Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation-acetalization of olefins

Article abstract of DOI:10.1039/c5cy01827g

A series of ionic phosphonium-based aminophosphines L1-L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1-L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3-Rh(acac)(CO)₂ system also exhibited good generality to hydroformylation-acetalization of a wide range of olefins in different alcohols.

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ARTICLE TYPE
Phosphonium-based aminophosphines as bifunctional ligands for
sequential catalysis of one-pot hydroformylation-acetalization of olefins
Peng Wang, Huan Liu, Yong-Qi Li, Xiao-Li Zhao, Yong Lu, Ye Liu*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
A series of ionic phosphonium-based aminophosphines of L1-L3 were prepared and fully characterized,
in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic
phosphonium were linked together by the stable chemical bonds and bridged by a simple N-atom. The
molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well
10 retained without incompatibility problem. The investigations on co-catalysis over L1-L3 showed that L3
exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine
fragment in L3 was responsible for hydroformylation with Rh-complex together and the phosphonium
acted as the Lewis acidic catalysts in charge of acetalization. L3-Rh(acac)(CO)2 system was also exhibited
good generality to hydroformylation-acetalization of a wide range of olefins in the different alcohols.
45 form reaction sequences to get the desired products based on
15 Introduction
the principles of atom economy and low energy consumption in
green chemistry [10-16]. For example, the one pot
hydroformylation-acetalization reaction is used to produce
acetals directly from olefins, which can be used as protecting
50 groups for carbonyl groups in organic synthesis as well as the
organic solvents, additives in fuels, and intermediates applied to
pharmaceutical, perfume and agricultural industries [13,16,17].
Traditionally, the preceding hydroformylation of olefins is usually
catalyzed by Rh-complexes in the presence of phosphine [P(III)]
55 ligands [9,18,19], while the sequential acetalization of aldehydes
is conducted in the presence of Lewis or Brønsted acid catalysts
[20-24]. Therefore, the development of bifunctional ligands in
combination of phosphines and phosphoniums together for
hydroformylation-acetalization of olefins is highly attractive if
60 the elegant strategy is applied to alleviate incompatibility
problem for the quenching of the activity of the Lewis acidic
phosphoniums by the Lewis bases of phosphines [5].
Co-catalysis as defined in the ways of synergetic catalysis,
cooperative catalysis, and sequential catalysis by combination of
transition metal catalysis with organocatalysis [1] has recently
emerged as a powerful strategy to promote new reactions and
20 improves the reactivity that cannot be achieved by transition
metal catalysis or organocatalysis individually. Various
organocatalysts such as Lewis/Brønsted acid catalysts,
amine/enamine catalysts, phase transfer catalysts and N-
heterocyclic carbene catalysts have been exploited in physical
25 combination with transition metal catalysts [2, 3]. Among
several organocatalysts, phosphonium cations [P(V)+] have been
proved to be a typical kind of Lewis acids [6] which not only can
catalyze isomerization of olefins, cationic polymerization, and
hydrosilation of olefins/acetylene without involvement of any
30 metal [4], but also exhibit activities towards C=O bond activation
such as in cyanosilylation of ketones, Baylis-Hillman reaction,
and Aldol and Micheal reactions of carbonyl compounds [5]
probably due to the bond-like interaction of Lewis acidic P(V)+
centres with sp2 hybrid O-atoms (in carbonyl compounds) for the
35 reaction promotion. In practice, the bifunctional ligands in
compatible combination of phosphines and organocatalysts by
intramolecular stable chemical bonds have unique advantages
because of the inherent coordination ability of phosphines to
transition metals (which corresponds to metal catalysis) and the
40 synergetic effect coming from the surrounding organocatalysts
[6-8].
Attracted by the concept of co-catalysis in the sequential way
in combination of phosphine-ligated Rh-complex (transition
65 metal catalysis) and Lewis acidic phosphoniums (organocatalysis)
by using the bifunctional ligands for one-pot hydroformylation-
acetalization of olefins, the phosphinoamino-phosphonium salts
of L1~L3 was prepared, in which the phosphine fragments and
phosphoniums were linked by the stable chemical bonds and
70 bridged by the same N-atoms without incompatibility problem.
Undoubtedly, the properties of the N-atom-bridged phosphine
fragments and phosphoniums are to be different to the ones
bridged by C-atom (such as in L5) due to the high electronegative
nature of N-atom.
Hydroformylation of olefins is an industrially important method
for production of the carbonyl compounds of aldehydes [9],
which can been widely involved in other organic reactions to
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ARTICLE TYPE
Ph
PPh2
Ph
PPh2
PPh2
H2C
PPh2
N
P+
N
P+
N
P+
I-
OTf-
Ph
PPh2
OTf-
Ph
P+
OTf-
O
Me
N
Me
Me
Ph
Ph
Me
Ph
Ph
PPh2
L4
Ph
Ph
L1
L2
L5
L3
Me
Me
O
O
PPh2
OTf-
Ph
Rh
N
Rh(acac)(CO)2
P+
O
Me
PPh2 CO
Me
N
P+
Ph
OTf-
Ph
O
Me
Me
L2
Ph
Rh-L2
OR'
OR'
R'O
OR'
R''
CHO
R''
Rh-complex/L, CO/H2
CHO
+
+
iso-octenes
R
+
R
R
R'OH
R
R
acetal
aldehyde
Scheme 1 The bifunctional ligands of L1-L3 containing phosphine fragment and phosphonium, and the corresponding Rh-complex of Rh-L2 for one-pot
hydroformylation-acetalization
L1-L3 can be retained independently without quenching problem.
The similar phenomenon of negligible interaction between -
Results and discussion
P+Ph2Me and -PPh2 moieties in other kinds of phosphine-
Synthesis and Characterization
5
35 functionalized phosphonium salts has also been observed in the
Firstly the aminobisphosphines as the precursors of L1-L3 were
prepared according to the reported methods [25-29], which then
reacted with MeI or MeOTf to afford the ionic L2-L3 by external
quaternarization and L1 by internal quaternarization (Scheme 1).
literature [30]. The low field resonances observed for the
phosphine fragments in L1-L3 also indicate that they are
featured with typical π-acceptor character due to the electron-
withdrawing effect of the adjacent N-atom.
10 L4 as a kind of aminobisphosphines was selected as the
comparison counterpart to L3. L5 was prepared in parallel
through quaternization of dppm by MeOTf selectively.
23.3
ꢀ27.4
2JPꢀP+= 66 Hz
The analysis of 31P NMR spectra in Fig. 1 shows that, as for L1-
L3 with N-atom bridged P(III)- and P(V)+- atoms, , the two duplet
15 resonances due to the P-P+ coupling are observed at the very
low field, in which the signals at the relatively lower field are
ascribed to -P+Ph2Me and the ones at the higher field to -PPh2. In
contrast, the 31P NMR analysis of L5 show two duplet resonances
at 23.3 and -27.2 ppm which are attributed to -P+Ph2Me and -
20 PPh2 respectively. In L1-L3, the intensive electron-withdrawing
inductive effect of N-atom (in comparison to C-atom in L5)
renders the neighbored phosphine fragment electron-deficient,
corresponding to the duplet resonances appeared at the very
low field. The low field resonance of 62.7 ppm (singlet) ascribed
25 to the two isotropic phosphine fragments in L4 further indicates
that the low field resonances for -PPh2 fragments in L1-L3 (L1,
44.4 for -PPh2; L2, 55.8 for -PPh2; L3, 53.6 for -PPh2) are
dominantly attributed to the electron-withdrawing effect of N-
atom with high electronegativity rather than that of the proximal
30 positive-charged phosphoniums. It is then believed that the
individual functions coming from -P+Ph2Me and -PPh2 moieties in
L5
62.7
L4
53.6
58.8
2JPꢀP+ = 110 Hz
L3
55.8
58.5
2JPꢀP+ = 110 Hz
2JPꢀP+ = 75 Hz
L2
64.2
44.4
L1
1JPꢀRh= 242 Hz
2JPꢀP+= 34 Hz
56.1
93.3
Rh-L2
100 90 80 70 60 50 40 30 20 10
Chemical shift (ppm)
0
-10 -20 -30
40
Fig. 1 31P NMR spectra of L1-L5 and Rh-L2 (RT, 202 MHz)
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Indeed, the coordinating behavior of the phosphine fragments
in L1-L3 is still as normal as the typical phosphines. The
complexation of L2 with Rh(acac)(CO)2 can afford the ionic
complex of Rh-L2 with yield of 78%. The molecular structure of
Rh-L2 depicted in Fig. 2 shows that the Rh(I)-complex cation
counteracted by OTf- anion is possessing the structural similarity
to our previously reported cationic Rh(I)-complexes [31] and
RhI(acac)(CO)(PPh3) [32], which is in a typical square-planar
geometry with the bond angles of P1-Rh1-O3 of 176.9(8) and
5
10 C34-Rh1-O2 of 177.0(15). The Rh(I)-center (d8) is coordinated by
one phosphine, one CO, and one chelated 2,4-pentanedionato
ligand. The bond distance of Rh-P (2.2161(10) Å) is shorter than
that in RhI(acac)(CO)(PPh3) (Rh-P, 2.242 Å) [31], indicating the
consolidated interaction in Rh-P linkage due to the π-
15 backdonation of L2 with typical π-acceptor character [32,33].
This is consistent with the observed CO vibrational frequency of
Rh-L2 (1996 cm-1), which is obviously higher than that of
RhI(acac)(CO)(PPh3) (1980 cm-1) [31]. It is also found that in Rh-
L2 the sum of the bond angles of C27-N1-P1 117.9(2), P1-N1-P2
20 121.9(2) and P2-N1-C27 118.1(2) is 358 o, which indicates that
50 Fig. 2 The single crystal structure of Rh-L2 (all H-atoms have been
omitted for clarity). Selected bond distances (Å): Rh1–P1 2.2161(10),
Rh1–C34 1.810(4), C34-O1 1.149(5), N1-P1 1.746(3), N1-P2 1.671(3),
P2
Rh1-O2 177.0(15), C27-N1-P1 117.9(2), P1-N1-P2 121.8(2), P2-N1-C27
…
O4 3.4535(38); Selected bond angles (o) P1-Rh1-O3 176.9(8), C34-
the four atoms of N1-P1-P2-C27 is located on the same plane 55 118.1(2).
with sp2 hybridizated N-atom. The co-planar structure for P(V)+-
N-P(III) skeleton in which the bond distance of N1-P2 [P2 = P(V)+]
[1.671(3) Å] is much shorter than that of N1-P1 [P1 = P(III),
Co-catalysis of L1-L3 for one-pot hydroformylation-
acetalization
25 1.746(3) Å)] has been observed before [34]. The structural
information of Rh-L2 indicates that the bi-functionalities of the
phosphine fragment and the Lewis acidic phosphonium in L2 are
well retained without incompatibility problem. However, the
acidity of phosphonium in L2 is able to be quenched by the
30 accessible electron-rich ether group when they are located in
the sterically convenient positions. It is noted that the gauche
conformation of the C26–C27 bond is observed in Rh-L2, and the
O-atom is projecting inward towards the P(V)+-atom (P2). The
P2–O4 distance (3.45 Å) is significantly shorter than the sum of
35 the Allinger radii of P and O (P, 2.22 Å; O, 1.82 Å) [34], indicating
the chemical bonding interaction in P…O linkage due to the
available Lewis acid-base pair interaction between the P(V)+-site
and the O-atom in the ether moiety.
The 31P NMR spectral analysis of Rh-L2 further supports its
40 structure in solid state shown in Fig. 2. The 31P NMR signals of
the involved phosphine fragment shift to the very low field (dd,
93.3 ppm) along with the intensive P-Rh coupling constant of 1JP-
Rh = 242 Hz after L2 is coordinated to the Rh-centre. On the other
hand, nearly the same resonances (d, 56.1 ppm) with the
45 relatively weak P-P+ coupling constant (2JP-P+ = 34 Hz) is observed
for -P+Ph2Me moiety, indicating that the coupling between -PPh2
and -P+Ph2Me still exists but in the much weakened mode due to
the simultaneous interaction of -PPh2 with Rh-centre.
The one-pot hydroformylation–acetalization of 1-octene in
60 methanol was firstly investigated as a model reaction. In Table 1,
Conv. (conversion of 1-octene) and Soxo (selectivity to the total
oxo products including nonanals and dimethoxynonanes
(acetals) were defined to evaluate the hydroformylation
efficiency over the Rh-P catalytic site, while Pacetals (percentage of
65 acetals in the total oxo-products) was defined to evaluate the
acetalization efficiency over the Lewis acidic phosphonium(V)
site in L.
Over Rh(acac)(CO)2-L1 system, the reaction conditions in
terms of temperature, syngas pressure, and P/Rh molar ratio
70 were firstly optimized in hydroformylation–acetalization of 1-
octene (Entries 1-7 in Table 1). It was found that under the
optimal reactions (syngas pressures of 4.0 MPa, 100 oC, P/Rh = 6),
the efficient hydroformylation was obtained over L1 with 99%
conversion of 1-octene and 97 % selectivity to the oxo-products.
75 But in the oxo-products, the final acetals was only 54 % (Entry 1).
Anyway, without the presence of any ligand, Rh(acac)(CO)2 itself
just exhibited the moderate activity toward the
hydroformylation (Entry 8, Conv. = 89 %; Sel. oxo = 66 %), and the
low efficiency to the acetalization as well (Pacetals = 13 %).
80 Comparatively, the involvement of L2 and L3 under the same
conditions all resulted in the excellent hydroformylation with
99% conversions of 1-octene and 97~99 % selectivities to the
oxo-products (Entries 9 and 10), in which the best Pacetals of 87 %
was obtained exclusively over L3 (Entry 10). The absence of
85 MeOH led to no formation of acetal products with negligible
effect on the preceding hydroformylation (Entry 11), suggesting
that the subsequent acetalization be not the driving force for the
preceding hydroformylation and the two reactions proceeded
independently over the two functional sites of L3 without
90 mutual interference. It was also found that when Rh-L2 was
used to replace Rh(acac)(CO)2 as the pre-catalyst, nearly the
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same catalytic performance was obtained in terms of the
phosphonium are segregated by C-atom instead of N-atom, it
efficiencies for hydroformylation and acetalization (Entry 15 vs 30 corresponded to the similar activity to the subsequent
9), indicating that the in situ formed Rh-L2 through complexation
of Rh(acac)(CO)2 with L2 exhibited the same activity as the as-
synthesized one. And the structural information of Rh-L2 (Fig. 2)
also rationally accounted for the lowered acetalization over L2 in
acetalization but the greatly depressed efficiency toward
hydroformylation in comparison to L3 (Entry 13 vs 1). The 31P
NMR analysis (Fig. 1) has shown that L5 is an electron-rich ligand
5
with the typical σ-donor character (δ-PPh = -27.4 ppm), whereas
2
comparison to that over L3 (Entries 9 and 15 vs 10). In L2, the 35 L3 is a strong electron-deficient π-acceptor ligand with indication
acid-base pair interaction between the electron-rich O-atom of
of the low field resonances due to the electron-withdrawing
methoxyethyl group and the electron-deficient phosphonium
effect of the adjacent N-atom δ-PPh 53.6 ppm). The
(
=
2
10 unavoidably occurred, with the indications of the O4-atom
projecting inward towards the P(V)+-atom and the much shorter
involvement of the π-acceptor ligands has been widely believed
to give rise to Rh-catalyzed hydroformylation [35-40]. Hence, the
P2–O4 distance (3.45 Å within the sum of the Allinger radii of P 40 hydroformylation of 1-octene over L3 proceeded more
and O, Fig. 2), which badly quenched the Lewis acidity of the
phosphonium and then resulted in the suppressed acetalization
15 of nonanals.
efficiently than that over L5 without discrimination to the
subsequent acetalization, because of the independent nature of
Lewis acidic phosphoniums in L3 and L5. These results indicated
that L1-L3 as a type of bifunctional ligands exhibited typical
As for L1, in comparison to L3 linked by
a rotatable
phenylethyl group at N-position with more accessibility to 45 sequential catalysis towards hydroformylation-acetalization, in
phosphonium site (Entry 10, Pacetals = 87 %), the five-member ring
fused N-P bond made the phosphonium site in L1 sterically
20 inaccessible, resulting in the relatively sluggish reaction rate for
acetalization (Entry 1, Pacetals = 54 %). The addition of L4 as a kind
which the phosphine was in charge of hydroformylation with Rh-
complex together and the phosphoniums acted as the Lewis
acidic catalysts responsible for acetalization independently. And
the strong π-acceptor character of these ligands further led to
of aminobis(phosphine) not only completely inhibited the 50 the more efficient hydroformlyation than that over L4, L5 and
acetalization of nonanals because of the lack of the acidic site,
but also went against hydroformylation due to the tight
25 chelation of L4 to Rh-center as a diphosphine ligand (not
facilitating the ligand dissociation to provide the unsaturation
site for the substrate insertion) (Entry 12).
PPh3 (Entries 1, 9, 10 vs 12-14).
55
As for L5 in which the phosphine fragment and the
Table 1 One-pot hydroformylation-acetalization of 1-oetene in methanol over Rh(acac)(CO)2 with the involvement of L1-L5 under different
conditionsa
CHO
CHO
CHO
CO/H2, MeOH
CHO
+
+
+
Rh(acac(CO)2 / Ligand
aldehydes
Acetalization
Side reaction
(Isomerization)
iso-octenes
H3CO
OCH3
+
H3CO
OCH3
H3CO
OCH3
OCH3
+
+
OCH3
acetals
e
Entry Ligand
P/Rh
Pressure
Temp.
(oC)
100
80
Conv.
(%)b
99
73
57
80
52
81
78
89
99
99
98
99
90
99
99
Soxo
Pacetal
(%)b,c
54
94
83
95
72
96
89
13
58
87
--
Siso-octenes
(%)b,c
3
L/Bd
TONoxo
(molar ratio) (MPa)
(%)b,c
97
51
28
63
73
81
69
66
97
98
96
52
78
90
96
1
L1
6
6
6
6
6
3
1
--
6
6
6
6
6
6
6
4.0
4.0
4.0
2.0
1.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
1.3
1.2
2.0
2.3
1.7
1.2
1.6
1.9
2.0
2.1
1.6
2.8
1.3
2.4
1.3
960
370
160
500
380
660
540
590
960
970
940
510
700
890
950
2
L1
48
72
35
14
18
21
34
2
2
4
48
22
10
4
3
L1
60
4
L1
100
100
100
100
100
100
100
100
100
100
100
100
5
L1
6
L1
7
L1
8
--
9
L2
10
11f
12
13
14
L3
L3
L4
L5
PPh3
Rh-L2
6
88
<2
60
15g
Rh(acac)(CO)2 0.005 mmol, 1-octene 5 mmol (S/C = 1000), CO/H2 =1/1 (v), MeOH 3 mL, reaction time 3 h; b Determined by GC; Soxo
60 (aldehydes + acetals)/(aldehydes + acetals + iso-octenes). Pacetals = acetals/(aldehydes + acetals), percentage of acetals in the total oxo-
products; Siso-octenes = iso-octenes/(aldehydes + acetals + iso-octenes); L/B = (linear aldehyde + linear acetal)/(branched aldehydes +
=
a
c
d
e
branched acetals); L/B, the ratio of linear nonanals and acetals to branched nonanals and acetals; TON, turnover number = mol of
oxo-products L2 (0.005 mmol) was used as precatalyst instead of Rh(acac)(CO)2 with the presence of
(mol of Rh)-l; f No MeOH added; g Rh
L2 (0.025 mmol).
⋅
-
4
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The good generality of Rh(acac)(CO)2-L3 for one-pot 15 However, the used alcohols had the obvious influence
hydroformylation–acetalization of olefins and alcohols was
observed in Table 2. For 2-octene, the selectivity to oxo-products
and the acetalization efficiency decreased slightly due to the
bulky steric hindrance in comparison to terminal 1-octene (Entry
specifically on the reaction rate of acetalization. Glycol and 1,2-
propylene glycol indeed gave more rise to acetalization than
MeOH due to the formation of thermodynamically stable five-
5
member 1,3-dioxolanyl ring (Entry 2 vs 9 and 10). The
2 vs 1). The other olefins such as styrene, derivatives of styrene, 20 acetalizations of nonanals with EtOH and i-PrOH were greatly
and cyclooctene all corresponded to the excellent
transformations in terms of hydroformylation as well as
acetalization without discrimination to the steric and electronic-
suppressed due to bulky steric hindrance but with negligible
influence on the preceding hydroformylation. Reasonably, not
like the bulky chelating diphosphorus ligands with the wide bite
angles (such as BISBI, Xantphos etc.) [41], L3 as a typical
10 effect for the applied olefins (Entries 3-6). It was noted when
styrene and its derivatives were used as the substrates, the 25 monophosphine had no ability to control the regioselectivity for
regioselectivities to the branched oxo-products were more
favoured due to the formation of a stable benzylic Rh-species
induced by the η2-electron donation from the benzene ring.
the preferential formation of n-aldehydes. As a result, the low
L/B ratio was universally observed herein.
Table 2 Generality of Rh(acac)(CO)2-L3 for one-pot hydroformylation–acetalization of different olefins in alcohols a
e
Entry Olefin
Alcohol
MeOH
MeOH
Linear acetal
Conv. (%)b Soxo (%)b,c
Pacetal (%)b,c Siso-olefins (%)b,c
L/Bd
2.1
TONoxo
OMe
OMe
1
2
1-Octene
99
98
98
91
87
81
2
9
970
MeO
OMe
2-Octene
Styrene
2.0
890
OMe
OMe
3
4
MeOH
MeOH
99
99
99
99
96
97
--
--
0.4
0.1
980
980
OMe
4-Florostyrene
OMe
F
OMe
5
4-Chlorostyrene MeOH
OMe
99
99
98
99
98
92
--
--
0.1
--
970
980
Cl
OMe
OMe
6f
Cyclooctene
MeOH
OEt
7
8
9
1-Octene
1-Octene
1-Octene
EtOH
99
99
99
99
98
92
65
40
95
1
2
6
1.5
0.9
2.0
980
970
910
OEt
O-i-Pr
i-PrOH
Glycol
O-i-Pr
O
O
O
O
1,2-propylene
glycol
Me
10
1-Octene
99
96
98
4
0.4
950
a
o
Rh(acac)(CO)2 0.005 mmol, olefin 5 mmol (S/C = 1000), L3 c0.03 mmol (P/Rh = 6), CO/H2 (1:1) 4.0 MPa, temperature 100 C, alcohol 3 mL,
b
30 reaction time 3 h; Determined by GC and GC-Mass. Soxo = (aldehydes + acetals)/(aldehydes + acetals + iso-octenes). Pacetals
=
d
acetals/(aldehydes + acetals),. Siso-octenes = iso-octenes/(aldehydes + acetals + iso-octenes); L/B = (linear aldehyde + linear acetal)/(branched
e
f
aldehydes + branched acetals); TON, turnover number = mol of oxo-products
(dimethoxymethyl)cyclooctane were formed without discrimination for the linear and the branched.
⋅
(mol of Rh)-l; The products of cyclooctanecarbaldehyde and
Reagent Co. Ltd. and Shanghai Aladdin Chemical Reagent Co.
Experimental
Ltd., and used as received. FT-IR spectra were recorded on a
35 Reagents and analysis
1
Nicolet NEXUS 670 spectrometer. The H and 31P NMR spectra
The chemical reagents were purchased from Adamas-beta
40 for the analyses of the common compounds were recorded on a
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[Catalysis Science & Technology], [year], [vol], 00–00 | 5

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DOI: 10.1039/C5CY01827G
Bruker Avance 500 spectrometer at ambient temperature. The
50
31P NMR spectra were referenced to 85% H3PO4 sealed in a
capillary tube as an internal standard. TG/DTG analysis was
performed using a Mettler TGA/SDTA 851e instrument and
STARe thermal analysis data processing system. Gas
N-(diphenylphosphino)-N-(methyldiphenylphosphonium)-2-
methoxyethanamine trifluoromethanesulfonate (L2) To
solution of 2-methoxyethanamine (150.2 mg, 2.0 mmol, 1.0
equiv) in dichloromethane (20 mL), suspension of
a
5
a
chromatography (GC) was performed on a SHIMADZU-2014 55 triethylamine (808.8 mg, 8.0 mmol, 4.0 equiv) in
equipped with a DM-1 capillary column (30 m × 0.25 mm × 0.25
ꢀm). GC-mass spectrometry (GC-MS) was recorded on an Agilent
6890 instrument equipped with an Agilent 5973 mass selective
dichloromethane (5 mL) was added dropwise under N2
atmosphere. The reaction was stirred at room temperature for
40
methoxyethanamine as a white solid in the yield of 85 %. To a
Elementar Vario EL III instrument. The UV-vis. spectra were 60 solution of N,N-bis(diphenylphosphino)-2-methoxyethanamine
h
to
afford
N,N-bis(diphenylphosphino)-2-
10 detector. Elemental analyses for CHN were obtained using an
recorded on
a
SHIMADZU-UV 2550 spectrophotometer
(443.4 mg, 1.0 mmol, 1.0 equiv) in diethyl ether (50 mL) was
added dropwise a solution of MeOTf (1.0 mmol, 164.1 mg, 1.0
equiv) in diethyl ether (5 mL) at -25 °C in 10 min under N2
atmosphere. The reaction mixture was stirred at -25 °C for
65 another 1 h and then warmed up naturally to room temperature
in 12 h. The obtained fitrate was dried vacuo to give L2 as a
(resolution ca. 1 nm).
15 Synthesis of the ligands of L1-L5
L1-L4 were synthesized according to the procedures reported
1
before [25-29] with some modifications.
white solid in the yield of 90 %. H NMR (δ, ppm, CDCl3): 7.89-
2
7.84 (4HPh, m), 7.70 (2HPh, t, JHH = 8Hz), 7.62-7.57 (4HPh, m),
PPh2
N
I-
Ph2PCl, NEt3
KI
7.46-7.42 (10HPh, m), 3.73-3.65 (2H, m, CH3OCH2CH2N), 3.15 (3H,
NH2.HBr
P
Br
R
Ph
MeCN, RT
DCM, 0 °C to RT
2
70 d, CH3P+, JP-H = 12 Hz), 2.97 (3H, s, CH3OCH2CH2N), 2.89 (2H, t,
Ph
L1
2
CH3OCH2CH2N, JH-H = 4 Hz). 31P NMR (δ, ppm, CDCl3): 58.5 (d,
2
2
P+Ph2Me, JP-P+ = 110 Hz), 55.8 (d, PPh2, JP-P+ = 110 Hz). CHN-
elemental analysis found for L2 (%): C 57.22, H 4.96, N 2.20
(Calcd: C 57.33, H 4.98, N 2.31).
PPh2
PPh2
PPh2
OTf-
P+Ph2Me
Ph2PCl, NEt3
DCM, 0 °C to RT
MeOTf
Et2O, -55°C to RT
NH2
R N
R
N
L4: R = Phenethyl
L2: R = Methoxyethyl
L3: R = Phenethyl
75
MeOTf
Et2O, -55°C to RT
Ph2P P+Ph2
Me
L5
Ph2P PPh2
dppm
N-(diphenylphosphino)-N-(methyldiphenylphosphonium)-2-
phenylethanamine trifluoromethanesulfonate (L3) and N,N-
bis(diphenylphosphino)-2-phenylethanamine (L4)
20 N-(diphenylphosphino)-N-(diphenylphosphonium)-1N,3P-
propane iodide (L1) To a solution of 3-bromopropylamine
hydrobromide (218.1 mg, 1.0 mmol, 1.0 equiv) in
dichloromethane (10 mL), a suspension of triethylamine (333.3
mg, 3.3 mmol, 3.1 equiv) in dichloromethane (10 mL) was added
25 dropwise under N2 atmosphere. After stirred at room
temperature for 30 minutes and then cooled down to 0 °C, the
reaction mixture was treated dropwise with a solution of
diphenylchlorophosphine (441.2 mg, 2.0 mmol, 2.0 equiv) in
dichloromethane (5 mL). The obtained mixture was stirred at 0
30 °C for another 1 h and then warmed up to ambient temperature
in 12 h. The resultant mixture was evaporated the solvent in
vacuo and then the collected residue was dissolved in dry THF
(15 mL). Through filtration to remove the formed salt of
triethylamine hydrochloride, the obtained filtrate was
35 evaporated in vacuo to remove THF solvent. Then the obtained
residue dissolved in acetonitrile was treated with excess KI
dropwise for 3 h under vigorously stirring and N2 atmosphere for
ion-exchange. After removal of the solvent of acetonitrile in
vacuo, the resultant residue was dissolved in dichloromethane
40 again. Upon filtration to remove the precipitates, the clear
solution was stripped of the solvent to give the solid reside
which was recrystallized in MeCN-EtOAc to afford L1 as a white
solid in the yield of 70%. 1H NMR (δ, ppm, CDCl3): 7.98-7.93
(4HPh, m), 7.82-7.80 (2HPh, m), 7.70-7.67 (4HPh, m), 7.47-7.41
45 (5HPh, m), 7.27-7.22 (5HPh, m), 3.77-3.64 (4H, m, PCH2CH2CH2P+),
2.65-2.54 (2H, m, PCH2CH2CH2P+). 31P NMR (δ, ppm, CDCl3): 64.2
L4 was obtained as a white solid in the yield of 86 % according to
80 the similar procedures as described for the preparation of L2
[26]. 1H NMR (δ, ppm, CDCl3): 7.46-7.42 (9H, m), 7.34-7.33 (11H,
m), 7.15-7.08 (3H, m), 6.75-6.74 (2H, m), 3.45-3.36 (2H, m), 2.30-
2.26 (2H, m). 31P NMR (δ, ppm, CDCl3): 62.7 (s, PPh2). CHN-
elemental analysis found for L4 (%): C 78.94, H 5.97, N 2.52
85 (Calcd: C 78.51, H 5.97, N 2.86).
L3 was obtained with the yield of 86 % as a white solid after
quaternization of L4 by MeOTf at -25 oC. 1H NMR (δ, ppm,
CD2Cl2): 7.93-7.86 (6H, m), 7.80-7.75 (4H, m), 7.59-7.54 (6H, m),
7.52-7.47 (4H, m), 7.09-7.08 (3H, m), 6.37-6.35 (2H, m), 3.48-
90 3.40 (2H, m), 2.91 (3H, dd, 2JPH = 12 Hz, 2JPH = 4Hz), 2.01-1.96 (2H,
2
m). 31P NMR (δ, ppm, CD2Cl2): 58.5 (d, JP-P+ = 110 Hz), 53.6 (d,
2JP-P+ = 110 Hz). CHN-elemental analysis found for L3 (%): C 58.73,
H 4.96, N 2.35 (Calcd: C 58.33, H 4.72, N 2.43).
95 N-(Diphenylphosphino)-N-(methyldiphenylphosphonium)-2-
phenylethanamine trifluoromethanesulfonate (L5) L5 was
obtained as a white solid in the yield of 90% after quaternization
o
of dppm [bis(diphenylphosphino)methane] by MeOTf at -55 C.
1H NMR (δ, ppm, CDCl3): 7.64-7.56 (m, 6HPh), 7.45-7.42 (m, 4HPh),
100 7.37-7.33 (m, 4HPh), 7.22-7.19 (m, 6HPh), 3.70 (2H, d, PCH2P+, 2JP-H
= 12 Hz), 2.40 (3H, d, 2JP-H = 12 Hz). 31P NMR (δ, ppm, CDCl3): 23.3
2
2
(d, P+Ph2Me, JP-P+ = 66 Hz), -27.4 (d, PPh2, JP-P+ = 66 Hz). CHN-
elemental analysis found for L5 (%): C 60.56, H 4.98 (Calcd: C
59.12, H 4.59).
105
2
2
(d, P+Ph2Me, JP-P = 75 Hz), 44.4 (d, PPh2, JP-P+ = 75 Hz). CHN-
+
Rh-complex ligated by L2 (Rh-L2) Rh-L2 was obtained as a
elemental analysis found for L1 (%): C 58.69, H 4.75, N 2.78
yellow solid according to the procedures as described in our
(Calcd: C 58.60, H 4.74, N 2.53).
6
| Catalysis Science & Technology, [year], [vol], 00–00
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DOI: 10.1039/C5CY01827G
1
previous work (Yield: 78%) [32]. H NMR (δ, ppm, CDCl3): 8.05-
In a typical experiment, 1-octene (5 mmol, or the other olefin),
the commercial complex of Rh(acac)(CO)2 (0.005 mmol), and the
30 isolated ligand (0.03 mmol) were added into MeOH (3 mL, or
the other alcohol) sequentially. The obtained mixture in a 50 mL
sealed Teflon-lined stainless steel autoclave was purged with
syngas (CO/H2 = 1:1, 0.5 MPa) for two times and then pressured
by syngas to 4.0 MPa. The reaction mixture was stirred
7.99 (4HPh, m), 7.89-7.86 (4HPh, m), 7.67-7.63 (2HPh, m), 7.59-
7.52 (10H, m), 5.26 (1H, s O=CCHC=O), 2.95 (3H, d, CH3P+, JP-H
2
=
12 Hz), 2.58 (3H, s, (CH3)C=O)), 2.47 (2H, t, CH3OCH2CH2N, J = 8
Hz), 1.86 (3H, s, (CH3)C=O)), 1.46 (3H, s, CH3OCH2CH2N), 0.88
(2H, t, CH3OCH2CH2N, J = 8Hz). 31P NMR (δ, ppm, CDCl3): 93.3
5
1
2
(dd, JP-Rh = 242 Hz), 56.1 (d, JP-P+ = 34 Hz). CHN-elemental
analysis found for Rh-L2 (%): C 49.52, H 4.57, N 1.37 (Calcd: C 35 vigorously at the appointed temperature for some time. Upon
49.95, H 4.91, N 1.66).
completion, the autoclave was cooled down to room
temperature and depressurized carefully. The reaction solution
was analyzed by GC to determine the conversions (n-dodecane
as internal standard) and the selectivities (normalization
40 method), and by GC-Mass to identify the products.
10
Table 3 Crystal data and structure refinement for Rh-L2
Rh-L2
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
[C34H37N1O4P2Rh1]C1F3O3S1
837.57
Conclusions
Monoclinic
P21/c
L1-L3 were featured as the bifunctional ligands by combination of
phosphine fragments with Lewis acidic phosphoniums through N-
atoms. The molecular structure of the L2-ligated Rh-complex (Rh-
45 L2) indicated that the bi-functionalities in L2 were well retained
without incompatibility problem for the quenching of the acidity
of phosphonium by the Lewis basic phosphine fragment.
However, the acidity of phosphonium in L2 was able to be
quenched by the accessible electron-rich ether group, leading to
50 the decreased efficiency for acetalization but with negligible
effect on the preceding hydroformylation. Among L1-L3, as well
as in comparison to L4 and L5, L3 featured with the strong π-
acceptor character as well without quenching problem for Lewis
acidic phosphonium exhibited the best sequential catalysis for
55 both hydroformylation and acetalization, in which the phosphine
fragment was in charge of hydroformylation with Rh-complex
together and the phosphonium acted as the Lewis acidic catalysts
responsible for acetalyzation individually. L3-Rh(acac)(CO)2
system was also exhibited good generality to hydroformylation-
60 acetalization of a wide range of olefins in the different alcohols.
11.2087(4)
15.5479(6)
20.7874(8)
90
b (Å)
c (Å)
α
β
γ
(o)
(o)
(o)
97.1850(10)
90
V (Å3)
3594.2(2)
4
Z
dcalc (g cm-3)
1.548
(Mo-Kα) (mm-1)
T (K)
(A)
0.687
ꢀ
296(2)
0.71073
41294
λ
Total reflections
Unique reflections (Rint
R1 [I>2σ(I)]
)
6342 (0.0527)
0.0436
wR2 (all data)
0.1168
F(000)
Goodness-of-fit on F2
1712
Acknowledgment
1.032
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21473058 and 21273077),
and 973 Program from Ministry of Science and Technology of
65 China (2011CB201403).
X-ray Crystallography
15 Intensity data were collected at 296(2) K for Rh-L2 on a Bruker
SMARTAPEX II diffractometer using graphite monochromated
Mo-Kα radiation (λ = 0.71073 Å). Data reduction included
absorption corrections by the multi-scan method. The structures
were solved by direct methods and refined by full matrix least-
20 squares using SHELXS-97 (Sheldrick, 1990), with all non-
hydrogen atoms refined anisotropically. Hydrogen atoms were
added at their geometrically ideal positions and refined
isotropically. The crystal data and refinement details of L2 are
given in Table 3.
Notes and references
a Shanghai Key Laboratory of Green Chemistry and Chemical Processes,
School of Chemistry and Molecular Engineering, East China Normal
70 University, 3663 North Zhongshan Road, 200062 Shanghai, China. Email:
yliu@chem.ecnu.edu.cn.
† CCDC-1430675 (Rh-L2) contain the supplementary crystallographic
data in this paper. These data can be obtained free of charge from the
Cambridge
Crystallographic
Data
Centre
via
75 www.ccdc.cam.ac.uk/data_request/cif.
1
2
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Table of contents graphic:
Ph
PPh2
Ph
PPh2
PPh2
H2C
P+
PPh2
N
N
P+
N
P+
I-
OTf-
Ph
PPh2
OTf-
Ph
P+
OTf-
O
Me
N
Me
Me
Ph
Ph
Me
Ph
Ph
PPh2
L4
Ph
Ph
L1
L2
L3
L5
Me
Me
O
O
PPh2
OTf-
Ph
Rh
N
Rh(acac)(CO)2
P+
O
Me
PPh2 CO
Me
N
P+
Ph
OTf-
Ph
O
Me
Me
L2
Ph
Rh-L2
OR'
OR'
R'O
OR'
R''
CHO
R''
Rh-complex/L, CO/H2
CHO
+
+
iso-octenes
R
+
R
R
R'OH
R
R
acetal
aldehyde
1