Catalytic redox isomerization of allylic alcohols with rhodium and iridium complexes with ferrocene phosphine-thioether ligands

Article abstract of DOI:10.1016/j.molcata.2016.08.014

Complexes [M(P,SR)(diene)X] where (P,SR) = CpFe[1,2-C₅H₃(PPh₂)(CH₂SR)] (M = Ir, R = tBu or Bn diene = cod, X = Cl; M = Rh, diene = cod or nbd; X = BF₄ or Cl) were used as precatalysts for the redox isomerization of various allylic alcohols (7a–e) to the corresponding saturated ketones (8a–e) and or hydrogenation to the saturated alcohol (9a–e). In optimization studies using 1-phenyl-2-propen-1-ol (7a) in THF and in iPrOH/MeONa, the only observed product was the saturated alcohol 1-phenyl-1-propanol (9a) when working under a 30 bar H₂ pressure, but activation for only 1 min under H₂ pressure and then continuation under 1 bar of H₂ or Ar led to increasing amounts of the allylic isomerization product propiophenone (8a). Continued reaction under H₂ converted (8a) into (9a). The Rh precatalysts were more active than the Ir analogues. For the rhodium precatalysts (3) and (4), the redox isomerization reaction could be carried out after precatalyst activation in iPrOH/MeONa under Ar at 82 °C (without H₂) with complete conversion in 1 h (1% catalyst loading). However, longer reaction times resulted in slow transfer hydrogenation of (8a) leading to (9a) with low enantiomeric excess. Extension of the H₂-free activation of the Rh precatalysts in iPrOH to other allylic alcohol substrates (7b–d) yielded the corresponding ketones with good to excellent yields and excellent chemoselectivities under appropriate conditions.

Full text of DOI:10.1016/j.molcata.2016.08.014

Accepted Manuscript
Title: Catalytic redox isomerization of allylic alcohols with
rhodium and iridium complexes with ferrocene
phosphine-thioether ligands
Author: Ekaterina M. Titova S.M.Wahidur Rahaman Elena S.
Shubina Rinaldo Poli Natalia V. Belkova Eric Manoury
PII:
S1381-1169(16)30338-7
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.molcata.2016.08.014
MOLCAA 10001
To appear in:
Journal of Molecular Catalysis A: Chemical
Received date:
Revised date:
Accepted date:
28-4-2016
5-8-2016
13-8-2016
Please cite this article as: Ekaterina M.Titova, S.M.Wahidur Rahaman, Elena
S.Shubina, Rinaldo Poli, Natalia V.Belkova, Eric Manoury, Catalytic redox
isomerization of allylic alcohols with rhodium and iridium complexes with
ferrocene phosphine-thioether ligands, Journal of Molecular Catalysis A: Chemical
http://dx.doi.org/10.1016/j.molcata.2016.08.014
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HIGHLIGHTS
.
.
.
.
Full hydrogenation of allylic alcohols under 30 bar dihydrogen
Redox isomerization of allylic alcohols
Rhodium and iridium complexes with ferrocene phosphine-thioether ligands
Activation of rhodium diene complexes under transfer hydrogenation reaction conditions

GRAPHICAL ABSTRACT
2

Catalytic redox isomerization of allylic alcohols with rhodium and iridium
complexes with ferrocene phosphine-thioether ligands.
a,b,c
a
c
a,b,d
Ekaterina M. Titova,
S. M. Wahidur Rahaman, Elena S. Shubina, Rinaldo Poli,
c
a,b
Natalia V. Belkova* and Eric Manoury*
a
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-
3
1077 Toulouse Cedex 4, France CNRS. Fax: +33-561553003; Tel: +33-561333174; E-mail:
eric.manoury@lcc-toulouse.fr.
b
Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4, France
c
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov
Street 28, 119991 Moscow, Russia; Fax: +7-499-1355085; Tel:+7-499-1356448; E-mail:
nataliabelk@ineos.ac.ru.
d
Institut Universitaire de France, 103, bd Saint-Michel, 75005 Paris, France.
ABSTRACT
Complexes [M(P,SR)(diene)X] where (P,SR) = CpFe[1,2-C
5
H
3
(PPh
2
2
)(CH SR)] (M = Ir, R =
tBu or Bn diene = cod, X = Cl; M = Rh, diene = cod or nbd; X = BF
4
or Cl) were used as
precatalysts for the redox isomerization of various allylic alcohols (7a-e) to the corresponding
saturated ketones (8a-e) and or hydrogenation to the saturated alcohol (9a-e). In optimization
studies using 1-phenyl-2-propen-1-ol (7a) in THF and in iPrOH/MeONa, the only observed
product was the saturated alcohol 1-phenyl-1-propanol (9a) when working under a 30 bar H
2
2
pressure, but activation for only 1 min under H pressure and then continuation under 1 bar of H
2
or Ar led to increasing amounts of the allylic isomerization product propiophenone (8a).
Continued reaction under H converted (8a) into (9a). The Rh precatalysts were more active than
the Ir analogues. For the rhodium precatalysts (3) and (4), the redox isomerization reaction could
be carried out after precatalyst activation in iPrOH/MeONa under Ar at 82°C (without H ) with
complete conversion in 1 h (1% catalyst loading). However, longer reaction times resulted in slow
transfer hydrogenation of (8a) leading to (9a) with low enantiomeric excess. Extension of the H
2
2
2
-
free activation of the Rh precatalysts in iPrOH to other allylic alcohol substrates (7b-d) yielded
the corresponding ketones with good to excellent yields and excellent chemoselectivities under
appropriate conditions.
3

Keywords: Allylic alcohols; Redox isomerization; Hydrogenation; Transfer hydrogenation;
Rhodium; Iridium; Hydrogen-free activation.
This article is dedicated to Pr Georgiy B. Shul'pin on the occasion of his 70th birthday.
4

1
. Introduction
The isomerization of primary and secondary allylic alcohols into the corresponding aldehydes
and ketones is of a great interest, especially because it is an atom economical reaction and
provides valuable synthetic intermediates [1-7]. Great effort has been devoted to the development
of this reaction leading to significant achievements. Efficient asymmetric catalytic systems have
been developed [8-22] as well as catalytic systems in green solvents [23-37] such as water or
supported versions [38-40]. An additional interest of this reaction is the possibility to couple it
with other transformations by taking advantage of the high reactivity of the enolate- intermediates
with various electrophiles [41]. Thus, tandem reactions were used for the preparation of α-
halogenoketones [42-44], β-hydroxy and β-amino ketones [45-48], cyclopentenones [49], etc [18,
2
1]. Allylic isomerization has also been coupled with hydrogenation or transfer hydrogenation to
yield saturated alcohols [17, 20, 31, 54]. Although various metals such as iron, copper, nickel or
palladium [46, 55] have been used, most of the catalysts used so far are based on ruthenium [56-
6
5], rhodium and iridium [66-70], mainly with phosphorus and nitrogen-donor ligands [1-6].
Figure 1. Structure of P,SR ligands used in this study.
In this article, we wish to present our results on the first use of chiral P,S ligands [71-75] in the
redox allylic isomerization reaction. Our group has contributed to the development of chiral
ligands based on P and S donor atoms with the synthesis of the 1,2-substituted ferrocenes (P,SR)
shown in Figure 1 [76]. These ligands can be efficiently obtained in enantiomerically pure form or
as a racemic mixture [76]. The use of these ligands in complexes of different metals has led to a
number of catalytic applications in asymmetric allylic substitution [77, 78], asymmetric
methoxycarbonylation of alkenes [79] and hydrogenation of alkynes, alkenes, imines and ketones
[80-84]. Here we report the application of the rhodium and iridium complexes [M(P,SR)(diene)X]
(M = Ir, Rh; diene = cyclooctadiene, norbornadiene; X = BF
4
, Cl, see Figure 2) [80, 81, 86] in the
isomerization of allylic alcohols.
5

Figure 2. Structure of the iridium and rhodium complexes used in this study.
2
. Experimental
2
.1. General Considerations.
All reactions were carried out under an argon atmosphere using standard Schlenk
techniques. Solvents were carefully dried by conventional methods and distilled under argon
before use. The iridium and rhodium complexes [M(P,SR)(diene)X] (M = Ir, Rh; R = tBu, Bz;
-
diene = NBD, COD; X = BF
4
, Cl) were prepared according to a published procedure from (R/S)-
[80,81],
[86]. Optical purities and the yields for the
2
-diphenylphosphanyl-(R-thiomethyl)ferrocene ligands (R = tBu, Bz) and [Ir(COD)Cl]
2
[
Rh(COD)Cl] , [Rh(NBD)Cl] or [Rh(COD) ]BF
2
2
2
4
hydrogenation experiments were determined by NMR spectoscopy and GC: Supelco
BETADEX™ 225 (reactions of 6a, isotherm at 105°C), Supelco SPB-20 (reactions of 6e, 30°C
for 7 minutes then heating 15°C/min up to new isotherm at 120°C), NMR yield determination
(reactions of 6b-d).
2
.2. General procedure for the 1-phenyl-2-propene-1-ol allylic isomerization in THF.
−3
A solution containing 6.4·10 mmol of precatalyst and 0.13 mmol of substrate (20 equiv.) in 2
mL of THF was transferred into a 5 mL glass vial which was then placed under argon into a
stainless steel autoclave equipped with a magnetic stirring bar. The reaction vessel was
pressurized with H
was released and the reaction vessel was stirred for the desired time at controlled temperature
under a dihydrogen atmosphere at 1 bar. Alternatively, after venting the H pressure used for the
2
to 30 bars and stirred for the desired time at room temperature. Then pressure
2
catalyst activation, the residual H
2
was purged with argon by continuous flushing before
6

continuing the reaction. The pure products were obtained by chromatography of the reaction
mixture on silica gel using dichloromethane as eluent and then analyzed by NMR spectrosopy and
chiral GC for the determination of the yields and enantiomeric excesses.
2
2
.3. General procedure for the 1-phenyl-2-propene-1-ol allylic isomerization in iPrOH
2
.3.1. Precatalyst activation by H .
−3
−2
3
A solution containing 6.4·10 mmol of precatalyst, 3.2·10 mmol of CH ONa (5 equiv.) and 0.64
mmol of substrate (100 equiv.) in 2 mL of isopropanol was transferred into a 5 mL glass vial
which was then placed under argon into a stainless steel autoclave equipped with a magnetic
2
stirring bar. The reaction vessel was pressurized with H to 30 bars and stirred for the desired time
at controlled temperature. The reaction was stopped by venting the H atmosphere. The pure
2
products were obtained by chromatography of the reaction mixture on silica gel using
dichloromethane as eluent and analyzed by NMR spectroscopy and chiral GC for the
determination of the yields and enantiomeric excesses.
2
.3.2. Precatalyst activation by iPrOH.
−3
−2
3
A solution containing 6.4·10 mmol of precatalyst, 3.2·10 mmol of CH ONa (5 equiv.) and 0.64
mmol of substrate (100 equiv.) in 2 mL of isopropanol was prepared in a Schlenk tube under an
argon atmosphere and stirred for the desired time at the reflux temperature. The pure products
were obtained by chromatography of the reaction mixture on silica gel using dichloromethane as
eluent and analyzed by NMR spectroscopy and chiral GC for the determination of the yields and
enantiomeric excesses.
3
. Results and discussion
3
.1. Catalytic studies carried out in THF
The substrate chosen for our initial studies was racemic 1-phenyl-2-propene-1-ol (7a). We first
attempted the thermal activation of the (1)-(6) precatalysts to carry out the redox isomerization of
allylic alcohol (7a), but no rearrangement was observed in refluxing THF overnight. This lack of
reactivity may be related to the need to activate the precatalyst by diene ligand removal, as
discussed previously [80, 83, 85]. We therefore decided to use a hydrogen source to reduce the
diene ligand in order to open the metal coordination sphere [14, 15, 19]. When the reaction was
7

carried out under pressure (30 bar of H
2
) and at room temperature, allylic alcohol was converted to
1
-phenyl-1-propanol (9a) (see Table 1). Interestingly, the rhodium catalysts were more efficient
than the iridium one in this process and, as already documented in the literature for other
hydrogenation reactions [87], the complexes bearing the nbd ligand are more active than the
corresponding complexes bearing the cod ligand. Although this phenomenon may be interpreted
as an effect of the diene nature on the catalytic activity, implying that the diene remains
coordinated to the metal in the active species, it is also consistent with the well known faster
removal of nbd by hydrogenation relative to cod and thus to a shorter induction time for the nbd
system in catalysis [87]. Alcohol (9a) can result from the direct hydrogenation of the C=C bond of
(
7a) or from the hydrogenation of the C=O double bond of the product of redox isomerization,
propiophenone (8a) (see scheme 1) [88]. No ketone (8a) has been observed during these
experiments, even after incomplete conversions showing that if any (8a) produced, it must be
quickly hydrogenated to (9a) under these experimental conditions. In addition, 1-phenyl-1-
propanol (9a) was found to be racemic indicating that either the ketone hydrogenation has very
low enantioselectivity or that (9a) results from the direct C=C double bond hydrogenation of
racemic (7a) without any chiral resolution, leaving the asymmetric carbon already present in (7a)
untouched.
Scheme 1. Possible pathways leading from (7) to (8) and (9).
Table 1
а
Hydrogenation of 1-phenyl-2-propene-1-ol (7a) in THF.
Entry
Catalyst
(R)-(2)
(R)-(3)
(R)-(5)
(R)-(4)
(R)-(2)
Conversion, % Yield of (8a), % Yield of (9a), %
1
2
3
4
5
55
100
100
75
0
0
0
0
0
55
100
100
75
100
100
а
-3
Reaction conditions: catalyst (6.4·10 mmol), 1-phenyl-2-propene-1-ol (7a) (0.13 mmol), T = 25 °C
and PH2 = 30 bar, reaction time 1 h, solvent = THF (2 mL). The conversions were determined by GC.
8

In order to avoid full substrate hydrogenation and to observe any possible isomerization to the
ketone intermediate, the autoclave was pressurized with H at 30 bar for only 1 min at room
2
temperature, then the pressure was released and the reaction vessel was stirred for the desired time
at reflux under a dihydrogen atmosphere of 1 bar. Under these conditions, the alcohol (9a) was
still the main reaction product but the redox isomerization product (8a) was also observed (see
Table 2, entries 1-3). By replacing dihydrogen by argon after the 1 minute activation time, it was
possible to obtain more ketone (Table 2, runs 4-9). The comparison of the results obtained after 2
h and 16 h suggests a fast C=C bond hydrogenation during the minute under dihydrogen and a
slower allylic alcohol isomerization at longer reaction times under argon. Ketone (8a) could even
be obtained with good selectivity (93%, Table 2, entry 9).
Table 2
Results of the isomerization/hydrogenation reaction of 1-phenyl-2-propene-1-ol (7a) in THF
а
under various reaction conditions.
Entry Catalyst Conversion, % Time, h Yield of (8a), % Yield of (9a), % (8a)/(9a)
b
1
2
3
4
5
6
7
8
9
(R)-(2)
(R)-(4)
(R)-(3)
(S)-(1)
(R)-(3)
(R)-(6)
(S)-(1)
(R)-(3)
(R)-(6)
35
92
79
2
2
2
5.5
4
33
86.5
75
6/94
6/94
b
b
2
5/95
c
9
2
2.5
2.5
8
6.5
12.5
22
27/73
17/83
27/73
78/22
83/17
93/7
c
15
30
56
52
2
c
c
c
2
16
16
16
44
43
93
12
9
c
100
7
а
-3
Reaction conditions: catalyst (6.4·10 mmol), 1-phenyl-2-propene-1-ol (7a) (0.13 mmol), solvent = THF (2 mL).
b
c
The conversions were determined by GC. PH2 = 30 bar, 25 °C, 1 min, then PH2 = 1 bar, 70 °C. PH2 = 30 bar, 25 °C, 1
min, then Ar, 70 °C.
3
.2. Catalytic studies carried out in isopropanol with dihydrogen activation
The reaction was also carried out in iPrOH instead of THF, in the presence of NaOMe (5 equiv
relative to the catalyst) under 30 bar of hydrogen, using only the more active rhodium precatalysts.
Excellent conversions were obtained like in THF (cf. Table 3 and Table 1) but again only racemic
1
-phenyl-1-propanol (9a) was obtained and no ketone isomerization product was observed.
9

Table 3
Results of the reaction of 1-phenyl-2-propene-1-ol (7a) in Pr OH.
i
а
Entry
Catalyst Conversion, % Yield of (8a), % Yield of (9a), %
1
2
3
(R)-(3)
(R)-(4)
(R)-(6)
95
0
0
95
100
100
100
100
0
a
-3
-2
Reaction conditions: catalyst (6.4·10 mmol), NaOMe (3.2·10 mmol), 1-phenyl-2-propene-1-ol (7a) (0.64
i
mmol), T = 25 °C and PH2 = 30 bar, reaction time 2 h, solvent = Pr OH (2 mL). The conversions were determined by
GC.
3
.3 Catalytic studies carried out in isopropanol without dihydrogen activation
Finally, again in order to avoid the hydrogenation reaction and increase the selectivity in favor
of the ketone, we checked whether the precatalyst could be activated by isopropanol itself under
transfer hydrogenation reaction conditions, in the absence of dihydrogen. It is in fact known from
the literature that [MCl(COD)L] compounds (M = Rh, Ir) react with β-H containing alkoxides at
room temperature to yield COD-containing hydride products by ketone elimination and these
species were shown to be active in transfer hydrogenation catalysis [89-93]. The reaction was
carried out in iPrOH in the presence of a base (NaOMe) under an argon atmosphere at reflux.
After 1 h (Table 4, entries 1-2), (7a) was selectively converted to the allylic isomerization product
(
8a) in good to excellent yields, proving the efficient activation of the precatalyst under these
conditions. When the reaction time was increased to 6 h, however, significant amounts of alcohol
9a) resulting from the transfer hydrogenation of (8a) could also be observed (Table 4, entries 3-
). The transfer hydrogenation was slow and only slightly enantioselective (ee up to 17%). With
(
4
this information in hands, we decided to check whether this dihydrogen-free procedure could be
used for catalytic redox isomerization of other allylic alcohols with good selectivity in favor of the
carbonyl compounds (see table 4). Indeed, the expected ketones (8) were obtained in good to
excellent yields and very high chemoselectivities for all investigated substrates (see table 4),
although the reaction was very slow for (7e) with both racemic rhodium complexes 3 and 4. Only
for substrate (7a) was a subsequent slow and poorly enantioselective transfer hydrogenation
observed over 6 h (entries 3-4), whereas for substrates (7b-d) no evidence of transfer
hydrogenation was observed over as many as 45 h.
Table 4
a
Results of the reaction of allylic alcohols (7) in the absence of H
2
.
1
0

b
Entry Catalyst Substrate t, h Conversion, % Yield of (8), % Yield of (9), % ee, %
1
2
3
4
5
6
7
8
9
1
(R)-(3)
(7a)
(7a)
(7a)
(7a)
(7b)
(7b)
(7c)
(7c)
(7d)
(7d)
(7e)
(7e)
1
1
100
56
100
100
88
84
100
54
56
99
4
100
100
66
81
88
84
100
54
56
99
4
0
0
-
-
(R)-(4)
(R)-(3)
6
34
19
0
17
14
-
(R)-(4)
6
(R/S)-(3)
(R/S)-(4)
(R/S)-(3)
(R/S)-(4)
(R/S)-(3)
(R/S)-(3)
(R/S)-(3)
(R/S)-(3)
16
16
16
16
20.5
45
16
0
-
0
-
0
-
c
0
-
c
0
0
-
11
0
-
1
2
16
2
2
0
-
a
-3
-2
Reaction condition: catalyst (6.4·10 mmol), NaOMe (3.2·10 mmol), allylic alcohol (0.64 mmol), T = 82 °C.
b
The conversion and ee were determined by GC. The ee is reported with respect to the R- configuration. c: Reaction
run at RT.
The nature of the active catalyst remains for the moment unknown. As stated above, hydride-
diene species should be formed upon interaction of methoxide or isopropoxide at room
temperature, but how these species evolve upon reflux is a question that has not been addressed in
detail in previous investigations. We are now carrying out studies in this direction and will report
the corresponding results in due course.
4
. Conclusions
In conclusion, the rhodium and iridium complexes of ferrocene phosphine-thioether ligands
described in this paper are efficient catalysts for the hydrogenation of the allylic alcohol (7a) to
racemic (9a), probably by direct hydrogenation of the C=C double bond. However, competitive
alcohol isomerization to the saturated ketone (8a) occurs upon replacing dihydrogen with argon
after a short activation step (1 minute under 30 bar of dihydrogen). Perhaps the most interesting
new discovery of our study is that the rhodium precatalysts can be activated in basic isopropanol
without using any hydrogen, yielding the allylic isomerization products in good to excellent yields
and very high chemoselectivities, comparing well with some other catalytic systems [1-6]. This
procedure does not require pressure reactor and then could be more practical on laboratory scale.
The catalytic reactions were carried out with rather good catalytic activities (only 1 mol% at
temperature ranging from RT to 82°C) [1-70]. Indeed, we have so far only tested a limited number
1
1

of substrates. To compare more accurately the performance of the catalytic systems described in
this article with other catalytic systems, an extension of this catalytic transformation to a broader
substrate scope will be necessary. Further work is in progress in our laboratories.
Acknowledgments
We are grateful to the European Commission, Contract No. 654198 (Marie Curie action
IIF) for a post-doctoral Fellowship to SMWR, the CNRS (Centre National de la Recherche
Scientifique) and the RFBR (Russian Foundation for Basic Research) for support through the
GDRI (Groupe de Recherche Internationale) “Homogeneous Catalysis for Sustainable
Development”, and the IUF (Institut Universitaire de France) for additional funding. EMT thanks
the Embassy of France in Moscow for a Ph.D. grant.
1
2

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