Synthesis of new thiol-derivatized aminophosphines and their catalytic activities in C-C coupling reactions

Article abstract of DOI:10.3906/kim-1505-91

A series of new aminophosphines [Ph₂ PHN-C₆H₄-R, where R = o-SH (4a), m-SH (4b) or p-SH (4c)] were readily synthesized from cheap starting materials by the phosphorylation reaction of o, m, and p-aminothiophenols with Ph2

Full text of DOI:10.3906/kim-1505-91

Turk J Chem
Turkish Journal of Chemistry
(2015) 39: 1257 – 1264
¨
http://journals.tubitak.gov.tr/chem/
˙
c
⃝ TUBITAK
doi:10.3906/kim-1505-91
Research Article
Synthesis of new thiol-derivatized aminophosphines and their catalytic activities
in C–C coupling reactions
∗
˙
Nermin BIRICIK , Nermin MERIC¸ , Cezmi KAYAN, Zeynep OZGEN,
˙
˙
˙
¨
˙
˘
¨
¨
Sevil S¸EKER AZIZOGLU, Bahattin GUMGUM
Department of Chemistry, Faculty of Science, Dicle University, Diyarbakır, Turkey
Received: 26.05.2015
•
Accepted/Published Online: 03.08.2015
•
Printed: 25.12.2015
Abstract:A series of new aminophosphines [Ph2 PHN-C6 H4 -R, where R = o-SH (4a), m-SH (4b) or p-SH (4c)] were
readily synthesized from cheap starting materials by the phosphorylation reaction of o, m, and p-aminothiophenols
with Ph2 PCl in the presence of triethyl amine. The new compounds were characterized by NMR and IR spectroscopy
and microanalysis. In addition, aminophosphine ligands–palladium systems were investigated as precatalysts in C–C
coupling reactions. Compounds 4b and 4c were proved to be excellent catalysts for Suzuki and Heck cross-coupling
reactions.
Key words: Aminophosphine, synthesis, catalysis, palladium, Suzuki–Heck
1. Introduction
The development of novel ligands remains the most attractive area in the field of transition metal-catalyzed
reactions. Accordingly, in the past few years many efforts have been devoted to developing new catalytic
systems.1−4 Aminophosphine ligands and their complexes play a key role in the development of valuable
compounds with these catalytic systems. Their catalytic applications are an area of growing interest and
they are virtually considered as all key types of ligands encountered in organometallic chemistry.5−9 Transition
metal catalyzed cross-coupling reactions leading to the formation of carbon–carbon and carbon–heteroatom
bonds are important in organic synthesis. Of these, the square-planar palladium complexes have received
considerable attention.10−14 The palladium-catalyzed reactions of aryl chlorides with both arylboronic acid
(Suzuki reaction) and alkenes (Heck reaction) are the most common methods for C–C bond formation and
hence have attracted much current interest.15−18 The square-planar palladium complexes of aminophosphine
ligands are an important class of compounds in this manner; they have trivalent phosphorus with a general
formula of R-NH–PPh2 or R-N(PPh2) and consequently they can be distinguished in terms of number of direct
phosphorus–nitrogen bonds (Figure 1).19
The aminophosphines and diphosphinoamines can be prepared from commercially available amines via
the classical phosphorylation reaction or aminolysis of chlorophosphines.20,21 The reaction usually takes place
in the presence of a base and the final aminophosphine or diphosphinoamine product can be easily separated
and isolated in high yields.
∗Correspondence: nbiricik@dicle.edu.tr
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Figure.
In the present study, a new type of amino phosphine ligand was synthesized and employed in Pd-catalyzed
Suzuki and Heck coupling reactions.22,23 In continuation of our studies on aminophosphines,24,25 we decided
to prepare a series of aminophosphines possessing SH substituents on an aryl ring and explore their chemistry
and catalytic functions in Suzuki and Heck cross-coupling reactions.
2. Results and discussion
Aminolysis of chlorophosphines or phosphorylation of an aromatic amine is an efficient method for preparing
aminophosphines with a general formula of R2 PN(H)R’ or (R2 P)2 NR’.19,20,26 The outcome of the phospho-
rylation reaction is influenced by the amine, the nature of the auxiliary base, and the solvent.19,27 As shown
in Scheme 1, we investigated the phosphorylation reactions of aniline derivatives possessing a thiol group with
Ph2 PCl in the presence of Et3 N (molar ratio 1:2:2 and 1:3:3) in THF affording new (phosphino)amine ligands
Ph2 PHN-C6 H4 -R [R = o-SH (4a), m-SH (4b), p-SH (4c)]. The formation of a P–S bond is also possible in
these reactions. However, under the present conditions, we did not observe the formation of products with a
P–S bond since we did not observe the characteristic P–S bond shift at 100–200 ppm in the 31 P NMR spectra.
The reaction of aminothiophenols with Ph2 PCl with a molar ratio of 1:3:3 gave mixtures containing P–N–P
and P–N–H while with a 1:1:1 ratio (Ph2 P–NHR) was found as the main product observed by 31 P NMR spec-
1
troscopy at 30–37 ppm. 31 P-{ H} NMR investigation of the reaction mixtures showed that all reactions were
completed after 1 h to give the anticipated products, aminophosphines 4a–c. No formation of iminobiphosphine
species (Ph2 P-PPh2 =NC6 H4 -R, where R = o-SH, m-SH, p-SH) was observed. However, the method cannot
be generalized for all anilines as earlier results showed that iminobiphosphines are formed as the major product
with some aniline derivatives.28 Additionally, the choice of solvent is also very important in determining the
outcome of the reaction. All compounds (4a–c) were isolated in good yields and fully characterized by elemental
1
1
analysis, and 1 H, 13 C-{ H} , 31 P-{ H} NMR, and IR spectroscopy consistent with earlier studies.29
Although compounds 4b and 4c are very stable in air and in organic solvents, compound 4a is somehow
unstable in ambient air and in solution. It is stable in air for only 2 days and then decomposes completely.
1
31 P-{ H} NMR spectra of compounds 4a–c showed one singlet with a chemical shift of around 30–37
1
ppm for each, a significantly high field from chlorodiphenylphosphine. In their 31 P-{ H} NMR spectra, the
chemical shifts of 4a–c were 34.59, 30.67, and 36.71 ppm, respectively, which are similar and within the expected
range of other reported structurally similar compounds.30−33 Broad signals at around 3.60–4.10 ppm in their
1 H NMR spectra are attributed to NH + SH protons. For compound 4b, no coupling is detected between the
SH and the NH protons. IR spectra of 4a–c contain absorptions at 744–738 cm−1 corresponding to the P–N–H
bonds, bands between 2338 and 2570 cm−1 that are characteristic of S–H bonds, and vibrations between 3313
and 3336 cm−1 , ascribed to N–H bonds. A comparison of IR spectra of 4a–c indicates the importance of the
position of the thiol group. The typical S–H band in the IR spectrum of 4a is around 200 cm−1 lower than that
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of 4b–c. The reason for the lower S–H band frequency for this compound may be associated with the possible
intramolecular hydrogen bond formation.
Scheme. The phosphorylation of a series of aminothiophenols with chlorodiphenylphosphine: i) THF, Et3 N, 0 ◦ C.
3. Catalysis
The palladium-catalyzed carbon–carbon bond forming reactions developed by Heck, Negishi, and Suzuki have
had a large impact on synthetic organic chemistry and found many applications in target-oriented synthesis.34,35
The cross-coupling of alkyl boronic acids with alkyl halides, known as the Suzuki reaction, is an efficient and
less toxic method to form a carbon–carbon bond.36−39 In a real catalytic process, the palladium complexes are
thought to be reduced to zero-valent palladium, which in many cases are nanosized particles that can directly
interact with the substrate.40,41 The catalytic activities of the complexes depend largely on the ability of the
ligands to activate and stabilize the zero-valent palladium nanoparticles. For this purpose, many palladium
complexes are prepared using bulky phosphine ligands. Although the compounds 4a–c are structurally very
similar, they showed different catalytic activities in C–C coupling reactions. Higher yields of stilbene were
obtained with 4b and 4c as compared with the other previously reported palladium-bis(phosphino)amine
complexes.42,43
3.1. Heck reaction
The Heck reaction is a powerful and efficient method for C–C bond formation in the presence of a palladium
catalyst to form a new alkene; it is strongly influenced by the choice of the solvent and base, as well as the
reaction temperature. Thus we studied the effect of the reaction temperature, solvent, and Cs2 CO3 , K2 CO3 ,
and K3 PO4 as a base in the reactions. Use of 0.01 mol of ligand (4a–c) and 2 equiv of K2 CO3 in DMF (1:1)
at 110 ◦ C led to the best conversion with a period of 48 h with 4a, 2 h with 4b, and 2.5 h with 4c. The
longer reaction times to achieve high yield for catalyst 4a may be attributed to the steric hindrance of ortho-
substitution. We initially evaluated the catalytic activity of ligands for the coupling of 4-bromoacetophenone
with styrene (Table 1, entries 1–3). Under the optimum reaction conditions, a wide range of aryl bromides
bearing electron-donating or electron-withdrawing groups were reacted with styrene, affording the coupled
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products in high yields by 4b and 4c (Table 1). As expected, the yields of the coupling product in reactions of
aryl bromides with electron-withdrawing substituents are higher than those with electron-releasing substituents.
Enhancements in activity, although less significant, are also observed when employing 4-bromobenzaldehyde
instead of 4-bromoacetophenone (Table 1, entries 4–6).
Table 1. Heck coupling reactions of aryl bromides with styrene[a]
.
Ligand (0.01 mmol)/
Pd(COD)Cl2 (0.005 mmol)
+ Br
R
K2CO3, DMF, 110 o
C
R
[d]
Entry
1
2
R
Ligand (L) Yield (%)[b] TOF (h−1
)
COCH3 4a
COCH3 4b
COCH3 4c
42 (91)[c]
96
95
40 (89)[c]
93
-
48
38
-
47
36
-
3
4
5
6
CHO
CHO
CHO
H
H
H
4a
4b
4c
4a
4b
4c
4a
4b
4c
4a
4b
4c
91
28 (75)[c]
7
8
9
81
78
41
31
-
29
22
-
[c]
10
11
12
13
14
15
OCH3
OCH3
OCH3
CH3
CH3
CH3
15 (60)
58
56
[c]
19 (66)
72
68
36
27
[a] Reaction conditions: 1.0 mmol of R-C6 H4 Br-p, 1.5 mmol of styrene, 2.0 mmol of K2 CO3 , 0.01 mmol of 4a–c
ligands, 0.005 mmol of Pd(COD)Cl2 , DMF (15 mL); [b] Purity of compounds was checked by 1 H NMR and yields are
based on aryl bromide, all reactions were monitored by GC, temperature 110 ◦ C, 24 h for 4a; 2 h for 4b; 2.5 for 4c;
[c] temperature 110 ◦ C, 48 h for 4a; [d] TOF = (mol product/mol Cat) × h−1
.
3.2. Suzuki coupling reaction
Compounds 4a–c were tested in a standard Suzuki reaction for the synthesis of biphenyl, and the results are
summarized in Table 2. From this table, it is evident that the ligands are an active catalyst for Suzuki cross-
coupling for a range of aryl halides with phenyl boronic acid in dioxane. The product yields are dependent on
the position of the thiol substituent in aminophosphine ligands. ortho-Isomer 4a does not show good catalytic
activity in the Suzuki reaction at 100 ◦ C in dioxane and 24 h, except at 100 ◦ C and 72 h in the presence of 0.01
mol% of ligand, 0.005 mmol Pd(COD)Cl2 , and 2.0 mmol Cs2 CO3 (Table 2, entries 1, 4, 7, 10, 13). The best
results were obtained at 72 h by 4a under the conditions described below (Table 2, entry 1, 4, 7, 10, 13). On
the other hand, compounds 4b and 4c were excellent catalysts for Suzuki cross-coupling reactions (Table 2).
4. Conclusion
A series of new phosphinoamines were prepared and obtained in good yields, which were then characterized by
NMR, IR, and microanalysis. These ligands form a new aminophosphine ligand–palladium system that could be
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applied as an efficient catalyst for Suzuki and Heck reactions. In these application reactions, in situ generated
catalytic species show different activities for C–C coupling reactions. Among the ligands, 4b and 4c have higher
activity compared with 4a in both Suzuki and Heck cross-coupling reactions. Very low catalyst loadings and
short reaction times are required for the quantitative coupling.
[a]
Table 2. Suzuki coupling reactions of aryl bromides with phenylboronic acid
.
Ligand (0.01 mmol)/
Pd(COD)Cl2 (0.005 mmol)
B(OH)2 + Br
R
R
Cs2CO3, Dioxane, 100 o
C
[d]
Entry
1
R
Ligand (L) Yield (%)[b] TOF (h−1
)
COCH3 4a
COCH3 4b
COCH3 4c
60 (91)c
-
2
96
48
48
-
3
96
58 (89)c
4
CHO
CHO
CHO
H
4a
4b
4c
4a
4b
4c
4a
4b
4c
4a
4b
4c
5
95
48
48
-
6
96
49 (80)c
7
8
H
82
41
45
-
9
H
89
29 (59)c
10
11
12
13
14
15
OCH3
OCH3
OCH3
CH3
CH3
CH3
65
33
34
-
67
38 (65)c
75
38
38
76
[a] Reaction conditions: 1.0 mmol of R-C6 H4 Br-p, 1.5 mmol of phenylboronic acid, 2.0 mmol of Cs2 CO3 0.01 mmol
of 4a–c ligands, 0.005 mmol of Pd(COD)Cl2 , dioxane (15 mL); [b] Purity of compounds was checked by 1 H NMR and
yields are based on aryl bromide, all reactions were monitored by GC, temperature 100 ◦ C, 24 h for 4a; 2.0 h for 4b
and 4c; [c] temperature 100 ◦ C, 72 h for 4a; [d] TOF = (mol product/mol Cat) × h−1
.
5. Experimental
5.1. Materials and methods
Unless otherwise stated, all reactions were carried out under an atmosphere of argon using conventional Schlenk
glassware, and solvents were dried using established procedures and distilled under argon immediately prior
to use. Analytical grade and deuterated solvents were purchased from Merck. PPh2 Cl and o,m, .eps
andp−aminothiophenol were purchased from Fluka and were used as received. The IR spectra were recorded on
a Mattson 1000 ATI UNICAM FT-IR spectrometer as KBr pellets. 1 H NMR (400.1 MHz), 13 C NMR (100.6
MHz), and 31 P NMR spectra (162.0 MHz) were recorded on a Bruker AV400 spectrometer, with δ referenced to
external TMS and 85% H3 PO4 . Elemental analysis was carried out on a Fisons EA 1108 CHNS-O instrument.
Melting points were recorded by a Gallenkamp Model apparatus with open capillaries.
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5.2. Synthesis and characterization of ligands
5.2.1. Synthesis of 4a
Chlorodiphenylphosphine (0.18 g, 0.79 mmol) was slowly added to a solution of 2-aminothiophenol (0.10 g, 0.79
mmol) and triethylamine (0.08 g, 0.79 mmol) in THF (25 mL) at 0 ◦ C with vigorous stirring. The mixture was
stirred at room temperature for 1 h, triethylammonium chloride was filtered off under argon, and the solvent was
removed under reduced pressure. The residue was then washed with cold diethylether (2 × 15 mL) and dried
in vacuo to produce a viscous oily compound 4a (yield: 0.21 g, 85.9%); 1 H NMR (CDCl3 , ppm): δ 7.28–7.65
(m, 11H, aromatic protons), 7.13 (t, J = 7.6 Hz, 1 H, aromatic protons), 6.76 (d, J = 8.0 Hz, 1H, aromatic
1
protons), 6.66 (t, J = 7.5 Hz, 1H, aromatic protons) 4.11 (br, 2H, NH + SH); 13 C{ H} NMR (CDCl3 , ppm):
δ 148.08 (C1-Ar), 138.03 (d, J = 25.2 Hz, i-carbons of NHPPh2), 136.14 (d, J = 5.0 Hz, C2-Ar), 132.78 (d,
J = 21.1 Hz, o-carbons of NHPPh2), 129.78 (C3-Ar), 129.38 (s, p-carbons of NHPPh2), 128.59 (d, J = 6.0
Hz, m-carbons of NHPPh2), 118.90 (C4-Ar), 116.67 (d, J = 13.1 Hz, C5-Ar), 115.41 (C6-Ar); assignment was
1
based on the 1 H–13 C HETCOR and 1 H–1 H COSY spectra; 31 P{ H} NMR (CDCl3 , ppm): δ 34.59 (s). IR
(KBr pellet in cm−1).epsυ 3313 (N–H), 3145, 3046 (aromatic C–H), 2338 (S–H), 1435 (P–Ph), 744 (P–NH);
C18 H16 NSP (mw: 309.37 g/mol): calcd. C, 69.88; H, 5.21; N, 4.53; found C, 69.10; H, 5.04; N, 4.12%.
5.2.2. Synthesis of 4b
Chlorodiphenylphosphine (0.17 g, 0.77 mmol) was slowly added to a solution of 3-aminothiophenol (0.10 g, 0.77
mmol) and triethylamine (0.08 g, 0.77 mmol) in THF (25 mL) at 0 ◦ C with vigorous stirring. The mixture was
stirred at room temperature for 1 h, triethylammonium chloride was filtered off under argon, and the solvent
was removed under reduced pressure. The residue was then washed with cold diethylether (2 × 15 mL) and
dried in vacuo to produce a viscous oily compound 4b (yield: 0.20 g, 84.7%); 1 H NMR (CDCl3 , ppm): δ
7.40–7.65 (m, 10H, aromatic protons), 7.07 (t, J = 7.8 Hz, 1H, aromatic protons), 6.91 (d, J = 7.8 Hz, 1H,
aromatic protons), 6.85 (d, J = 1.6 Hz, 1H, aromatic protons), 6.56 (m, 1H, aromatic protons), 3.66 (br, 2H,
1
NH + SH); 13 C{ H} NMR (CDCl3 , ppm): δ 146.92 (C1-Ar), 137.58 (d, J = 24.1 Hz, i-carbons of NHPPh2),
132.75 (d, J = 21.1 Hz, o-carbons of NHPPh2), 129.77 (C4-Ar), 129.31 (s, p-carbons of NHPPh2 + C2-Ar),
128.60 (d, J = 7.0 Hz, m-carbons of NHPPh2), 121.70 (d, J = 8.0 Hz, C3-Ar), 117.82 (d, J = 10.1 Hz, C6-Ar),
1
113. 89 (C5-Ar); assignment was based on the 1 H–13 C HETCOR and 1 H–1 H COSY spectra; 31 P{ H} NMR
(CDCl3 , ppm): δ 30.67 (s). IR (KBr pellet in cm−1).epsυ 3336 (N–H), 3057 (aromatic C–H), 2570 (S–H),
1435 (P–Ph), 744 (P–NH); C18 H16 NSP (mw: 309.37 g/mol): calcd. C, 69.88; H, 5.21; N, 4.53; found C, 69.15;
H, 5.09; N, 4.21%.
5.2.3. Synthesis of 4c
Chlorodiphenylphosphine (0.17 g, 0.78 mmol) was slowly added to a solution of 4-aminothiophenol (0.10 g, 0.78
mmol) and triethylamine (0.08 g, 0.78 mmol) in THF (25 mL) at 0 ◦ C with vigorous stirring. The mixture was
stirred at room temperature for 1 h, triethylammonium chloride was filtered off under argon, and the solvent
was removed under reduced pressure. The residue was then washed with cold diethylether (2 × 15 mL) and
dried in vacuo to produce an off-white solid compound 4c (mp 67–68 ◦ C; yield: 0.21 g, 88.1%); 1 H NMR
(CDCl3 , ppm): δ 7.02–7.91 (m, 12H, aromatic protons), 6.50 (d, J = 8.4 Hz, 2H, aromatic protons), 3.69
1
(br, 2H, NH + SH); 13 C{ H} NMR (CDCl3 , ppm): δ 146.38 (C1-Ar), 138.15 (d, J = 26.2 Hz, i-carbons
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of NHPPh2), 134.78 (C4-Ar), 134.73 (C2-Ar), 132.77 (d, J = 21.1 Hz, o-carbons of NHPPh2), 129.16 (s, p-
carbons of NHPPh2), 128.50 (d, J = 6.0 Hz, m-carbons of NHPPh2), 115.68 (C3-Ar); assignment was based on
1
the 1 H–13 C HETCOR and 1 H–1 H COSY spectra; 31 P{ H} NMR (CDCl3 , ppm): δ 36.71 (s). IR (KBr pellet
in cm−1).epsυ 3278 (N–H) 3147, 3016 (aromatic C–H), 2532 (S–H), 1431 (P–Ph), 738 (P–NH); C18 H16 NSP
(mw: 309.37 g/mol): calcd. C, 69.88; H, 5.21; N, 4.53; found C, 69.21; H, 5.00; N, 4.09%
6. General procedure for Heck coupling reaction
The aminophosphine ligands (4a–4c, 0.01 mmol), Pd(COD)Cl2 (0.005 mmol), aryl bromide (1.0 mmol), styrene
(1.5 mmol), base (2 mmol), and solvent (15 mL) were added to a Schlenk tube under argon atmosphere and the
reaction was monitored at various conditions and parameters (temperature, time, base, etc.). After completion
of the reaction, the mixture was cooled, extracted with ethyl acetate–hexane (1:5), filtered through a pad of
silica gel with copious washing, concentrated, and purified using flash chromatography on silica gel. The purity
of the compounds was checked immediately using GC and 1 H NMR. Yields are based on aryl halides.
7. General procedure for Suzuki cross-coupling reaction
The aminophosphine ligands (4a–4c, 0.01 mmol), Pd(COD)Cl2 (0.005 mmol), aryl bromide (1.0 mmol),
phenylboronic acid (1.5 mmol), base (2 mmol), and solvent (15 mL) were added to a Schlenk tube under
argon atmosphere and the reaction was followed at various conditions and parameters (temperature, time, base,
etc.). After completion of the reaction, the mixture was cooled, extracted with ethyl acetate–hexane (1:5),
filtered through a pad of silica gel with copious washing, concentrated, and purified using flash chromatography
on silica gel. The purity of the compounds was checked immediately using GC and 1 H NMR. Yields are based
on aryl halides.
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