Highly selective palladium-catalysed aminocarbonylation of aryl iodides using a bulky diphosphine ligand

Article abstract of DOI:10.1002/adsc.201200114

An efficient methodology for the synthesis of amides via palladium-catalysed aminocarbonylation of aryl iodides is reported using the bulky cis-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane ligand under atmospheric pressure of carbon monoxide. Excellent conversions (up to 99%) and chemoselectivities (up to 99%) were obtained for a range of aryl iodides and amine nucleophiles. The effect of the substituents on the substrate and nucleophiles on the catalytic performance was investigated. An NMR study was also carried out and key intermediates of the catalytic cycle were detected and characterised. Copyright

Full text of DOI:10.1002/adsc.201200114

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DOI: 10.1002/adsc.201200114
Highly Selective Palladium-Catalysed Aminocarbonylation of
Aryl Iodides using a Bulky Diphosphine Ligand
Verꢀnica de la Fuente,a Cyril Godard,a Carmen Claver,a,* and Sergio Castillꢀnb,*
a
Departament de Quꢁmica Fꢁsica i Inorgꢂnica, Universitat Rovira i Virgili, C/Marcel·lꢁ Domingo s/n, 43007 Tarragona,
Spain
Fax : (+34)-977-559-563; e-mail: carmen.claver@urv.cat
Departament de Quꢁmica Analꢁtica i Orgꢂnica, Universitat Rovira i Virgili, C/Marcel·lꢁ Domingo s/n, 43007 Tarragona,
b
Spain
Fax : (+34)-977-558-446; e-mail: sergio.castillon@urv.cat
Received: February 12, 2012; Revised: April 6, 2012; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200114.
Abstract: An efficient methodology for the synthesis the substituents on the substrate and nucleophiles on
of amides via palladium-catalysed aminocarbonyla- the catalytic performance was investigated. An NMR
tion of aryl iodides is reported using the bulky cis- study was also carried out and key intermediates of
1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane
the catalytic cycle were detected and characterised.
ligand under atmospheric pressure of carbon monox-
ide. Excellent conversions (up to 99%) and chemose- Keywords: amide synthesis; diphosphines; a-keto
lectivities (up to 99%) were obtained for a range of amides; NMR studies; palladium-catalysed amino-
aryl iodides and amine nucleophiles. The effect of carbonylation
Introduction
system using Pd/14 as catalyst, achieving chemoselec-
tivities up to 86% (Scheme 1).[18] The carbon monox-
The Pd-catalysed aminocarbonylation reaction pro- ide pressure influences the chemoselectivity of the re-
vides an easy and practical method for the synthesis action since under low pressures, the formation of
of amides, which are valuable products for the phar- amides (2 in Scheme 1) is favoured whereas high CO
maceutical industry.[1a,b] This reaction is used industri- pressures are required for the synthesis of a-keto
ally to produce Lazabemide, a monoamine oxidase B amides (3, Scheme 1).[18]
inhibitor, in one step from 2,5-dichloropyridine.[1c] Al-
The catalytic cycle using monodentate phosphine li-
though the Pd-catalysed aminocarbonylation, where gands is now well established.[2–13] However, some un-
the nucleophile is an amine, is related to the Pd al- certainty and disagreements remain in the last steps
koxycarbonylation, where the nucleophile is an alco- of the catalytic cycle.[2–13]
hol, the former reaction has been much less studied.
Heck first reported on palladium complexes nylation reaction of aryl halides is presented in
[PdX2A(PPh3)2] (X=Br, I) which were active in the Pd- Scheme 2, A and consists of: (i) oxidative addition of
The most accepted mechanism for the aminocarbo-
A
CHTUNGTRENNUNG
catalysed aminocarbonylation of various aryl halides the aryl halide at the Pd(0) species (a) to form the
under 1 atm of carbon monoxide at 1008C.[2] Later, Pd(II) complex (b); (ii) coordination of carbon mon-
various catalytic systems were reported for this pro- oxide to give the pentacoordinated intermediate (c),
cess.[3–21] However, the Pd/PPh3 remains the most effi- (iii) carbonyl migratory insertion to yield the acyl pal-
cient for this reaction.[15–17]
ladium complex (d), and (iv) nucleophilic attack at
In this process, the use of bidentate phosphine li- the acyl produces the final product and regenerates
gands has been less explored, and mixtures of amides the initial Pd(0) species. An alternative mechanism
(2), a-keto amides (3) or dehalogenation products has also been proposed (Scheme 2, B) in which the
were usually obtained (Scheme 1).[18,22] Palladium nucleophilic attack occurs at the terminal Pd CO of
À
complexes bearing ligands 4–13 afforded the corre- species (e) to form the intermediate (f), which produ-
sponding amides with moderate chemoselectivities ces the amide and the initial Pd(0) species via a reduc-
under 3 bar of carbon monoxide at 1008C tive elimination step.[13]
(Scheme 1).[22] Hang et al. reported the most efficient
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Scheme 1. Pd-catalysed aminocarbonylation of aryl iodides using Pd/diphosphine ligands.[18,22]
Scheme 2. Proposed mechanisms for the Pd-catalysed aminocarbonylation of aryl halides.[12,13]
However, to the best of our knowledge there are bonylation of ethene and is the most active and selec-
no mechanistic studies reported on Pd systems bear- tive system reported to date.[23]
ing bidentate phosphine ligands for this transforma-
tion.
Here, we report the successful use of a palladium
catalytic system bearing the bidentate phosphine
ligand 15 (Figure 1) in the Pd-catalysed aminocarbo-
nylation of aryl iodides. This system was recently re-
ported by our group in the Pd-catalysed methoxycar-
Figure 1. cis-1,2-Bis[(di-tert-butylphosphino)methyl]cyclo-
hexane.
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Highly Selective Palladium-Catalysed Aminocarbonylation of Aryl Iodides
Table 1. Pd-catalysed aminocarbonylation of 1-iodo-4-methoxybenzene in the presence of n-butylamine: optimisation of re-
action conditions.[a]
Entry
Pd precursor
Solvent
Conversion [%][b]
Selectivity 2a/3a[b]
1[c]
2
3
4
5
Pd2dba3
Pd2dba3
Pd2dba3
Pd2dba3
CH2Cl2
CH2Cl2
THF
toluene
CH2Cl2
CH2Cl2
12
96
59
76
92
95
99/1
99/1
99/1
94/6
99/1
99/1
Pd
ACHTUNGTRENNUNG
6
[Pd
ACHTUNGTRENNUNG
[a]
[Pd] (0.01 mmol), ligand 15 (0.011 mmol), aryl iodide (0.5 mmol), pyridine (1 mmol), n-butylamine (1.2 mmol), solvent
(1 mL), CO (1 bar), 458C and 14 h.
Determined by H NMR and GC-MS.
[b]
[c]
1
Without base.
Results and Discussion
Using pyridine as base, excellent conversion and
chemoselectivity to 2a were obtained (entry 2,
The catalytic reaction conditions were optimised Table 1). The effect of the solvent was examined,
using 1-iodo-4-methoxybenzene as substrate and n- achieving the highest activity when dichloromethane
butylamine as nucleophile (Table 1).
was used. The chemoselectivity remained excellent in
The first reaction was performed under atmospher- all cases (entries 2–4, Table 1). A decrease in conver-
ic carbon monoxide pressure in refluxing dichlorome- sion was observed when THF and toluene were used
thane in the absence of base, achieving low conver- as solvents (entries 3 and 4, Table 1), which is in
sion but excellent chemoselectivity to the amide prod- agreement with previously reported results.[17]
uct 2a (entry 1, Table 1).
Table 2. Pd-catalysed aminocarbonylation of aryl iodides with n-butylamine.[a]
Entry
1
Aryl iodide
Product
Conversion [%][b]
96
Selectivity [%][b]
99
2
3
85
76
99
99
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Table 2. (Continued)
Entry
Aryl iodide
Product
Conversion [%][b]
Selectivity [%][b]
4
95
99
5
6
95
91
99
99
7
85
92
99
99
99
99
8
9
10
94
77
99
99
11
[a]
Pd2dba3 (0.005 mmol), ligand (0.011 mmol), aryl iodide (0.5 mmol), pyridine (1 mmol), n-butylamine (1.2 mmol), dichloro-
methane (1 mL), CO (1 bar), 458C and 14 h.
Determined by H NMR and GC-MS.
[b]
1
Other palladium precursors such as Pd
[Pd (m-Cl)]2 were tested and also gave excel- ing amide in 95% conversion (entry 4, Table 2). When
(h3-C3H5)
lent conversions and chemoselectivities (entries 2 vs. 5 iodobenzene 1e was used as substrate, excellent con-
and 6, Table 1). version and selectivity to the formation of the amide
ACHTUNGRTEN(NUGN OAc)2 or thoxy derivative afforded exclusively the correspond-
N
ACHTUNGTRENNUNG
Next, a range of aryl iodides was used as substrates 2e were achieved (entry 5, Table 2). When substrates
(Table 2). For all the substrates used, conversions be- 1f, 1h, 1i with alkyl groups at the para-position of aryl
tween 85–99% and total chemoselectivities were ach- group (entries 6, 8 and 9, Table 2) were used, the con-
ieved, showing that this catalytic system is suitable for versions were between 91 and 99% together with
the selective transformation of a wide range of aryl 99% chemoselectivity. For 3,5-dimethyl-1-iodoben-
iodide substrates. For ortho- and meta-iodoanisoles zene 1g, 85% conversion into the amide 2g was
(entries 2 and 3, Table 2), the conversions slightly de- achieved (entry 7, Table 2). When an electron-with-
À
creased when compared to that obtained with the drawing substituent such as CN was present at the
para isomer of this substrate. The position of the sub- para-position, the conversion and selectivity remained
stituent therefore only affects the conversion of the excellent (94% and 99%, respectively) (entry 10,
reaction. Interestingly, the reaction of the 2,4-dime- Table 2).
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Highly Selective Palladium-Catalysed Aminocarbonylation of Aryl Iodides
Table 3. Pd-catalysed aminocarbonylation of 1-iodo-4-methoxybenzene with different nucleophiles.[a]
Entry
1
Nucleophile
Product
Conversion [%][b]
89
Selectivity [%][b]
99
2
3
4
5
91
96
99
92
96
99
99
99
6
97
83
99
99
7
[a]
Pd2dba3 (0.005 mmol), ligand 15 (0.011 mmol), aryl iodide (0.5 mmol), pyridine (1 mmol), nucleophile (1.2 mmol), di-
chloromethane (1 mL), CO (1 bar), 458C and 14 h.
Determined by H NMR and GC-MS.
[b]
1
When 1-iodonaphthalene was used as substrate the for the palladium-catalysed aminocarbonylation of
conversion was 77% (entry 11, Table 2). Interestingly, a wide range of aryl iodides and nucleophiles under
these results show that the presence of substituents mild conditions. However, this system was found to
with distinct electronic and/or steric properties on the be inactive when aryl bromides and chlorides were
substrate does not affect the chemoselectivity of the used as substrates.
reaction.
To extend the scope of this process, various primary
and secondary amines were tested as nucleophiles NMR Study of the Pd-Catalysed Aminocarbonylation
(Table 3). Conversions of 83–96% and chemoselectivi- of 1-Iodo-4-methoxybenzene using the P,P Ligand 15
ties of 96–99% (entries 1–7, Table 3) were achieved.
The results obtained with primary (16–18) or secon- In order to gain information about the mechanism of
dary amines (19–22) were very similar in terms of the Pd/15-catalysed aminocarbonylation reaction of
chemoselectivity (entries 1–3 versus 4–7) although the aryl iodides, an NMR study was carried out
use of bulky amines leads to a decrease of the conver- (Figure 2).
sion (entry 7).
First, the palladium precursor [Pd2ACTHUNGTERNU(NG dba)3] was treat-
These results show that the palladium system bear- ed with ligand 15 in toluene at room temperature for
ing the bulky electron-rich bidentate phosphine 20 min and a 31P-{1H} NMR spectrum was recorded at
ligand 15 constitutes a very efficient catalytic system this temperature. A singlet at 22.5 ppm was detected
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Figure 2. 31P{1H} NMR spectra: a) of the Pd2dba3/15 under 1 bar of CO in toluene at À908C; b) of the Pd2dba3/15 under
1 bar of carbon monoxide plus addition of 1-iodo-4-methoxybenzene under nitrogen in toluene at À908C after being heated
for 1 h at 608C; c) the previous solution pressurised with 1 bar of CO at À908C; d) the previous solution pressurised with
1 bar of CO and heated at 608C for 15 minutes; e) addition of n-butylamine to the previous solution at room temperature
and spectrum acquired at À908C.
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Highly Selective Palladium-Catalysed Aminocarbonylation of Aryl Iodides
Scheme 3. Reaction carried out with Pd/15.
and readily assigned to the free diphosphine 15. the solution was then heated for 1 hour at 608C and
When the temperature was decreased to À908C, two again cooled to À908C. The 31P{1H} NMR spectra ac-
singlet signals were detected at 24.2 and 22.1 ppm, quired at this temperature showed the complete dis-
corresponding to both boat and chair conformers of appearance of the signals for 23, while two new sets
the free ligand. It was therefore concluded that under of two doublets at 54.8 and 15.0 ppm (2J=14 Hz) and
these conditions the coordination of 15 to Pd does at 50.9 and 12.8 ppm (2J=14 Hz) (ratio 3.5:1), were
not occur. This is in agreement with previous findings detected (Figure 2, b). These signals were attributed
by our group in the Pd-catalysed methoxycarbonyla- to the boat and chair conformers of the ligand in com-
tion reaction.[23]
However, when carbon monoxide was bubbled ly detected in Pd-ethyl complexes.[23]
through a toluene solution containing [Pd2A(dba)3] and These isomers could also be detected by H NMR
15 (Scheme 3, a), the colour of solution changed im- via the presence in the aromatic region of two set of
mediately from purple to dark green.
signals, at 8.18 and 6.46 ppm (3J=12.4 Hz) for the
plex 24 (Scheme 2, b). Related isomers were previous-
1
CTHUNGTRENNUNG
The 31P{1H} NMR spectrum of this solution at room major isomer and at 8.06 and 6.14 ppm (3J=12.4 Hz)
temperature showed two new broad signals at 68.0 for the minor species. Additionally, in the
and 51.2 ppm. In addition, resonances corresponding 13C{1H} NMR spectra recorded at À608C, the four sig-
to the oxidised ligand (64.3–62.8 ppm) were also de- nals arising from quaternary aromatic carbons corre-
tected. When the temperature was decreased to sponding to two isomers, were detected at 164.2,
À908C, the broad signals resolved into two doublets 162.4, 161.8 and 161.1 ppm. No signals corresponding
at 74.2 and 50.4 ppm (2JP, P =11 Hz) (Figure 2, a), that to CO containing species were detected.
were attributed to a palladium complex containing
Next, the solution was pressurised with 1 bar of
two conformationally inequivalent phosphorus atoms. carbon monoxide at room temperature and
The two signals corresponding to the free ligand were
a
31P{1H} NMR spectrum was recorded at À908C. Sig-
again detected. When a 13C{1H} NMR spectrum was nals corresponding to species 23 (at 74.2 and
recorded at À608C, a broad signal at 195.3 ppm was 50.4 ppm, 2J=11 Hz) and 24 at 54.8 and 15.0 ppm
observed. The resonance was assigned to the palladi- (2J=14 Hz) and 50.9 and 12.8 ppm (2J=14 Hz) (ratio
um carbonyl diphosphine complex (23) according to 3.5:1) were readily detected. Additionally, two new
previous reports in Pd-catalysed aminocarbonylation sets of signals appeared as doublets at 72.9 and
reaction (Scheme 3, a).[24] However, the coordination 42.8 ppm with a coupling constant of JP, P =26 Hz. Two
of a solvent molecule to the Pd centre of 23 cannot other broad singlets were detected at 63.9 and
be discarded.
40.3 ppm (Figure 2, c) and attributed to a palladium
This result indicated that in the presence of carbon complex containing two conformationally inequiva-
monoxide, the coordination of the bidentate ligand 15 lent phosphorus atoms. The two signals corresponding
to palladium rapidly yields the complex 23. In the ab- to the free ligand were also detected. When the solu-
sence of CO no palladium/phosphine species were de- tion was heated for 15 min at 608C, the signals corre-
tected, probably due to the slow reactivity of the Pd sponding to the complex 24 were not detected any-
complex under these conditions. Indeed, previous re- more (Figure 2, d). Broad signals corresponding to
sults from our group showed that Pd
reacts in the presence of 15 to form [PdAHCUTNGTRENNUNG
(dba)3 slowly the ligand oxide and to the free ligand 15 at 65 ppm
(dba)(15)].[23] and at 26 ppm were also present. In the 13C{1H} NMR
At this point, 20 equivalents of 1-iodo-4-methoxy- spectra, two broad signals at 218 and 197 ppm were
benzene with respect to palladium were added, and detected. These values are in agreement with the
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Scheme 4. Proposed mechanism for the Pd-catalysed carbonylation of aryl iodides with the catalytic system Pd/15.
chemical shift of an acyl and a terminal CO group, re-
Based on these results, a possible mechanism for
spectively (Scheme 2, c).[24] In this context the two the Pd-catalysed carbonylation of aryl iodides with
sets of signals present in the 31P{1H} NMR spectrum the catalytic system Pd/15 is proposed (Scheme 4).
were attributed to the two conformers of the penta- These results suggest that the species 23 is the resting
1
coordinated carbonyl-acyl species 25. The H NMR state of the cycle under these conditions and under-
spectrum showed two doublets at 7.91 and 6.13 ppm goes oxidative addition of the substrate to form the
with a coupling constant of 13 Hz indicating again the complex 24 at 608C. Then, carbon monoxide coordi-
À
presence of a unique acyl species.
nation and insertion into the Pd Ar bond affords the
Interestingly, when the solution containing 24 was acyl species 25, which yields the aminocarbonylated
pressurized with CO (1 bar), the species 23 was again product after the nucleophilic attack.
observed, thus suggesting that the oxidative addition
process is reversible. Indeed, the absence of nucleo-
phile in this experiment rules out the regeneration of Conclusions
23 through completion of the catalytic cycle. Howev-
er, the presence of traces of water that could act as The catalytic system Pd/15 is very efficient in the Pd-
nucleophile and form the hydroxycarbonylation prod- catalysed aminocarbonylation of aryl iodides and pro-
uct cannot be discarded.
vides high conversions and total selectivity to amides
Next, n-butylamine (20 equiv.) was added at room for a wide range of aryl iodides and amine nucleo-
temperature to the solution and the corresponding philes under mild conditions. This is the most active
31P{1H} NMR spectra exhibited broad signals previ- and selective system reported to date for a broad
ously attributed to 23. When the mixture was cooled range of substrates and nucleophiles.
down to À908C the two doublets at 74.2 and
In this study, the steric and electronic properties of
50.3 ppm, corresponding to 23, were again detected the aryl substrates were observed to not affect the se-
(Figure 2, e).
lectivity and only slightly impact on the conversion.
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Highly Selective Palladium-Catalysed Aminocarbonylation of Aryl Iodides
[2] A. Schoenberg, R. F. Heck, J. Org. Chem. 1974, 39,
The NMR study described here led to the identifi-
cation and characterisation of several intermediates
of the catalytic cycle.
1427.
[3] M. Hidai, M. Kokura, Y. Uchida, J. Organomet. Chem.
1973, 52, 412.
[4] M. Hidai, T. Hikita, Y. Wada, Y. Fujikura, Y. Uchida,
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Experimental Section
General Procedure for the Pd-Catalysed
Aminocarbonylation of Aryl Iodides
A tube was charged under an N2 atmosphere with the corre-
sponding aryl iodide (0.5 mmol), Pd2dba3 (0.005 mmol), the
bidentate ligand 15 (0.011 mmol), pyridine (1 mmol) and the
amine nucleophile (1.2 mmol) in dichloromethane (1 mL).
Then, the tube was purged and pressurised with 1 bar of
carbon monoxide. The reaction mixture was stirred at 458C
for 14 h. After the reaction, the mixture was filtered over
celite, and washed with water (3ꢄ5 mL). The organic phase
was dried over anhydrous MgSO4. The drying agent was fil-
tered off and the solvent was removed under reduced pres-
sure. The conversion and chemoselectivity were determined
by GC-MS chromatography.
[10] P. E. Garrou, R. F. Heck, J. Am. Chem. Soc. 1976, 98,
4115.
[11] W. R. Moser, A. W. Wang, N. K. Kildahl, J. Am. Chem.
Soc. 1988, 110, 2816.
[12] D. Milstein, J. Chem. Soc. Chem. Commun. 1986, 817.
[13] F. Ozawa, N. Kawasaki, H. Okamoto, T. Yamamoto, A.
Yamamoto, Organometallics 1987, 6, 1640.
[14] A. Takꢆcs, A. R. Abreu, A. F. Peixoto, M. Pereira, L.
Kollꢆr, Synth. Commun. 2009, 39, 1534.
[15] A. Takꢆcs, B. Jakab, A. Petz, L. Kollꢆr, Tetrahedron
Acknowledgements
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The authors are grateful to the Spanish Ministerio de Educa-
ciꢀn
y Ciencia (CTQ2010-14938/BQU, CTQ2008-01569-
[17] Z. Szarka, A. Kuik, R. Skoda-Fçldes, L. Kollꢆr, J. Or-
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[18] M.-Z. Cai, C.-S. Song, X. Huang, Synth. Commun.
BQU, Consolider Ingenio 2010, and Ramon y Cajal fellow-
ship to C. Godard) and the Generalitat de Catalunya (for fi-
nancial support 2009SGR116 and for awarding a research
grant to Verꢀnica de la Fuente (FI program-2008)
1997, 27, 361.
[19] R. J. Perry, B. D. Wilson, J. Org. Chem. 1996, 61, 7482.
[20] Y. Ben-David, M. Portnoy, D. Milstein, J. Am. Chem.
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[21] J. S. Kim, A. Sen, J. Mol. Catal. A 1999, 143, 197.
[22] C. F. J. Barnard, Org. Process Res. Dev. 2008, 12, 566.
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S. Castillꢀn, C. Claver, Chem. Eur. J. 2010, 16, 6919.
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10 Highly Selective Palladium-Catalysed Aminocarbonylation
of Aryl Iodides using a Bulky Diphosphine Ligand
Adv. Synth. Catal. 2012, 354, 1 – 10
Verꢀnica de la Fuente, Cyril Godard, Carmen Claver,*
Sergio Castillꢀn*
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