Efficient water-soluble catalytic system RhI-CAP for biphasic hydroformylation of olefins

Article abstract of DOI:10.1016/j.mencom.2018.05.011

Rhodium-catalysed hydroformylation of styrene and aliphatic olefins under biphasic conditions in the presence of watersoluble 1,4,7-triaza-9-phosphatricyclo[5.3.2.1^4,9]tridecane (CAP) chemoselectively affords aldehydes. Multiple catalyst reuse without loss in performance is demonstrated.

Full text of DOI:10.1016/j.mencom.2018.05.011

Mendeleev
Communications
Mendeleev Commun., 2018, 28, 264–266
i
Efficient water-soluble catalytic system Rh -CAP
for biphasic hydroformylation of olefins
a
a
b
Oleg L. Eliseev,* Tatyana N. Bondarenko, Sergey N. Britvin,
a,c
a,c
Polina P. Khodorchenko and Albert L. Lapidus
a
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow,
Russian Federation. E-mail: oleg@server.ioc.ac.ru
Department of Crystallography, St. Petersburg State University, 199034 St. Petersburg, Russian Federation
I. M. Gubkin Russian State University of Oil and Gas, 119991 Moscow, Russian Federation
b
c
DOI: 10.1016/j.mencom.2018.05.011
Me
Rhodium-catalysed hydroformylation of styrene and aliphatic
olefins under biphasic conditions in the presence of water-
soluble 1,4,7-triaza-9-phosphatricyclo[5.3.2.14 ]tridecane
CO, H2
CHO
R
R
+
R
CHO
Rh(acac)(CO)2
P
,9
–
water-soluble catalyst
(CAP) chemoselectively affords aldehydes. Multiple catalyst
N
N
– biphasic catalysis
– multiple recycle
reuse without loss in performance is demonstrated.
N
2
5
Hydroformylation of alkenes is one of the most important
transition metal catalysed reactions with huge industrial imple­
butylphosphane and tricyclohexylphosphane. Large differences
31
between the P NMR chemical shifts of CAP (+47 ppm) and
PTA (–96 ppm) were detected along with unusual atrane­like steric
behavior. Unusual stereoelectronic properties of CAP in combina­
1–3
mentation. Modified rhodium catalysts are widely used because
4
26
of high reaction rate at low pressure and temperature. Molecular
and electronic structure of supporting ligand plays a crucial role
in catalyst composition, governing its activity, chemo­ and regio­
selectivity. Although a large number of ligands have been proposed
tion with its hydrophilicity make it an interesting candidate for
study of its catalytic activity. Indeed, Rh(acac)(CO) /CAP turned
2
out to be very active and selective system in hydroformylation of
styrene and aliphatic olefins.
5
–7
to this reaction, development of new ones remains topical.
Among them, water­soluble species attract special attention
because they can immobilize rhodium in aqueous phase thus
We chose Rh(acac)(CO) as a popular rhodium source and at
2
first compared its performance in combination with CAP, PTA and
triphenylphosphine ligands under one­ and two­phase conditions.
IR spectra of Rh(acac)(CO) and Rh(acac)(CO) + 2CAP were
7
solving problem of catalyst separation and reuse. In particular,
8
tris(3­sulfophenyl)phosphine sodium salt (TPPTS) found com­
2
2
mercial application in Ruhrchemie/Rhône­Poulenc biphasic process
recorded in dichloromethane. Symmetric and asymmetric CO
9,10
–1
of propene hydroformylation into butanal. Besides TPPTS and
stretches of Rh(acac)(CO) are at 2084 and 2012 cm , which
2
1
1–16
29
other sulfonated phosphanes,
other types of water­soluble
corresponds to reported data. Addition of two equivalents of CAP
ligands in olefin hydroformylation are scarce.1
7–19
to Rh(acac)(CO) solution leads to disappearing these bands and
2
–
1
Recently cationic water­soluble phosphanes, e.g., tricyclic cage
arising a new one at 1962 cm . We conclude that one carbonyl
ligand in Rh coordination sphere is replaced by CAP giving
Rh(acac)(CO)(CAP) complex. Reported n(CO) frequencies for
analogous complexes Rh(acac)(CO)(PPh ), Rh(acac)(CO)(PPhCy )
1
,3,5­triaza­7­phosphaadamantane (PTA) and its derivatives, attract
20,21
increasing interest in catalysis and medicinal chemistry.
The
distinctive features of PTA are sterically undemanding adamantane
structure, water solubility, chemical and thermal stability. The
Rh­PTA complexes were tested, among some other transition
metal catalysed reactions, in olefin hydroformylation.2
3
2
–
1
and Rh(acac)(CO)(PCy ) are 1977, 1968 and 1959 cm , respec­
tively. One can conclude that electron­donor ability of CAP
3
3
0
2–24
ligand is high and comparable with that of PCy , as has been
3
25
predicted by DFT computations in our previous work.
P
P
Catalyst activity was estimated based on olefin conversion
and average turnover frequency (TOF) which was calculated as
amount of formed aldehydes per mole of Rh per hour (Table 1).
N
N
N
N
N
N
In hydroformylation of styrene in toluene solution, PPh gave more
3
PTA
CAP
active catalyst than CAP. Nevertheless, selectivity to branched
aldehyde is much higher for the latter (entries 1, 2). In biphasic
toluene + water medium, both activity and regioselectivity of
Very recently we accessed a new symmetric cage­like triaza­
phosphane, viz. 1,4,7­triaza­9­phosphatricyclo[5.3.2.14,9]tridecane
Rh(acac)(CO) + 2CAP system increased substantially as TOF
2
–
1
(CAP) possessing a tris(homoadamantane) cage architecture (cf.
reached 285 h and branched to linear aldehyde ratio was of
94:6, more than three times higher than that under single phase
conditions (entry 3). Under the same reaction conditions, the
refs. 25, 26). Like PTA, CAP is solid, air­ and thermally stable
water­soluble phosphane. From the structural point of view, both
phosphanes can be regarded as macrocyclic homologues. How­
ever, computations of Tolman’s electronic parameter show that
CAP possesses essentially higher electron­donating ability than
PTA and in this respect approaches strong donors such as tri­tert­
combination of Rh(acac)(CO) and PTA seemed to be much less
2
active and unselective, both isomeric aldehydes were formed in
almost the same amount (entry 4). As Tolman cone angles of
both ligands are close, observed dramatic difference in activity
©
2018 Mendeleev Communications. Published by ELSEVIER B.V.
–
264 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2018, 28, 264–266
Table 1 Hydroformylation of olefins in the presence of Rh(acac)(CO) and various ligands.a
2
Me
Rh(acac)(CO)2,
ligand
CHO
R
+ CO + H2
R
+
R
CHO
Ligand, L:Rh
molar ratio
Branched/linear
ratio
Entry
Substrate
Solvent
T/°C
P/bar
Conversion (%)
Average TOF/h–1
1
2
3
4
5
6
7
8
9
Styrene
Toluene
Toluene
PPh , 2
80
80
80
80
80
80
80
80
60
20
20
20
20
20
20
10
30
20
20
20
20
20
20
30
20
20
100
28
60
17
78
79
24
73
37
67
37
55
40
13
58
35b
50b
479
133
285
75
62:38
82:18
94:6
3
Styrene
CAP, 2
CAP, 2
PTA, 2
CAP, 3
CAP, 4
CAP, 2
CAP, 2
CAP, 3
CAP, 3
CAP, 1
CAP, 2
CAP, 3
PTA, 2
CAP, 2
CAP, 2
CAP, 2
Styrene
Toluene–H O
2
Styrene
Toluene–H O
55:45
94:6
2
Styrene
Toluene–H O
381
390
105
358
178
319
183
258
194
55
2
Styrene
Toluene–H O
93:7
2
Styrene
Toluene–H O
87:13
94:6
2
Styrene
Toluene–H O
2
Styrene
Toluene–H O
98:2
2
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
Styrene
Toluene–H O
100
81:19
28:72
29:71
30:70
26:74
30:70
28:72
27:73
2
Hex­1­ene
Hex­1­ene
Hex­1­ene
Hex­1­ene
Hex­1­ene
Non­1­ene
Dodec­1­ene
H O
80
80
80
80
80
80
80
2
H O
2
H O
2
H O
2
H O
266
174
230
2
H O
2
H O
2
a
b
Run conditions: olefin (4.4 mmol), Rh(acac)(CO) (0.0044 mmol), ligand, toluene (optionally, 5 ml), H O (optionally, 2 ml), 2 h. In addition to aldehydes,
2
2
internal olefins are also formed (8 and 14% for entries 16, 17, respectively).
and regioselectivity should be attributed to their different basicity
rather than steric hindrance.25
60
0.5
5
4
3
0
0
0
Raising CAP:Rh ratio from 2:1 to 3:1 led to substantial increase
in activity while regioselectivity remained the same. Further
increase in CAP amount gave almost no activity gain and disproved
the selectivity (entries 3, 5, 6). We conclude that CAP:Rh ratio
of 3:1 is optimal. Syngas pressure promotes both catalyst activity
and selectivity to 2­phenylpropanal (entries 7, 8). Reaction tem­
perature of 80°C seems to be optimal. Raising temperature to
0
0
0
0
.4
.3
.2
.1
20
1
0
0
1
00°C resulted in decreasing both activity and regioselectivity
(entries 5, 10). At 60°C, branched to linear aldehyde ratio was
0.0
very high, however, styrene conversion was poor (entry 9).
Next, we examined CAP in hydroformylation of neat hex­1­ene.
As expected, linear heptanal was the favoured product, with
branched to linear aldehyde ratio being 29:71. Remarkably, regio­
selectivity was almost unaffected by changing CAP:Rh ratio
1
2
3
4
5
6
Run number
Figure 1 Yields of products (columns) and branched/linear ratio (line) in
catalyst recycling in hex­1­ene hydroformylation (for the reaction conditions,
see Table 1, entry 12).
(entries 11–13). By increasing syngas pressure to 30 bar, an
insignificant improvement in selectivity to branched aldehyde
was achieved (entry 15). For comparison, we tested PTA under
the same reaction conditions and found that hexene conversion
was much lower (entries 12, 14).
In hydroformylation of hex­1­ene with CAP ligand, no migra­
tion of double bond in the substrate occurs. We detected only
trace amount of internal hexenes in reaction mixture of some
runs (<0.2%). On the contrary, PTA gives considerable amount
of isomers under the same conditions (entry 14). However, for
higher homologues such as non­1­ene and dodec­1­ene double
bond migration occurs with CAP, too. The thus formed less reactive
internal olefins (8 and 14% yields, entries 16, 17, respectively)
do not undergo hydroformylation.
sequent runs, substrate conversion, aldehydes yield and branched
to linear aldehyde ratio were almost unchanged (Figure 1).
In conclusion, water­soluble cage­like triazaphosphine CAP
was successfully applied for the first time as a stabilising ligand for
i
Rh ­catalysed biphasic hydroformylation of styrene and aliphatic
olefins. In styrene hydroformylation, excellent activity and regio­
selectivity to branched aldehyde were achieved. Attractive feature
of the catalyst is high chemoselectivity, aldehydes always are the
sole products. Catalyst can be easily separated from the products
by simple decantation of the organic layer of the reaction mixture.
Multiple catalyst reuse without loss in performance was demon­
strated. Thus, proposed catalytic system promises a shortcut access
to 2­arylpropionic aldehydes, valuable precursors of pharma­
3
1,32
Note that excellent chemoselectivity of Rh(acac)(CO) + CAP
ceutical products of the Profen class.
2
system was determined. In all experiments with this ligand,
hydrogenation products (ethylbenzene, alkanes) were absent in
the reaction mixture or detected in trace amounts. Reportedly,
electron­donating phosphanes promote direct formation of alcohols
under hydroformylation conditions in protic solvents.2 However,
no alcohols were formed in our experiments with CAP.
This work was supported by the St. Petersburg State University
(grant nos. 0.37.235.2015 and 3.37.222.2015).
7,28
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Received: 14th November 2017; Com. 17/5407
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