-catalyst was damaged badly. For example, when one
phosphine-fragment in Xantphos was methylated by MeOTf
(methyl trifluoromethansulfonate), the resultant mono-phosphine
of L1 led to the sluggish transformation to benzamide only with
46% conversion of phenyl iodide (Entry 16).
amide upon the attack by NH4HCO3. Hence, only Xantphos with
77
relatively intensive -acceptor character (1J31 Se = 758 Hz) and
P-
wide natural bite angle of 111o corresponded to the best efficiency
for Pd-catalyzed aminocarbonylation due to the preference for
forming active mono-metallic intermediate (a) instead of inert
bimetallic complex. On the other hand, Xantphos had the ability
to attenuate Pd-phenyl bond (in b) and Pd-CO bond (in c) to
facilitate the insertion of CO and the release of amide product.
It has been known that the catalytic performance of transition
metal complexes is greatly dependent on the ligand environment
of the metal centre. The exclusive spurring effect of Xantphos on
performance of PdCl2(CH3CN)2 urged us to discern the unique
coordinating characters of Xantphos different from the other
diphosphines. As for a diphosphine, its coordinating ability and
natural biting angle (P-M-P, n) have enormous impact on stability
and catalytic performance of a transition metal complex. The
magnitudes of 1J31 Se is able to be used to measure the -donor
77
P-
1
77
ability of a phosphine[32-34]. An increase of J31
indicates an
P- Se
increase in the character of less -donor ability of a phosphine[33]
.
Hence, the magnitudes of J31 Se and the bite angle of several
1
77
P-
phosphines were compared in Table 3. Obviously, only Xantphos
based on a rigid xanthene backbone with 1J31 Se of 758 Hz and
77
P-
natural biting angle of 111o[35] exhibited a pronounced effect on
the catalytic performance of Pd-complex (Entry 2). In Xantphos,
the rigid xanthene backbone has a marked preference for active
mono-metallic intermediate with bite angles of approximately
110 °, between cis- and trans-coordination modes to the metal
center[35]. In contrast, Dppf and Dppp with natural bite angle of
~90 o are inclined to form the stable and cis-positioned bimetallic
Scheme 1 Proposed mechanism for aminocarbonylation of PhI with NH4HCO3
catalyzed by PdCl2(CH3CN)2 with involvement of Xantphos
The scope of the reaction was then explored with various aryl
halides by using NH4HCO3 dually as ammonia surrogate and
base, and the results were summarized in Table 3. The steric and
electronic effects of the substituents of the applied substrates
indeed influenced the reaction rate dramatically. The
aminocarbonylations of aryl iodides with ortho-, meta-, and para-
methyl substituent performed smoothly to generate the
corresponding amides in excellent yields (Entries 1-3). As for aryl
iodides with electron-withdrawing substituents (like –NO2 and -
CF3) at meta-position, the excellent yields of 99% to the targeted
amides were obtained (Entries 4 and 5). In contrast, aryl iodide
with the electron-donating group of methoxyl corresponded to
84% yield (Entry 6). However, only a trace amount of the desired
amide was detected when ortho- or para-NO2 substituted
iodobenzene was applied (Entry 7 and 8), due to the difficult
complexes[36]
,
which are the inactive catalysts towards
aminocarbonylation. Additionally, the relatively stronger -donor
1
77
1
ability of Dppf and Dppp (Dppf, J31
= 736 Hz; Dppp, J31
P- Se
P-
77
Se = 722 Hz) doesn’t favour CO insertion and migration, resulting
in the failed aminocarbonylation (Entries 1 and 2). As indicated in
the proposed mechanism for aminocarbonylation (Scheme 1)[16,17]
the applied Xantphos as an more intensive -acceptor with 1J31
,
P-
77
Se of 758 Hz can develop a more consolidated Pd-P bonds in the
corresponding Pd-complex catalyst (a) due to the - backdonation
interaction between Pd and P linkages. The consolidated Pd-P
bond leads to the weakened Pd-phenyl bond in Pd-phenyl
intermediate (b) and Pd-CO bond in Pd-acyl intermediate (c),
which favor CO insertion and then the subsequent release of
3
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Table 3 Aminocarbonylation of aryl halides to primary amides with NH4HCO3 as
ammonia surrogate. [a]
21[e]
99
99
Entry
1
Aryl halides
Primary amides
Yield (%)[b]
22[c]
>99
[a] PdCl2(CH3CN)2 (0.01 mmol), Xantphos (0.01 mmol), P/Pd =2/1 (molar ratio),
CO (1.0 MPa), aryl halide (2 mmol), NH4HCO3 (2.5 eq.), solvent CH3CN (4 mL),
120 oC, 3 h; [b] Determined by GC-MS; [c] PdCl2(CH3CN)2 (0.02 mmol),
Xantphos (0.02 mmol), 12 h; [d] Isolated yield; [e] PdCl2(CH3CN)2 (0.01 mmol),
Xantphos (0.01 mmol), P/Pd =2/1 (molar ratio), CO (1.0 MPa), aryl halide (2
mmol), NH4HCO3 (5.0 eq.), solvent CH3CN (4 mL), 120 oC, 3 h.
2
3
>99
>99
Ar-I oxidative addition to Pd-catalyst arising from the markedly
conjugated and inductive effects of ortho- or para-positioned –
NO2 on phenyl ring. Reasonably, ortho-OCH3 substituted
iodobenzene with electron-donating effect led to much higher
yield (99%) of the amide in comparison to meta-OCH3 substituted
one (Entries 9 vs 6). Comparatively, aryl iodides with ortho-
substituents gave relatively lower yields of the primary amides
due to the steric hindrance effect but without obvious
discrimination on the electronic effect (Entries 10-12).
Interestingly, 2-iodoaniline underwent aminocarbonylation with
NH4HCO3 instead of the amine, affording an excellent yield of
anthranilamide (Entry 13). Methyl 4-iodobenzoate with alkali-
sensitive ester group was transformed into the corresponding
amide without hydrolysis of ester (Entry 14). 1-Iodonaphthalene
also produced the corresponding amide in an excellent yield
(Entry 15). As for heteroaryl halides such as 2-iodopyridine or 2-
iodothiophene, the corresponding primary amides were obtained
in the high yields (Entry 16 and 17). The transformation of aryl
bromides to primary amides required relatively harsh conditions.
When the reaction time was prolonged to 12 h and the
concentration of PdCl2(CH3CN)2 was increased up to 1 mol %,
bromobenzene and 3-bromobenzotrifluoride gave excellent yields
of the primary amides (Entries 18 and 19) whereas 2-
bromobenzotrifluoride only corresponded to a trace amount of the
desired product (Entry 20). The aminocarbonylation of
diiodobenzene with NH4HCO3 firstly led to the formation of 2-
iodobenzamide, which was followed by intramolecular cyclization
to afford phthalimine as the final product along with the release of
HI (Entry 21). When 1-bromo-2-iodobenzene was used as a
substrate, only Ar-I aminocarbonylation happened to afford 2-
bromobenzamide with 99% yield (Entry 22). The introduced ortho-
amide group with electron-withdrawing effect badly deactivated
the reactivity of Ar-Br for next aminocarbonylation.
4
5
6
>99
>99
84
7
8
Trace
Trace
9
>99
66
10
11
60
12
13
61
>99
14
70[d]
15
16
>99
>99
Conclusions
17
81
Over Xantphos-based Pd-catalyst, the efficient synthesis of
primary aromatic amides was developed via aminocarbonylation
of (hetero) aryl iodides (or aryl bromides) with NH4HCO3. Without
addition of auxiliary base, the uses of solid and cheap NH4HCO3
dually as ammonia surrogate and base not only facilitated
aminocarbonylation against dehydration and hydrolysis of amides
due to the weak basicity of NH4HCO3, but also made the reaction
manipulation clean and simplified without presence of stinky NH3
18[c]
19[c]
>99
>99
20[c]
Trace
or organic amines. The use of Xantphos ligand with relatively
77
intensive -acceptor character (1J31
= 758 Hz) and wide
P- Se
natural bite angle (n = 111o) essentially guaranteed the high
4
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efficiency of this protocol. Xantphos with the rigid xanthene
backbone has a marked preference to form the mono-metallic
intermediate (a) which serves as the active catalyst for
aminocarbonylation. Meanwhile, the relatively intensive -
acceptor character in Xantphos is also responsible for attenuation
of Pd-phenyl bond (in intermediate b) and Pd-CO bond (in
intermediate c) to facilitate the insertion of CO and then the
release of amide product.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21673077 and 21473058).
Keywords: Aminocarbonylation • NH4HCO3 • Primary amides •
Xantphos ligand • Palladium complex
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5
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10.1002/cctc.201700893
ChemCatChem
·FULL PAPER
Entry for the Table of Contents
FULL PAPER
Dong-Liang Wang, Huan Liu, Da Yang,
Peng Wang, Yong Lu and Ye Liu*
Page No. – Page No.
Aminocarbonylation of aryl halides to
produce primary amides using
NH4HCO3 dually as ammonia
surrogate and base
By using cheap and solid NH4HCO3 dually as ammonia surrogate and base, a
series of aryl halides were efficiently converted into the corresponding primary
aromatic amides by means of aminocarbonylation over Xantphos-based Pd
catalyst.
6
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