Chiral ferrocene-based P,S ligands for Ir-catalyzed hydrogenation of minimally functionalized olefins. Scope and limitations

Article abstract of DOI:10.1016/j.tet.2015.01.047

A family of 12 modular ferrocenyl planar chiral phosphine-thioethers (P,S) has been studied in the asymmetric hydrogenation of minimally functionalized alkenes. These ligands differ by the substituent on sulfur or by the linker between the ferrocene moiety and the sulfur atom (no linker, methylene or methyl substituted methylene linker bearing an additional element of chirality). The cationic iridium(cod) complexes of the different P,S ligands have been efficiently synthesized. For the majority of the ligands, coordination yielded only a single diastereoisomer with full control of the absolute configuration on sulfur. The different iridium complexes have been used in the hydrogenation of various di, tri, and tetrasubstituted minimally functionalized olefins. Conversions and enantioselectivities are highly dependent on the ligand and substrate structure. Full conversions and low-to-excellent enantioselectivities could be obtained (maximum ee from 14 to 94% for 1,1-disubsituted alkenes, from 17 to 99% for trisubstituted olefins, and 34% for the tetrasubstituted alkene).

Full text of DOI:10.1016/j.tet.2015.01.047

Accepted Manuscript
Chiral ferrocene-based P-S ligands for Ir-catalyzed hydrogenation of minimally
functionalized olefins. Scope and limitations
Maria Biosca, Mercè Coll, Florian Lagarde, Emma Brémond, Lucie Routaboul, Eric
Manoury, Oscar Pàmies, Rinaldo Poli, Montserrat Diéguez
PII:
S0040-4020(15)00102-7
10.1016/j.tet.2015.01.047
TET 26370
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 13 November 2014
Revised Date: 9 January 2015
Accepted Date: 22 January 2015
Please cite this article as: Biosca M, Coll M, Lagarde F, Brémond E, Routaboul L, Manoury E, Pàmies
O, Poli R, Diéguez M, Chiral ferrocene-based P-S ligands for Ir-catalyzed hydrogenation of minimally
functionalized olefins. Scope and limitations, Tetrahedron (2015), doi: 10.1016/j.tet.2015.01.047.
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ACCEPTED MANUSCRIPT
Chiral ferrocene-based P-S ligands for Ir-catalyzed
hydrogenation of minimally functionalized olefins.
Scope and limitations
a
a
b,c
b,c
Maria Biosca, Mercè Coll, Florian Lagarde, Emma Brémond, Lucie
b,c
b,c*
a
b,c,d
Routaboul, Eric Manoury , Oscar Pàmies, Rinaldo Poli,
a,*
Montserrat Diéguez
a
Departament de Química Física i Inorgànica. Universitat Rovira i Virgili. C/ Marcel·li
Domingo, s/n. 43007 Tarragona, Spain. Fax: 34-977559563; Tel: 34-977558780; email:
montserrat.dieguez@urv.cat.
b
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP
4
4099, F-31077 Toulouse Cedex 4, France CNRS. Fax: +33-561553003; Tel: +33-
61333174; E-mail: eric.manoury@lcc-toulouse.fr.
5
c
Université de Toulouse, INPT, UPS, Toulouse, France.
d
Institut Universitaire de France, 103, bd Saint-Michel, 75005 Paris, France.
Abstract
A family of 12 modular ferrocenyl planar chiral phosphine-thioethers (P,S) has been
studied in the asymmetric hydrogenation of minimally functionalized alkenes. These
ligands differ by the substituent on sulfur or by the linker between the ferrocene moiety
and the sulfur atom (no linker, methylene or methyl substituted methylene linker
bearing an additional element of chirality). The cationic iridium(cod) complexes of the
different P,S ligands have been efficiently synthesized. For the majority of the ligands,
coordination yielded only a single diasteroisomer with full control of the absolute
configuration on sulfur. The different iridium complexes have been used in the
hydrogenation of various di, tri and tetrasubstituted minimally functionalized olefins.
Conversions and enantioselectivities are highly dependent on the ligand and substrate
structure. Full conversions and low-to-excellent enantioselectivities could be obtained
1

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(maximum ee from 14 to 94% for 1,1-disubsituted alkenes, from 17 to 99% for
trisubstituted olefins and 34% for the tetrasubstituted alkene).
Introduction
One of the most challenging tasks of organic chemistry is the synthesis of chiral
compounds, which are necessary intermediates in the preparation of a wide range of
1
pharmaceutical, agrochemical, fine chemical and natural products. Up to date,
asymmetric hydrogenation, the atom-economical addition of H to a C=X (X = C, N or
2
O) bond to obtain chiral compounds is one of the most efficient, sustainable and
,
2
straightforward chirality-generating process.1 For the enantioselective hydrogenation
of minimally functionalized olefins, Ir complexes with chiral P,N ligands have shown to
be effective catalysts that complement the well-developed Rh/Ru catalysts for
3
functionalized olefins. Since the application of Ir-phosphine-oxazoline PHOX chiral
4
catalysts in 1998 by Pfaltz and coworkers, researchers have focused on Ir-catalysts
5
based on a wide range of P-oxazoline ligands. These new Ir-catalysts have significantly
broadened the substrate scope. Despite the advances in Ir-based P-N catalysts, their
activity and selectivity for reducing some significant minimally functionalized olefins
still needs to be improved, especially since the demand for new optically active chiral
centers has moved researchers into the Ir-catalyzed asymmetric reduction of more
"exotic" substrates. This will require novel, highly efficient chiral ligands that are easier
to handle, readily accessible, and that enhance the application range. In this respect,
research has progressed to heterodonor P,X-ligands bearing more robust X-donor
6
7
8
9
10
groups than oxazolines (pyridines, amides, thiazoles, thiazolines, oxazoles, etc.).
Some of us have recently described the successful use of non-N-donor heterodonor
ligands, the phosphorus-thioether ligands, for the enantioselective Ir-catalyzed reduction
1
1
of minimally functionalized olefins. Ir-complexes modified with two families of P-
thioether ligands efficiently catalyzed the hydrogenation of a large range of olefins, with
results comparable to the best ones reported in the literature. Despite this success, other
2

ACCEPTED MANUSCRIPT
thioether-P ligands have not yet been reported and research is in progress to study the
possibilities of this new class of ligands for this process.
Some of us have been involved for several years in the development of chiral
1
2
ferrocene-based ligands for asymmetric catalysis. Ferrocene-based ligands have been
1
3
successfully employed in asymmetric catalysis for more than three decades. They are
particularly interesting because of the facile introduction of different chiralities (planar
and central), their particular stereoelectronic properties and their high stability.
Although they have emerged as a privileged ligand structures for asymmetric catalysis,
their use in the Ir-catalyzed hydrogenation of minimally functionalized olefins has been
1
4
scarce.
Because we are interested in more versatile and robust Ir-catalysts, we took one
further step and tested new ligands that incorporate the advantages of ferrocenes and the
robustness of the thioether moiety. To this end, we tested a family of modular ferrocene
phosphine-thioether ligands 1-12 (Figure 1) in the Ir-catalyzed hydrogenation of 34
minimally functionalized alkenes, including concrete examples with neighboring polar
groups. The selection of chiral ligands contemplates systematic variations of the
1
5
electronic and steric properties of the thioether moiety (ligands 1-9), the removal of
1
6
the methylene spacer between the ferrocene and the thioether groups (ligand 10), as
well as introducing a second stereogenic center in the methylene spacer (ligands 11-
1
7
1
2) .
Figure 1. Ferrocene-based phosphine-thioether ligands 1-12
3

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Results and discussion
Synthesis of Ir-catalyst precursors
The Ir-catalyst precursors were prepared in a two-step, one-pot procedure (Scheme
1
). In the first step, the appropriate ligand reacts with 0.5 equivalent of [Ir(µ-Cl)(cod)]2
-
-
F
for 1 h at reflux. Then, Cl /BAr counterion exchange was achieved by a reaction with
sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBAr ) (1 equiv) in the
F
presence of water at room temperature. The iridium catalyst precursors were isolated in
pure form as air-stable orange solids in excellent yields (89-91%).
Scheme 1. Preparation of Ir-catalyst precursors [Ir(cod)(1-12)]BArF
The elemental analyses were in agreement with the assigned structures. The HRMS-
ESI spectra of [Ir(cod)(1-12)]BAr displayed the heaviest ions at m/z which correspond
F
to the loss of the BAr anion from the molecular species. Crystals suitable for X-ray
F
diffraction analysis of [Ir(cod)(4)]BAr complex were also obtained in order to
F
determine the coordination mode of the ferrocene-based phosphine-thioether ligands
(Figure 2). The six-membered chelate ring adopted a boat conformation, with the
thioether substituent in an equatorial position and the sulfur in an R configuration as has
1
8
already been observed for similar complexes.
4

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Figure 2. X-ray structure of [Ir(cod)(4)]BAr (CCDC 1033867) (the hydrogen atoms
F
-
F
and BAr anion have been omitted for clarity)
1
13
31
The H, C, and P NMR spectra show the expected pattern for these C -complexes.
1
The VT-NMR spectra in CD Cl (+35 to -75 °C) indicate the presence of a single isomer
2
2
in all cases except for [Ir(cod)(8)]BAr and [Ir(cod)(12)]BAr that were mixtures of two
F
F
isomers in equilibrium at a ratio of 1:2 and 1:6, respectively. These isomers may be
attributed to the two possible diastereoisomers formed when the thioether coordinates to
the metal atom (note that the coordinated S atom is a stereogenic center), to different
conformers for the six-membered chelate ring, or to both. To obtain the spatial
orientation of the thioether substituent and the conformation adopted by the six-
membered chelate ring we initially performed NOESY experiments of [Ir(cod)(4)]BArF
and [Ir(cod)(12)]BAr . Since the NOE contacts for Ir/4 were not conclusive, we studied
F
the [Ir(cod)(9)]BAr analogue instead.
F
For complex [Ir(cod)(9)]BAr and the major isomer of [Ir(cod)(12)]BAr , the NOE
F
F
indicated interactions between one of the methyl groups of the thioether xylyl substituent
and the phenyl group of the phosphine moiety and of that same methyl group with either
the methyl substituent (for Ir/12) or one of the hydrogen atoms (for Ir/9) at the alkyl
backbone chain (Figure 3a). In addition, the NOE indicated interactions of the other
xylyl methyl group with the other hydrogen of the alkyl backbone chain and with the
unsubstituted cyclopentadiene ring. These interactions can be explained assuming an
equatorial disposition of the thioether group and a boat conformation of the six-
5

ACCEPTED MANUSCRIPT
membered chelate ring with an R configuration of the sulfur atom (Figure 3a), as in the
X-ray structure of [Ir(cod)(4)]BAr (see Figure 2).
F
Figure 3. Main NOE contacts for (a) [Ir(cod)(9)]BAr (X= H) and major isomer of
F
[
Ir(cod)(12)]BAr (X= Me) and (b) minor isomer of [Ir(cod)(12)]BAr .
F F
For the minor isomer of [Ir(cod)(12)]BAr , we found NOE interactions between one
F
of the xylyl methyl groups and the phenyl group of the phosphine moiety and with the
hydrogen at the alkyl backbone chain (Figure 3b). We also observed NOE contacts
between the methyl substituent at the alkyl backbone chain and the substituted
cyclopentadiene ring. All these NOE contacts are in agreement with a boat conformation
of the six-membered chelate ring and the thioether substituent in an equatorial
disposition but, in contrast to previous isomers, with an S configuration of the sulfur
atom (Figure 3b). The assignments of the isomers of [Ir(cod)(12)]BAr were further
F
confirmed by DFT studies. Figure 4 shows these calculated structures and the relative
values of the formation enthalpy, being the isomer with an R configuration of the sulfur
atom the most stable. Complexes [Ir(cod)(8)]BAr and [Ir(cod)(12)]BAr are the first
F
F
examples of incomplete control of the sulfur chirality upon coordination for ferrocenyl
phosphine-thioethers with this type of backbone: only one diastereoisomer was observed
1
8,19
for all previously reported complexes, whatever the metal or the oxidation state.
6

ACCEPTED MANUSCRIPT
Major isomer (0 KJ/mol)
Minor isomer (11.8 KJ/mol)
Figure 4. Calculated structures (DFT) for cationic species of complex [Ir(cod)(12)]BArF
and their relative formation enthalpies.
Asymmetric Ir-catalyzed hydrogenation
Asymmetric hydrogenation of minimally functionalized olefins is highly sensitive to
the steric demands of the substrate.3 Unlike trisubstituted olefins, 1,1-disubstituted
olefins have not been successfully hydrogenated until very recently.3e,h This is because
the catalyst must control not only the face selectivity coordination (only two
substituents compared with the three in trisubstituted olefins), but also the isomerization
of the olefins to form the more stable E-trisubstituted substrates, which are
hydrogenated to form the opposite enantiomer. Tetrasubstituted olefins also remain an
unsolved class of substrate.3f,h The only Ir-catalysts that react with them with high
yields and enantioselectivities contain the less bulky phosphanylmethyloxazoline
2
0
ligands reported by Pfaltz. In order to evaluate the efficiency of ferrocene-based P-S
ligands 1-12 in the hydrogenation of olefins with different steric demands, we initially
tested them in the asymmetric reduction of the model tri-, di- and tetrasubstituted
substrates S1-S3 (Table 1).
Although low-to-moderate enantioselectivities were achieved in the reduction of
tetrasubstituted substrate S3, high enantioselectivities were obtained in the
hydrogenation of model tri- and disubstituted substrates (ee's up to 85% and 82% for S1
and S2, respectively). The results also indicated that the ligand components need to be
properly tuned for each substrate to maximize the enantioselectivities. For instance,
7

ACCEPTED MANUSCRIPT
while for S1 the best enantioselectivities were obtained with ligand 12 (entry 12),
containing both planar and central chirality and a bulky 2,6-dimethylphenyl thioether
substituent, the highest enantioselectivities for S2 were achieved with ligands 4 and 10
(entries 4 and 10), containing only planar chirality and a bulky tert-butyl thioether
group. Interestingly, for disubstituted substrate S2 both enantiomers of the
hydrogenated products could be obtained in high enantioselectivity by simply selecting
the planar chirality.
a
Table 1. Ir-catalyzed hydrogenation model substrates S1-S3
b
c
b
c
b
c
Entry Ligand
% Conv % ee
% Conv % ee
% Conv % ee
1
2
3
4
5
6
7
8
9
1
2
100
100
100
100
100
100
100
100
100
100
100
100
25 (S)
100
100
100
100
100
100
100
100
100
100
100
100
22 (S)
75
<5
<5
70
9 (R)
0
30 (S)
33 (S)
81 (S)
73 (S)
34 (S)
16 (S)
32 (S)
26 (S)
82 (R)
3 (R)
nd
3
10 (S)
50 (R)
46 (S)
11 (S)
30 (S)
24 (S)
50 (R)
15 (S)
29 (S)
85 (S)
nd
4
32 (R)
34 (R)
6 (R)
8 (R)
6 (R)
10 (S)
4 (R)
9 (R)
12 (S)
5
60
6
85
7
35
8
65
9
49
1
0
1
2
10
11
12
95
1
100
100
1
46 (R)
a
Reactions carried out at room temperature using 0.5 mmol of substrate and 1 mol% of Ir-catalyst
precursor at 100 bar of H (for substrates S1 and S3) and 1 bar (for S2) with dichloromethane (2
2
b
1
mL) as solvent. Conversion measured by H-NMR after 4 h (for S1 and S2) and after 18 h (for
S3). Enantiomeric excess determined by GC.
c
We next evaluated the new Ir/1-12 catalyst precursors in the hydrogenation of a
selected range of trisubstituted substrates, most of them with neighbouring polar groups.
8

ACCEPTED MANUSCRIPT
The reduction of substrates with neighbouring polar groups has a large interest because
they are relevant intermediates for the synthesis of highly valued chemicals. The most
remarkable results are shown in Figure 5 (see SI for a complete set of results).
Figure 5. Selected results for the hydrogenation of trisubstituted olefins S4-S23 using
[
Ir(cod)(1-12)]BArF catalyst precursors. Reaction conditions: 1 mol % catalyst
a
precursor, CH Cl as solvent, 100 bar H , 4 h. Reaction carried out for 18 h.
2
2
2
We first considered the reduction of aryl/alkyl substrates with Z-geometry S4-S6,
which are usually hydrogenated less enantioselectively than E-trisubstituted olefins like
S1.
3 Unfortunately, as previous studies had already suggested, enantiocontrol was only
moderate (ee's up to 46%). On the other hand, [Ir(cod)(4)]BAr was very efficient in the
F
2
1
reduction of several α,β-unsaturated esters S7-S11. The ee's were between 95-98%
and quite independent on the electronic nature of the substrate phenyl ring and on the
substituent cis to the ester group. Being able to hydrogenate α,β-unsaturated esters at
9

ACCEPTED MANUSCRIPT
such high ee's is of great importance because chiral carboxylic ester derivatives with
tertiary benzylic aliphatic stereogenic centres are found in many fragrances,
2
2
pharmaceuticals and natural products. This methodology represents a more sustainable
route for producing these chiral carboxylic esters than other common methods such as
the Co-catalyzed asymmetric conjugated reduction of α,β-unsaturated esters using
2
3
sodium borohydride and the Cu- and Rh-catalyzed 1,4-reduction using very moisture-
2
4
sensitive hydrosilane reagents . We then studied the reduction of alkenylboronic esters
S12 and S13 which would form versatile chiral C-B bonds that can later become C-N,
C-O and C-C bonds. The hydrogenation of alkenes containing one or two pinacolato-
boron groups proceeded smoothly with enantioselectivities as high as 76%. Another
important class of substrates that is receiving much attention are the α,β-unsaturated
enones. The hydrogenation of these substrates is an elegant path for obtaining ketones
with a stereogenic center in the α position of the carbonyl moiety. Nonetheless, they
have been less studied and less successfully hydrogenated than other trisubstituted
olefins.5i,u,v,25 The hydrogenation of the model α,β-unsaturated enone S14 proceeded
with moderate enantiocontrol (ee's up to 47%). However, it was very interesting to find
that enantioselectivities increased up to 85% in the hydrogenation of more challenging
cyclic enones S15 and S16.5v These latter results prompted us to focus on the
2
6
27
hydrogenation of other difficult olefins, such as enamide S17, lactone S18 and enol
2
8
phosphinates S19-S23 . Very few catalytic systems can provide high
enantioselectivities for these substrates so it was remarkable that we could achieve high-
to-excellent enantioselectivities in all of them by carefully tuning the ligand
components. Thus, in the reduction of enamide S17 and lactone S18, the highest
enantioselectivities (up to 90%) were achieved using [Ir(cod)(11)]BArF and
[
Ir(cod)(10)]BAr , respectively. [Ir(cod)(10)]BArF was also extremely efficient in the
F
reduction of a range of sterically demanding enol phosphinates, including examples of
pure alkyl-substituted enol phosphinates (Figure 5; S19-S23), providing comparable
high enantioselectivities to those achieved with the best ones reported (ee's between 92-
9
9%). The effective hydrogenation of this type of substrates opens up an appealing
1
0

ACCEPTED MANUSCRIPT
route for obtaining chiral organophosphinates, which can be easily transformed into
high-value compounds such as alcohols and phosphines.
Then we focused our attention on extending the range of disubstituted substrates
(Figure 6). Our results with several α-alkylstyrenes bearing decreasingly sterically
demanding alkyl substituents (S2, S24 and S25) indicated that enantioselectivity is
affected by the nature of the alkyl chain (ee's ranging from 14% to 82%). A plausible
explanation is the competition between direct hydrogenation and isomerization. This is
supported by the fact that the hydrogenation of substrate S2 bearing a tert-butyl group,
which cannot isomerize, provides the highest enantioselectivity. We then tested a wide
range of α-tert-butylstyrene type substrates (S26-S32) to evaluate how the electronic
and steric properties of the aryl group of the substrate affected the catalytic
performance. The highest enantioselectivities (up to 90%) of the series were achieved in
the reduction of substrates containing electrondonating groups at the para-position of
the aryl group (substrates S26 and S27).
Figure 6. Selected results for the hydrogenation of 1,1-disubstituted olefins S24-S34
using [Ir(cod)(1-12)]BAr catalyst precursors. Reaction conditions: 1 mol % catalyst
F
a
precursor, CH Cl as solvent, 1 bar H , 4 h. Reactions carried out for 18 h.
2
2
2
1
1

ACCEPTED MANUSCRIPT
Finally, we studied whether the excellent enantioselectivities obtained in the
hydrogenation of trisubstituted enol phosphinates (S19-S23, Figure 5) are maintained
for the even more demanding disubstituted analogues S33 and S34. Again,
[
Ir(cod)(10)]BAr was able to successfully hydrogenate these substrates with excellent
F
2
9
enantioselectivities comparable to the best ones reported.
Conclusions
Stable cationic iridium(cod) complexes with different P,S ligands proved to be good
precatalysts for the asymmetric hydrogenation of minimally functionalized olefins in
terms of activities and enantioselectivities. For many substrates, the ligand fine tuning,
thanks to its high modularity, enabled achieving good to excellent levels of
enantioselectivity, underlining their promising potential.
Experimental Section
General considerations
All reactions were carried out using standard Schlenk techniques under an argon
atmosphere. Solvents were purified and dried by standard procedures. Phosphine-
1
7b
30
1
13
31
thioether ligands 11 and 12 were prepared as previously reported. H, C, and P
NMR spectra were recorded using a 400 MHz or a 300 MHz spectrometer. Chemical
1
13
31
shifts are relative to that of SiMe ( H and C) as internal standard or H PO ( P) as
4
3
4
1
13
1
1
external standard. H and C assignments were made on the basis of H- H gCOSY and
1
13
H- C gHSQC. Geometries of isomers of [Ir(cod)(12)]BAr were optimized using the
F
3
1
32
Gaussian 09 program,
employing the B3LYP
density functional and the
3
3
LANL2DZ basis set for iridium and iron and the 6-31G* basis set for all other
3
4
elements. Solvation correction was applied in the course of the optimizations using the
3
5
PCM model with the default parameters of dichloromethane. The complexes were
treated with the charge +1 and in singlet state. No symmetry constraints were applied.
1
2

ACCEPTED MANUSCRIPT
3
6
The energies were further refined by applying dispersion correction using the DFT-D3
model. All energies reported are Gibbs free energies at 298.15 K and calculated as
Greported = G6-31G* + EDFT-D3
General procedure for the preparation of ligands 1-9
1
5a
Ligands 1-4 and 6-7 were prepared as previously reported. The ligands 5, 8 and 9
were prepared using the same method from enantiomerically pure (R)-(2-
12c
diphenylthiophosphinoferrocenyl)methanol (100 mg, 0.23 mmol)
and the
corresponding thiol in protecting form 5-S, 8-S and 9-S as thiophosphine-thioethers.
The deprotected (P,S) ligands were obtained by reaction of the protected forms with
15a
P(NMe2)3 and immediately engaged in the coordination reaction.
3
1
1
1
5
-S: Yield 131 mg (97%). P{ H} NMR (121 MHz, CDCl ), δ: 41.7. H NMR (300
3
MHz, CDCl ), δ: 1.63 (m, 6H, CH , Ad), 1.75 (m, 6H, CH , Ad), 1.97 (m, 3H, CH, Ad),
3
2
2
2
2
3
.72 (s, 1H, CH=, Cp), 3.90 (br d, 1H, CH , J = 13.0 Hz), 3.98 (br d, 1H, CH , J
2 H-H 2 H-H
=
13.0 Hz), 4.29 (s, 1H, CH=, Cp), 4.36 (s, 5H, CH=, Cp), 4.66 (s, 1H, CH=, Cp), 7.55-
1
3
1
7
.35 (m, 6H, CH=), 7.66 (m, 2H, CH=), 7.86 (m, 2H, CH=). C{ H} NMR (75 MHz,
CDCl ), δ: 23.7 (CH ), 29.7 (CH, Ad), 36.3 (CH Ad), 43.3 (CH Ad), 44.8 (C Ad),
3
2
2,
2,
,
6
9.0 (d, JC-P = 10.5 Hz, CH=, Cp), 70.9 (Cp), 73.4 (d, JC-P = 9.3 Hz, CH=, Cp), 74.0 (d,
JC-P = 94.6 Hz, C, Cp,) 74.2 (d, JC-P = 12.7 Hz, CH=, Cp), 90.2 (d, JC-P = 12.0 Hz, C,
Cp), 128.0 (d, JC-P = 12.4 Hz, CH=), 128.1 (d, JC-P = 12.5 Hz, CH=), 131.1 (d, JC-P = 3.0
Hz, CH=), 131.2 (d, JC-P = 3.0 Hz, CH=), 132.1 (d, JC-P = 10.6 Hz, CH=),1 32.3 (d, JC-P
=
10.6 Hz, CH=), 133.6 (d, JC-P = 86.0 Hz, C), 134.6 (d, JC-P = 87.1 Hz, C). HR/MS
(
ESI) m/e: 582.1273 (M, 100 %; calculated for C H PS Fe: 582.1267).
3
3
35
2
3
1
1
5
: Yield 114 mg (92%). P NMR (162 MHz, CDCl ), δ: -23.5. H NMR (400 MHz,
3
CDCl ), δ: 1.64 (m, 6H, CH , Ad), 1.77 (m, 6H, CH , Ad), 1.98 (m, 3H, CH, Ad), 3.62
3
2
2
2
(
dd, 1H, CH , J = 13.2 Hz, JH-P = 2.4 Hz), 3.73 (b, 1H, CH=, Cp), 3.75 (d, 1H, CH2,
2 H-H
2
JH-H = 13.2 Hz), 4.02 (s, 5H, CH=, Cp), 4.26 (m, 1H, CH=, Cp), 4.55 (m, 1H, CH=,
1
3
1
Cp), 7.1-7.3 (m, 5H, CH=), 7.40 (m, 3H, CH=), 7.57 (m, 2H, CH=). C{ H} NMR (100
1
3

ACCEPTED MANUSCRIPT
MHz, CDCl ), δ: 24.5 (d, J = 12.2 Hz, CH ), 29.8 (CH, Ad), 36.5 (CH Ad), 43.4
3
C-P
2
2,
(
CH Ad), 44.9 (C Ad), 69.5 (CH=, Cp), 70.0 (CH=, Cp), 71.1 (d, J = 3.8 Hz, CH=,
2, , C-P
Cp), 71.5 (d, JC-P = 3.8 Hz, C, Cp,) 75.7 (d, JC-P = 10.2 Hz, CH=, Cp), 91.3 (d, JC-P
=
=
2
7
1
5.1 Hz, C, Cp), 125.4 (C), 127.8 (CH=), 128.0 (d, JC-P = 6.0 Hz, CH=), 128.3 (d, JC-P
.6 Hz, CH=), 128.4 (C), 129.2 (d, JC-P = 6.2 Hz, CH=), 132.6 (d, JC-P = 17.5 Hz, CH=),
35.3 (d, JC-P = 21.3 Hz, CH=), 137.7 (d, JC-P = 8.3 Hz, C), 140.0 (d, JC-P = 9.1 Hz, C).
+
TOF-MS (ESI+): m/z = 550.1546, calcd. for C H FePS [M] : 550.1547).
3
3
35
3
1
1
1
8
-S: Yield 110 mg (83%). P{ H} NMR (121 MHz, CDCl ), δ: 41.4. H NMR (300
3
2
MHz, CDCl ), δ: 3.83 (m, 1H, CH=, Cp), 4.26 (s, 1H, CH=, Cp), 4.29 (d, 1H, CH , J
3
2
H-
2
=
13.0 Hz), 4.32 (s, 5H, CH=, Cp) 4.42 (s, 1H, CH=, Cp), 4.60 (d, 1H, CH , J
=
H
2
H-H
1
3
1
1
3.0 Hz), 7.55-7.35 (m, 10H, CH=), 7.9-7.7 (m, 6H, CH=), 8.23 (m, 1H, CH=). C{ H}
NMR (75 MHz, CDCl ), δ: 33.5 (CH ), 69.2 (d, J = 10.4 Hz, CH=, Cp,), 71.0 (CH=,
3
2
C-P
Cp), 73.8 (d, JC-P = 9.2 Hz, CH=, Cp,), 74.1 (d, JC-P = 96.3 Hz, C, Cp,), 74.6 (d, JC-P
=
1
1
1
1
1
2.7 Hz, CH=, Cp,), 88.8 (d, JC-P = 12.0 Hz, C, Cp,), 125.4 (CH=), 125.5 (CH=),
26.1(CH=), 126.2 (CH=), 127.3 (CH=),128.1 (d, JC-P = 12.6 Hz, CH=), 128.2 (d, JC-P
2.7 Hz, CH=), 128.4 (CH=), 128.9 (CH=), 131.3 (d, JC-P = 2.7 Hz, 2C), 132.1 (d, JC-P
=
=
0.8 Hz, CH=), 132.2 (d, JC-P = 10.7 Hz, CH=), 132.9 (C), 133.6 (d, JC-P = 70.2 Hz, C),
33.9 (C), 134.0 (C), 134.5 (d, JC-P = 71 Hz, C). HR/MS (ESI) m/e: 574.0642 (M, 75
%
; calculated for C H PS Fe: 574.0641), 415.0364(M-S(naphthyl), 100 %).
3
3
27
2
3
1
1
8
: Yield 92 mg (89%). P NMR (162 MHz, CDCl ), δ: -24.1. H NMR (400 MHz,
3
CDCl ), δ: 3.86 (m, 1H, CH=, Cp), 4.04 (s, 5H, CH=, Cp), 4.21 (b, 2H, CH ), 4.29 (m,
3
2
1
H, CH=, Cp), 4.43 (m, 1H, CH=, Cp), 7.33 (m, 5H, CH=), 7.4-7.5 (m, 4H, CH=), 7.53
(m, 3H, CH=), 7.61 (m, 2H, CH=), 7.76 (m, 1H, CH=), 7.85 (m, 1H, CH=), 8.30 (m,
1
3
1
1
H, CH=). C{ H} NMR (100 MHz, CDCl ), δ: 34.6 (d, J = 12.2 Hz, CH ), 69.8
3 C-P 2
(
CH=, Cp,), 70.0 (CH=, Cp), 71.6 (d, JC-P = 3.8 Hz, CH=, Cp,), 71.8 (d, JC-P = 3.8 Hz,
CH=, Cp,), 76.1 (d, JC-P = 8.4 Hz, C, Cp,), 89.9 (d, JC-P = 25.9 Hz, C, Cp,), 125.6 (d, JC-P
6.8 Hz, CH=), 126.3 (d, JC-P = 20.6 Hz, CH=), 127.6 (CH=), 128.1 (CH=), 128.2 (d,
JC-P = 6.1 Hz, CH=), 128.4 (d, JC-P = 5.9 Hz, CH=), 128.6 (CH=), 129.3 (CH=), 132.6
CH=), 132.7 (CH=), 133.2 (C), 134.0 (C), 134.3 (C), 135.1 (CH=), 135.4 (CH=),
=
(
1
4

ACCEPTED MANUSCRIPT
1
37.6 (d, JC-P = 7.6 Hz, C), 139.7 (d, JC-P = 9.1 Hz, C). TOF-MS (ESI+): m/z =
+
5
42.0919, calcd. for C H FePS [M] : 542.0921).
3
3
27
3
1
1
1
9
-S: Yield 118 mg (93%). P{ H} NMR (162 MHz, CDCl ), δ: 41.3. H NMR (400
3
2
MHz, CDCl ), δ: 2.42 (s, 6H, CH ), 3.78 (m, 1H, CH=, Cp), 3.86 (d, 1H, CH , J
=
3
3
2
H-H
2
1
2.7 Hz), 4.30 (m, 1H, CH=, Cp), 4.33 (d, 1H, CH , J = 12.7 Hz), 4.34 (s, 5H, CH=,
2 H-H
Cp), 4.45 (m, 1H, CH=, Cp), 7.0-7.2 (m, 3H, CH=), 7.4-7.6 (m, 6H, CH=), 7.7-7.8 (m,
1
3
1
2
H, CH=),7.8-7.9 (m, 2H, CH=). C{ H} NMR (100 MHz, CDCl ), δ: 22.2 (CH ),
3
3
3
3.6 (CH ) 69.2 (d, J = 10.3 Hz, CH=, Cp), 70.9 (CH=, Cp), 73.3 (d, JC-P = 9.2 Hz,
2
C-P
CH=, Cp), 74.4 (d, JC-P = 95.1Hz, C, Cp), 74.5 (d, JC-P = 12.5 Hz, CH=, Cp), 89.6 (d, JC-
12.2 Hz, C, Cp), 128.0 (CH=), 128.1 (CH=), 128.1 (CH=), 128.2 (CH=), 131.2 (d,
JC-P = 3.5 Hz, CH=), 131.3 (d, JC-P = 3.5 Hz, CH=), 132.1 (d, JC-P = 10.8 Hz, CH=),
=
P
1
8
32.3 (d, JC-P = 10.7 Hz, CH=),133.5 (d, JC-P = 85.5 Hz, C), 134.2 (C), 134.4 (d, JC-P =
6.6 Hz, C), 143.2 (C).
3
1
1
9
: Yield 101 mg (91%). P NMR (162 MHz, CDCl ), δ: -24.0. H NMR (400 MHz,
3
2
CDCl ), δ: 2.43 (s, 6H, CH ), 3.46 (d, 1H, CH , J = 11.2 Hz), 3.79 (b, 1H, CH=,
3
3
2
H-H
2
Cp), 3.84 (d, 1H, CH , J = 11.2 Hz), 4.00 (s, 5H, CH=, Cp), 4.27 (b, 1H, CH=, Cp),
2
H-H
4
7
1
.37 (b, 1H, CH=, Cp), 7.07 (m, 3H, CH=), 7.39 (m, 5H, CH=), 7.55 (m, 3H, CH=),
13
1
.59 (m, 2H, CH=). C{ H} NMR (100 MHz, CDCl ), δ: 22.0 (CH ), 34.3 (d, J =
C-P
3
3
2.9 Hz, CH ) 69.6 (CH=, Cp), 69.7 (CH=, Cp), 71.3 (b, CH=, Cp), 75.9 (d, JC-P = 7.6
2
Hz, C, Cp), 90.4 (d, JC-P = 25.9 Hz, C, Cp), 127.8 (CH=), 127.9 (CH=), 128.0 (CH=),
1
1
1
28.1 (CH=), 128.2 (CH=), 129.1 (CH=), 132.5 (d, JC-P = 18.2 Hz, CH=), 134.2 (C),
35.2 (d, JC-P = 21.3 Hz, CH=), 137.6 (d, JC-P = 8.3 Hz, C), 139.7 (d, JC-P = 9.1 Hz, C),
+
43.1 (C). TOF-MS (ESI+): m/z = 520.1074, calcd. for C H FePS [M] : 520.1077).
3
1
29
General procedure for the preparation of [Ir(cod)(1-12)]BArF
The corresponding ligand (0.074 mmol) was dissolved in CH Cl (5 mL) and [Ir(µ-
2
2
Cl)(cod)] (25.0 mg, 0.037 mmol) was added. The reaction mixture was refluxed at 40
2
ºC for 1 hour. After 5 min at room temperature, NaBAr (77.2 mg, 0.080 mmol) and
F
water (5 mL) were added and the reaction mixture was stirred vigorously for 30 min at
1
5

ACCEPTED MANUSCRIPT
room temperature. The phases were separated and the aqueous phase was extracted
twice with CH Cl . The combined organic phases were dried with MgSO . Evaporation
2
2
4
of the solvent gave a brown-orange solid, which was purified by flash chromatography
on neutral silica (dichloromethane/petroleum ether (1/1) as eluent) to produce the
corresponding complex as an orange solid.
3
1
[
Ir(cod)(1)]BAr : Yield 105.9 mg (89%). P NMR (162 MHz, CDCl ), δ: 9.5 (s);
F
3
1
3
H NMR (400 MHz, CDCl ), δ: 1.12 (t, 3H, J
= 7.6 Hz, CH ), 1.56 (m, 1H, CH ,
3
H-H
3
2
cod), 1.71 (m, 1H, CH , cod), 2.06 (m, 1H, CH , cod), 2.32 (m, 1H, CH , cod), 2.45 (m,
2
2
2
2
3
1
1
H, CH , cod), 2.64 (m, 1H, CH , Et), 2.78 (d, 1H, J
= 12.4 Hz, CH -S), 2.91 (m,
2
2
H-H
2
2
H, CH , Et), 3.47 (m, 1H, CH=, cod), 3.57 (m, 1H, CH=, cod), 4.00 (d, 1H, J
=
2
H-H
2.4 Hz, CH -S), 4.05 (s, 1H, CH=, Cp), 4.41 (m, 1H, CH=, Cp), 4.47 (s, 6H, CH=,
2
1
3
Cp), 4.63 (m, 1H, CH=, cod), 4.94 (m, 1H, CH=, cod), 7.3-7.8 (m, 22H, CH=); C
NMR (100 MHz, CDCl ), δ: 14.6 (CH ), 27.4 (CH , cod), 29.2 (CH , cod), 31.2 (CH ),
3
3
2
2
2
1
3
1.6 (CH , cod), 33.7 (CH , Et), 35.0 (CH , cod), 63.7 (d, J = 63.6 Hz, C, Cp), 68.8
2 2 2 C-P
(d, JC-P = 5.2 Hz, CH=, Cp), 70.9 (CH=, cod and CH=, Cp), 72.3 (CH=, cod), 73.2
2
(
CH=, Cp), 76.0 (d, JC-P = 7.0 Hz¸CH=, Cp), 84.3 (d, J = 15.5 Hz, C, Cp), 90.5 (d,
C-P
JC-P = 14.6 Hz, CH=, cod), 90.7 (d, JC-P = 14.6 Hz, CH=. cod), 117.4 (b, CH=, BArF),
1
1
20.4-134.2 (aromatic carbons), 134.7 (b, CH=, BAr ), 161.7 (q, J = 48.8 Hz, C-B,
F
C-B
+
BAr ). TOF-MS (ESI+): m/z = 745.1336, calcd. for C H BF FeIrPS [M-BAr ] :
F
65 49
24
F
7
4
45.1332). Anal. calcd (%) for C H BF FeIrPS: C, 48.55; H, 3.07; S, 1.99; found: C,
65 49 24
8.34; H, 3.06; S, 1.95.
Ir(cod)(2)]BAr : Yield 108.0 mg (90%). P NMR (162 MHz, CDCl ), δ: 9.1 (s);
3
1
[
F
3
1
3
i
3
H NMR (400 MHz, CDCl ), δ: 1.18 (d, J = 6.8 Hz, 3H, CH , Pr), 1.41 (d, 3H, J
H-H
3
H-H
3
i
=
6.8 Hz, 3H, CH , Pr), 1.62 (m, 1H, CH , cod), 1.78 (m, 1H, CH , cod), 2.17 (m, 2H,
3 2 2
CH , cod), 2.41 (m, 1H, CH , cod), 2.51 (m, 2H, CH , cod), 2.57 (m, 1H, CH , cod),
2
2
2
2
2
2
i
2
.84 (d, 3H, J = 11.6 Hz, CH -S), 3.24 (q, 1H, J = 6.8 Hz, CH, Pr), 3.55 (m, 1H,
H-H 2 H-H
CH=, cod), 3.59 (m, 1H, CH=, Cp), 4.05 (d, 1H, JH-H = 11.6 Hz, CH -S), 4.08 (s, 1H,
2
CH=, Cp), 4.47 (s, 1H, CH=, Cp), 4.54 (s, 5H, CH=, Cp), 4.57 (s, 1H, CH=, Cp), 4.81
1
3
(
m, 1H, CH=, cod), 5.04 (m, 1H, CH=, cod), 7.4-7.8 (m, 22H, CH=); C NMR (100
1
6

ACCEPTED MANUSCRIPT
i
i
MHz, CDCl ), δ: 21.7 (CH , Pr), 23.1 (CH , Pr), 24.8 (b, CH S), 27.3 (CH , cod), 29.0
3
3
3
2
2
i
1
(
CH , cod), 31.5 (CH , cod), 35.2 (b, CH , cod), 43.3 (CH, Pr), 63.7 (d, J = 63.9 Hz,
2 2 2 C-P
C, Cp), 68.7 (d, JC-P = 6.2 Hz, CH=, Cp), 69.9 (CH=, cod), 71.0 (CH=, Cp), 71.5 (CH=,
3
2
cod), 73.4 (d, J = 2.1 Hz, CH=, Cp), 76.2 (d, JC-P = 6.1 Hz, CH=, Cp), 84.0 (d, J
C-P
C-P
=
16.0 Hz, C, Cp), 90.3 (d, JC-P = 11.4 Hz, CH=, cod), 90.8 (d, JC-P = 11.4 Hz, CH=,
cod), 117.4 (b, CH=, BAr ), 120.4-134.2 (aromatic carbons), 134.7 (b, CH=, BAr ),
F
F
1
1
61.7 (q, J
= 50.1 Hz, C-B, BAr ). TOF-MS (ESI+): m/z = 759.1485, calcd. for
C-B
F
+
C H BF FeIrPS [M-BAr ] : 759.1489. Anal. calcd (%) for C H BF FeIrPS: C,
66
51
24
F
66 51
24
4
8.87; H, 3.17; S, 1.98; found: C, 48.69; H, 3.15; S, 1.95.
3
1
[
Ir(cod)(3)]BAr : Yield 111.9 mg (91%). P NMR (162 MHz, CDCl ), δ: 9.1 (s);
F
3
1
H NMR (400 MHz, CDCl ), δ: 1.14 (m, 2H, CH ), 1.51 (m, 4H, CH ), 1.76 (m, 1H,
3
2
2
CH ), 1.91 (m, 2H, CH ), 2.09 (m, 1H, CH ), 2.17 (m, 2H, CH ), 2.43 (m, 1H, CH ),
2
2
2
2
2
2
2
.51 (m, 2H, CH ), 2.57 (m, 1H, CH ), 2.85 (m, 1H, CH-S), 2.90 (d, 1H, J = 10.8
H-H
2
2
2
Hz, CH -S), 3.51 (m, 1H, CH=, cod), 3.54 (m, 1H, CH=, cod), 4.06 (d, 1H, J = 10.8
2
H-H
Hz, CH -S), 4.08 (s, 1H, CH=, Cp), 4.46 (b, 1H, CH=, Cp), 4.53 (s, 6H, CH=, Cp), 4.76
2
1
3
(
m, 1H, CH=, cod), 5.04 (m, 1H, CH=, cod), 7.4-7.8 (m, 22H, CH=); C NMR (100
3
MHz, CDCl ), δ: 24.4 (CH ), 26.0 (d, J = 3.8 Hz, CH -S), 27.1 (CH ), 27.3 (CH ),
3
2
C-P
2
2
2
3
2
8.7 (CH ), 29.7 (CH ), 31.5 (CH ), 32.3 (CH ), 34.1 (CH ), 35.2 (d, J = 3.8 Hz,
2 2 2 2 2 C-P
1
CH -S), 51.9 (CH-S), 64.2 (d, J = 63.8 Hz, C, Cp), 68.6 (d, JC-P = 6.1 Hz, CH=, Cp),
2
C-P
6
9.6 (CH=, cod), 71.0 (CH=, Cp), 71.3 (CH=, cod), 73.3 (d, JC-P = 3.1 Hz, CH=, Cp),
2
7
6.1 (d, JC-P = 6.9 Hz, CH=, Cp), 84.4 (d, J = 16.7 Hz, C, Cp), 90.2 (d, JC-P = 11.4
C-P
Hz, CH=, cod), 90.7 (d, JC-P = 11.4 Hz, CH=, cod), 117.4 (b, CH=, BAr ), 120.4-134.3
F
1
(
aromatic carbons), 134.7 (b, CH=, BAr ), 161.7 (q, J = 50.1 Hz, C-B, BAr ). TOF-
F
C-B
F
+
MS (ESI+): m/z = 799.1779, calcd. for C H BF FeIrPS [M-BAr ] : 799.1802. Anal.
6
9
55
24
F
calcd (%) for C H BF FeIrPS: C, 49.86; H, 3.34; S, 1.93; found: C, 49.76; H, 3.31; S,
6
9
55
24
1
.90.
Ir(cod)(4)]BAr : Yield 108.9 mg (90%). P NMR (162 MHz, CDCl ), δ: 10.3 (s);
3
1
[
F
3
1
t
H NMR (400 MHz, CDCl ), δ: 1.35 (s, 9H, CH , Bu), 1.52 (m, 1H, CH , cod), 1.69
3
3
2
(
m, 1H, CH , cod), 2.18 (m, 2H, CH , cod), 2.37 (m, 1H, CH , cod), 2.53 (m, 3H, CH ,
2 2 2 2
1
7

ACCEPTED MANUSCRIPT
2
2
cod), 2.80 (d, 1H, J = 12.0 Hz, CH -S), 3.51 (m, 2H, CH=, cod), 4.15 (d, 1H, J =
H-H
H-H
2
1
2.0 Hz, CH -S), 4.17 (s, 1H, CH=, Cp), 4.48 (s, 1H, CH=, Cp), 4.56 (m, 6H, CH=,
2
1
3
Cp), 5.35 (m, 1H, CH=, cod), 5.45 (m, 1H, CH=, cod), 7.4-7.8 (m, 22H, CH=); C
NMR (100 MHz, CDCl ), δ: 27.4 (CH , cod), 28.4 (d, J = 2.4 Hz, CH , cod), 30.3 (d,
3
2
C-P
2
3
t
JC-P = 4.6 Hz ,CH -S), 31.8 (CH , Bu), 32.1 (d, J = 2.3 Hz, CH , cod), 35.7 (d, J =
C-P
2
3
C-P
2
t
1
4
.7 Hz, CH , cod), 59.1 (C, Bu), 62.6 (d, J = 60.4 Hz, C, Cp), 68.2 (CH=, cod), 69.0
2 C-P
(d, JC-P = 6.2 Hz, CH=, Cp), 69.1 (CH=, cod), 71.1 (CH=, Cp), 73.9 (d, JC-P = 3.1 Hz,
2
CH=, Cp), 76.5 (d, JC-P = 7.0 Hz, CH=, Cp), 84.8 (d, J = 16.3 Hz, C, Cp), 89.8 (d,
C-P
JC-P = 10.9 Hz, CH=, cod), 90.5 (d, JC-P = 11.6 Hz, CH=, cod), 117.6 (b, CH=, BArF),
1
1
20.6-134.3 (aromatic carbons), 134.9 (b, CH=, BAr ), 161.8 (q, JC-B= 50.4 Hz, C-B,
F
+
BAr ). TOF-MS (ESI+): m/z = 773.1644, calcd. for C H BF FeIrPS [M-BAr ] :
F
67 53
24
F
7
73.1645. Anal. calcd (%) for C H BF FeIrPS: C, 49.19; H, 3.27; S, 1.96; found: C,
67 53 24
4
9.11; H, 3.25; S, 1.95. Suitable crystals for X-ray diffraction were achieved by slow
diffusion of petroleum ether to an isopropanol solution.
3
1
[
Ir(cod)(5)]BAr : Yield 114.2 mg (90%). P NMR (162 MHz, CDCl ), δ: 10.3 (s);
F
3
1
H NMR (400 MHz, CDCl ), δ: 1.28 (m, 1H, CH), 1.48 (m, 1H, CH , cod), 1.59-1.72
3
2
(
m, 6H, CH ), 1.84 (m, 4H, CH ), 2.05-2.17 (m, 6H, CH ), 2.19 (m, 3H, CH , cod), 2.33
2 2 2 2
2
(
m, 1H, CH , cod), 2.53 (m, 2H, CH , cod), 2.58 (m, 1H, CH , cod), 2.82 (d, 1H, J
=
=
2
2
2
H-H
2
1
1
4
2.4 Hz, CH -S), 4.17 (s, 1H, CH=, Cp), 3.48 (m, 2H, CH=, cod), 4.13 (d, 1H, J
2
H-H
2.4 Hz, CH -S), 4.18 (b, 1H, CH=, Cp), 4.46 (b, 1H, CH=, Cp), 4.51 (b, 1H, CH=, Cp),
2
1
3
.55 (s, 5H, CH=, Cp), 5.49 (m, 2H, CH=, cod), 7.4-7.8 (m, 22H, CH=); C NMR (100
MHz, CDCl ), δ: 22.6 (CH , Ad), 27.2 (CH , cod), 27.8 (d, J = 4.6 Hz, CH , cod),
3
2
2
C-P
2
2
7.9 (CH -S), 30.5 (CH , Ad), 32.0 (CH , cod), 35.3 (CH , Ad), 35.6 (d, J = 4.5 Hz,
2 2 2 2 C-P
1
CH , cod), 43.9 (CH , Ad), 62.7 (d, J = 63.8 Hz, C, Cp), 67.4 (CH=, cod), 68.6
2
2
C-P
(CH=,cod), 68.7 (d, JC-P = 6.0 Hz, CH=, Cp), 70.9 (CH=, Cp), 73.6 (d, JC-P = 3.8 Hz,
2
CH=, Cp), 76.2 (d, JC-P = 7.6 Hz, CH=, Cp), 84.7 (d, J = 16.7 Hz, C, Cp), 89.7 (d,
C-P
JC-P = 10.6 Hz, CH=, cod), 90.5 (d, JC-P = 12.2 Hz, CH=, cod), 117.4 (b, CH=, BArF),
1
1
20.4-134.4 (aromatic carbons), 134.7 (b, CH=, BAr ), 161.7 (q, J = 50.2 Hz, C-B,
F
C-B
+
BAr ). TOF-MS (ESI+): m/z = 851.2112, calcd. for C H BF FeIrPS [M-BAr ] :
F
73 59
24
F
1
8

ACCEPTED MANUSCRIPT
8
51.2115. Anal. calcd (%) for C H BF FeIrPS: C, 51.15; H, 3.47; S, 1.87; found: C,
7
3
59
24
5
1.11; H, 3.44; S, 1.85.
Ir(cod)(6)]BAr : Yield 109.1 mg (89%). P NMR (162 MHz, CDCl ), δ: 8.8 (s);
3
1
[
F
3
1
H NMR (400 MHz, CDCl ), δ: 1.72 (m, 2H, CH , cod), 1.96 (m, 1H, CH -S, cod), 2.24
3
2
2
2
(
m, 1H, CH , cod), 2.46 (m, 2H, CH , cod), 2.57 (m, 2H, CH , cod), 3.31 (d, 1H, J
=
2
2
2
H-H
1
2.8 Hz, CH ), 3.70 (m, 1H, CH=, cod), 3.72 (m, 1H, CH=, cod), 3.94 (m, 1H, CH=,
2
2
cod), 4.17 (s, 1H, CH=, Cp), 4.43 (d, 1H, JH-H = 12.8 Hz, CH ), 4.51 (s, 1H, CH=, Cp),
2
4
.59 (s, 1H, CH=, Cp), 4.65 (s, 5H, CH=, Cp), 4.88 (m, 1H, CH=, cod), 7.3-7.8 (b, 27H,
1
3
CH=); C NMR (100 MHz, CDCl ), δ: 27.1 (CH , cod), 29.8 (d, J = 2.4 Hz, CH2,
3
2
C-P
3
cod), 30.9 (d, JC-P = 2.4 Hz, CH , cod), 34.8 (d, J = 4.6 Hz, CH , cod), 38.7 (d, J =
C-P
2
C-P
2
1
3
.5 Hz, CH -S), 64.2 (d, J = 63.6 Hz, C, Cp), 68.6 (d, JC-P = 7.0 Hz, CH=, Cp), 70.9
2 C-P
(CH=, cod), 71.1 (CH=, Cp), 72.9 (CH=, cod), 73.5 (d, JC-P = 3.2 Hz, CH=, Cp), 76.2
2
(
d, JC-P = 6.2 Hz, CH=, Cp), 84.0 (d, JC-P = 16.3 Hz, C, Cp), 90.8 (d, JC-P = 11.7 Hz,
CH=, cod), 94.4 (d, JC-P = 10.8 Hz, CH=, cod), 117.4 (b, CH=, BAr ), 120.4-134.2
F
1
(
aromatic carbons), 134.7 (b, CH=, BAr ), 161.6 (q, J = 49.6 Hz, C-B, BAr ). TOF-
F
C-B
F
+
MS (ESI+): m/z = 793.1330, calcd. for C H BF FeIrPS [M-BAr ] : 793.1332. Anal.
6
9
49
24
F
calcd (%) for C H BF FeIrPS: C, 50.04; H, 2.98; S, 1.94; found: C, 49.98; H, 2.96; S,
6
9
49
24
1
.92.
Ir(cod)(7)]BAr : Yield 112.5 mg (91%). P NMR (162 MHz, CDCl ), δ: 8.9 (s);
3
1
[
F
3
1
H NMR (400 MHz, CDCl ), δ: 1.71 (m, 2H, CH , cod), 1.85 (m, 1H, CH , cod), 2.21
3
2
2
2
(
m, 2H, CH , cod), 2.41 (m, 1H, CH , cod), 2.54 (m, 3H, CH , cod), 2.67 (d, 1H, J
=
=
2
2
2
H-H
2
1
1
1
5
2.4 Hz, CH ), 3.64 (m, 1H, CH=, cod), 3.72 (m, 1H, CH=, cod), 3.76 (d, 1H, J
2
H-H
2
2.4 Hz, CH ), 3.83 (d, 1H, J = 13.2 Hz, CH -Ph), 4.11 (s, 1H, CH=, Cp), 4.22 (d,
2
H-H
2
2
H, J
= 13.2 Hz, CH -Ph), 4.41 (s, 1H, CH=, Cp), 4.42 (s, 1H, CH=, Cp), 4.47 (s,
2
H-H
H, CH=, Cp), 4.90 (m, 1H, CH=, cod), 5.13 (m, 1H, CH=, cod), 7.1-7.8 (b, 27H,
1
3
CH=); C NMR (100 MHz, CDCl ), δ: 27.9 (d, J = 1.6 Hz, CH , cod), 29.6 (d, J =
C-P
3
C-P
2
2
3
.4 Hz, CH , cod), 31.8 (d, J = 2.3 Hz, CH , cod), 32.8 (d, J = 4.7 Hz, CH -S),
2 C-P 2 C-P 2
1
5.1 (d, JC-P = 4.7 Hz, CH , cod), 44.5 (CH -Ph), 64.5 (d, J = 63.6 Hz, C, Cp), 69.1
2
2
C-P
(d, JC-P = 7.0 Hz, CH=, Cp), 71.2 (CH=, Cp), 72.1 (CH=, cod), 73.4 (CH=, cod), 73.5
1
9

ACCEPTED MANUSCRIPT
2
(
d, JC-P = 3.9 Hz, CH=, Cp), 76.2 (d, JC-P = 7.0 Hz, CH=, Cp), 84.3 (d, J = 16.3 Hz,
C-P
C, Cp), 90.7 (d, JC-P = 11.6 Hz, CH=, cod), 91.2 (d, JC-P = 11.6 Hz, CH=, cod), 117.6 (b,
1
CH=, BAr ), 120.6-134.2 (aromatic carbons), 135.0 (b, CH=, BAr ), 161.8 (q, J
=
F
F
C-B
4
9.7 Hz, C-B, BAr ). TOF-MS (ESI+): m/z = 807.1488, calcd. for C H BF FeIrPS
F 70 51 24
+
[
M-BAr ] : 807.1489. Anal. calcd (%) for C H BF FeIrPS: C, 50.34; H, 3.08; S,
F
70 51
24
1
.92; found: C, 50.27; H, 3.06; S, 1.89.
3
1
[
Ir(cod)(8)]BAr : Yield 114.9 mg (91%). P NMR (162 MHz, CDCl ), δ: 6.6 (s);
F
3
1
H NMR (400 MHz, CDCl ), δ: 1.62 (m, 3H, CH , cod), 1.78 (m, 2H, CH , cod), 2.28
3
2
2
(
m, 3H, CH , cod and CH -S), 2.46 (m, 1H, CH , cod, and CH -S), 3.71 (m, 1H, CH=,
2 2 2 2
Cp), 3.86 (m, 1H, CH=, cod), 4.04 (m, 1H, CH=, cod), 4.26 (m, 1H, CH=, cod), 4.51
m, 1H, CH=, Cp), 4.59 (s, 1H, CH=, Cp), 4.69 (s, 5H, CH=, Cp), 4.70 (m, 1H, CH=,
(
1
3
cod), 7.4-7.9 (b, 29H, CH=); C NMR (100 MHz, CDCl ), δ: 27.8 (b, CH , cod), 29.7
3
2
1
(
b, CH , cod), 30.2 (b, CH , cod), 31.4 (CH -S), 33.4 (CH -S), 64.3 (d, J = 64.2 Hz,
2 2 2 2 C-P
C, Cp), 68.7 (d, JC-P = 6.4 Hz, CH=, Cp), 71.3 (CH=, Cp and CH=, cod), 73.8 (CH=,
2
cod), 76.3 (d, JC-P = 5.9 Hz, CH=, Cp), 84.9 (d, J = 20.4 Hz, C, Cp), 90.9 (d, JC-P
=
C-P
1
0.8 Hz, CH=, cod), 95.0 (d, JC-P = 12.2 Hz, CH=, cod), 117.4 (b, CH=, BAr ), 120.4-
F
1
1
34.2 (aromatic carbons), 134.8 (b, CH=, BAr ), 161.7 (q, J = 49.4 Hz, C-B, BArF).
F
C-B
+
TOF-MS (ESI+): m/z = 843.1487, calcd. for C H BF FeIrPS [M-BAr ] : 843.1489.
7
3
51
24
F
Anal. calcd (%) for C H BF FeIrPS: C, 51.39; H, 3.01; S, 1.88; found: C, 51.33; H,
7
3
51
24
3
1
1
2
.99; S, 1.85. Major isomer (66%): P NMR (162 MHz, CDCl , 228 K), δ: 6.7 (s); H
3
NMR (400 MHz, CDCl , 228 K), δ: 1.5 - 2.5 (b, 8H, CH , cod), 3.64 (m, 2H, CH=,
3
2
2
cod), 3.70 (d, 1H, J = 12.0 Hz, CH ), 3.88 (m, 1H, CH=, cod), 3.99 (b, 1H, CH=,
H-H
2
2
Cp), 4.17 (d, 1H, J = 12.0 Hz, CH ), 4.50 (b, 1H, CH=, Cp), 4.60 (m, 1H, CH=, Cp),
H-H
2
4
.63 (b, 1H, CH=, cod), 4.67 (s, 5H, CH=, Cp), 6.6-8.5 (m, 29H, CH=). Minor isomer
3
1
1
(
33%): P NMR (162 MHz, CDCl , 228 K), δ: 8.8 (s); H NMR (400 MHz, CDCl , 228
3
3
2
K), δ: 1.5 - 2.7 (b, 8H, CH , cod), 3.28 (d, 1H, J = 12.0 Hz, CH ), 3.64 (m, 2H, CH=,
2
H-H
2
cod), 3.94 (m, 1H, CH=, cod), 4.20 (b, 1H, CH=, Cp), 4.45 (b, 1H, CH=, Cp), 4.60 (b,
H, CH=, Cp), 4.73 (s, 5H, CH=, Cp), 4.88 (m, 1H, CH=, cod), 6.6-8.5 (m, 29H, CH=).
1
2
0

ACCEPTED MANUSCRIPT
3
1
[
Ir(cod)(9)]BAr : Yield 113.4 mg (91%). P NMR (162 MHz, CDCl ), δ: 5.9 (s);
F
3
1
H NMR (400 MHz, CDCl ), δ: 1.76 (m, 2H, CH , cod), 2.06 (m, 1H, CH , cod), 2.20
3
2
2
(
s, 3H, CH ), 2.29 (m, 3H, CH , cod), 2.41 (m, 1H, CH , cod), 2.56 (m, 1H, CH , cod),
3 2 2 2
2
2
1
4
.78 (s, 3H, CH ), 3.42 (d, 1H, J = 13.2 Hz, CH ), 3.70 (m, 1H, CH=, cod), 3.83 (m,
3 H-H 2
2
H, CH=, cod), 3.92 (m, 2H, CH=, cod and Cp), 3.99 (d, 1H, JH-H = 13.2 Hz, CH2),
1
3
.51 (m, 2H, CH=, cod and Cp), 4.65 (s, 6H, CH=, Cp), 7.1-7.8 (b, 25H, CH=); C
NMR (100 MHz, CDCl ), δ: 22.9 (CH ), 23.1 (CH ), 27.9 (b, CH , cod), 30.6 (b, CH ,
3
3
3
2
2
cod), 30.8 (d, JC-P = 2.3 Hz, CH , cod), 33.9 (d, J = 4.6 Hz, CH , cod), 35.2 (b, CH -
2
C-P
2
2
1
S), 64.1 (d, J = 63.9 Hz, C, Cp), 68.5 (CH=, cod), 68.7 (d, JC-P = 6.1 Hz, CH=, Cp),
C-P
7
1.2 (CH=, Cp), 73.0 (CH=, cod), 73.9 (d, JC-P = 2.1 Hz, CH=, Cp), 76.3 (d, JC-P = 7.8
2
Hz, CH=, Cp), 85.3 (d, JC-P = 16.0 Hz, C, Cp), 89.9 (d, JC-P = 12.2 Hz, CH=, cod), 94.2
(
d, JC-P = 11.4 Hz, CH=, cod), 117.4 (b, CH=, BAr ), 120.4-134.0 (aromatic carbons),
F
1
1
34.7 (b, CH=, BAr ), 140.3 (C), 142.0 (C), 161.6 (q, J
= 49.6 Hz, C-B, BArF).
F
C-B
+
TOF-MS (ESI+): m/z = 821.1642, calcd. for C H BF FeIrPS [M-BAr ] : 821.1645.
7
1
53
24
F
Anal. calcd (%) for C H BF FeIrPS: C, 50.64; H, 3.17; S, 1.90; found: C, 50.61; H,
7
1
53
24
3
.16; S, 1.88.
Ir(cod)(10)]BAr : Yield 108.0 mg (90%). P NMR (162 MHz, CDCl ), δ: 25.0 (s);
3
1
[
F
3
1
t
H NMR (400 MHz, CDCl ), δ: 1.09 (s, 9H, CH , Bu), 1.68 (m, 1H, CH , cod), 1.84
3
3
2
(
m, 1H, CH , cod), 2.16 (m, 2H, CH , cod), 2.32 (m, 1H, CH , cod), 2.42 (m, 1H, CH ,
2 2 2 2
cod), 2.52 (m, 2H, CH , cod), 3.79 (m, 1H, CH=, cod), 4.32 (s, 5H, CH=, Cp), 4.49 (b,
2
1
H, CH=, Cp), 4.60 (m, 1H, CH=, cod), 4.79 (m, 1H, CH=, cod), 4.95 (b, 1H, CH=,
1
3
Cp), 5.21 (s, 1H, CH=, Cp), 5.54 (s, 1H, CH=, cod), 7.3-7.8 (m, 22H, CH=); C NMR
(
100 MHz, CDCl ), δ: 27.4 (d, J = 2.3 Hz, CH , cod), 29.1 (d, J = 2.2 Hz, CH2,
3
C-P
2
C-P
t
cod), 31.0 (CH , Bu), 33.2 (b, CH , cod), 35.5 (d, J = 4.5 Hz, CH , cod), 61.8 (C,
3
2
C-P
2
t
Bu), 70.8 (CH=, Cp), 71.7 (CH=, cod), 72.7 (CH=, Cp), 73.2 (CH=, cod), 73.6 (d, JC-P
1
=
9.1 Hz, CH=, Cp), 79.2 (d, J = 62.1 Hz, C, Cp), 80.2 (d, JC-P = 14.5 Hz, CH=, Cp),
C-P
2
8
5.2 (d, J = 26.4 Hz, C, Cp), 86.4 (d, JC-P = 14.5 Hz, CH=, cod), 94.3 (d, JC-P = 9.9
C-P
Hz, CH=, cod), 117.4 (b, CH=, BAr ), 120.4-133.1 (aromatic carbons), 134.7 (b, CH=,
F
BAr ), 161.7 (q, J = 49.4 Hz, C-B, BAr ). TOF-MS (ESI+): m/z = 759.1484, calcd.
F
C-B
F
2
1

ACCEPTED MANUSCRIPT
+
for C H BF FeIrPS [M-BAr ] : 759.1489. Anal. calcd (%) for C H BF FeIrPS: C,
6
6
51
24
F
66 51
24
4
8.87; H, 3.17; S, 1.98; found: C, 48.81; H, 3.15; S, 1.94.
3
1
[
Ir(cod)(11)]BAr : Yield 111.2 mg (90%). P NMR (162 MHz, CDCl ), δ: 3.9 (s);
F
3
1
3
H NMR (400 MHz, CDCl ), δ: 0.71 (d, 3H, J
= 6.8 Hz, CH ), 1.69 (m, 2H, CH ,
3
H-H
3
2
cod), 2.01 (m, 1H, CH , cod), 2.17 (m, 1H, CH , cod), 2.42 (m, 2H, CH , cod), 2.46 (m,
2
2
2
1
H, CH , cod), 2.56 (m, 1H, CH , cod), 3.48 (m, 1H, CH=, cod), 3.54 (m, 1H, CH=,
2 2
cod), 4.11 (s, 1H, CH=, Cp), 4.32 (m, 1H, CH=, cod), 4.50 (s, 7H, CH=, Cp), 4.61 (q,
3
13
1
H, J = 6.8 Hz, CH), 4.72 (m, 2H, CH=, cod), 7.5-7.8 (b, 22H, CH=); C NMR
H-H
(
100 MHz, CDCl ), δ: 22.9 (CH , cod), 29.7 (CH , cod), 31.0 (CH , cod), 34.9 (CH ,
3 2 2 2 2
1
cod), 47.7 (CH), 63.5 (d, JC-P = 61.5 Hz, C, Cp), 69.1 (d, JC-P =6.9 Hz, CH=, Cp), 70.9
(CH=, cod), 71.5 (CH=, Cp), 72.1 (CH=,cod), 74.1 (CH=, cod), 74.5 (d, JC-P = 6.1 Hz,
2
CH=, Cp), 90.8 (d, J = 16.7 Hz, C, Cp), 93.4 (d, JC-P = 10.6 Hz, CH=, cod), 93.8 (d,
C-P
JC-P = 10.6 Hz, CH=, cod), 117.4 (b, CH=, BAr ), 120.4-134.2 (aromatic carbons),
F
1
1
34.7 (b, CH=, BAr ), 135.0 (CH=, Cp), 161.7 (q, J = 49.8 Hz, C-B, BAr ). TOF-
F
C-B
F
+
MS (ESI+): m/z = 807.1488, calcd. for C H BF FeIrPS [M-BAr ] : 807.1489. Anal.
7
0
51
24
F
calcd (%) for C H BF FeIrPS: C, 50.34; H, 3.08; S, 1.92; found: C, 50.31; H, 3.06; S,
7
0
51
24
1
.90.
[
Ir(cod)(12)]BAr : Yield 111.9 mg (89%). TOF-MS (ESI+): m/z = 835.1801, calcd.
F
+
for C H BF FeIrPS [M-BAr ] : 835.1802. Anal. calcd (%) for C H BF FeIrPS: C,
7
2
55
24
F
72 55
24
3
1
5
0.93; H, 3.26; S, 1.89; found: C, 50.88; H, 3.24; S, 1.84. Major isomer (85%): P
1
3
NMR (162 MHz, CDCl ), δ: 3.0 (s); H NMR (400 MHz, CDCl ), δ: 0.71 (d, 3H, J
H-H
3
3
=
6.8 Hz, CH ), 1.83 (m, 2H, CH , cod), 2.10 (m, 1H, CH , cod), 2.30 (m, 1H, CH ,
3 2 2 2
cod), 2.39 (m, 2H, CH , cod), 2.46 (m, 1H, CH , cod), 2.57 (m, 1H, CH , cod), 2.62 (s,
2
2
2
3
4
H, CH -Ar), 2.79 (s, 3H, CH -Ar), 3.36 (m, 1H, CH=, cod), 3.58 (m, 1H, CH=, cod),
3 3
.00 (m, 1H, CH=, cod), 4.11 (b, 1H, CH=, Cp), 4.52 (s, 6H, CH=, Cp), 4.62 (m, 2H,
1
3
CH and CH=, Cp), 4.64 (m, 1H, CH=, cod), 7.2-7.7 (m, 25H, CH=); C NMR (100
MHz, CDCl ), δ: 21.2 (CH ), 23.1 (CH -Ar), 24.8 (CH -Ar), 26.8 (CH , cod), 29.8
3
3
3
3
2
1
(
CH , cod), 31.2 (CH , cod), 34.8 (d, J = 3.2 Hz, CH , cod), 47.0 (CH), 63.8 (d, J
2 2 C-P 2 C-P
=
61.5 Hz, C, Cp), 69.0 (d, JC-P =6.9 Hz, CH=, Cp), 69.7 (CH=, cod), 70.3 (CH=,cod),
2
2

ACCEPTED MANUSCRIPT
7
9
1.4 (CH=, Cp), 74.3 (d, JC-P = 6.9 Hz, CH=, Cp), 74.8 (d, JC-P = 3.8 Hz, CH=, Cp),
2
0.8 (d, J = 16.8 Hz, C, Cp), 92.6 (d, JC-P = 11.4 Hz, CH=, cod), 94.2 (d, JC-P = 10.6
C-P
Hz, CH=, cod), 117.4 (b, CH=, BAr ), 120.4-134.7 (aromatic carbons), 134.7 (b, CH=,
F
1
BAr ), 140.4-143.9 (aromatic carbons), 161.9 (q, J = 49.4 Hz, C-B, BAr ). Minor
F
C-B
F
3
1
1
isomer (15%): P NMR (162 MHz, CDCl ), δ: 5.7 ppm (s); H NMR (400 MHz,
3
3
CDCl ), δ: 1.35 (d, 3H, J
= 6.8 Hz, CH ), 1.92 (m, 1H, CH , cod), 2.11 (m, 1H,
3 2
3
H-H
CH , cod), 2.23 (s, 3H, CH -Ar), 2.2 - 2.6 (m, 6H, CH , cod), 2.74 (s, 3H, CH -Ar),
2
3
2
3
3
.63 (m, 2H, CH and CH=, cod), 3.75 (m, 2H, CH=, cod), 3.93 (m, 1H, CH=, Cp), 4.52
(b, 1H, CH=, cod), 4.56 (m, 1H, CH=, Cp), 4.66 (s, 5H, CH=, Cp), 4.73 (m, 1H, CH=,
1
3
Cp), 7.2-7.7 (m, 25H, CH=); C NMR (100 MHz, CDCl ), δ: 17.1 (CH ), 22.8 (CH -
3
3
3
Ar), 23.7 (CH -Ar), 27.6 (CH , cod), 29.6 (CH , cod), 34.3 (d, J = 3.3 Hz, CH , cod),
3
2
2
C-P
2
1
4
2.8 (CH), 64.8 (d, J = 60.8 Hz, C, Cp), 69.3 (b, CH=, Cp), 71.1 (CH=, Cp), 72.3
C-P
(CH=,cod), 74.4 (d, JC-P =5.8 Hz, CH=, Cp), 75.2 (d, JC-P = 3.2 Hz, CH=, Cp), 89.3 (d,
2
JC-P = 19.1 Hz, C, Cp), 90.1 (d, JC-P = 10.4 Hz, CH=, cod), 95.7 (d, JC-P = 14.3 Hz,
1
CH=, cod), 134.7 (b, CH=, BAr ), 140.4-143.9 (aromatic carbons), 161.7 (q, J
=
F
C-B
4
9.4 Hz, C-B, BArF).
General procedure for the hydrogenation of olefins
The alkene (0.5 mmol) and Ir complex (1 mol %) were dissolved in CH Cl (2 mL)
2
2
in a high-pressure autoclave, which was purged four times with hydrogen. Then, it was
pressurized to the desired pressure. After the desired reaction time, the autoclave was
depressurized and the solvent evaporated off. The residue was dissolved in Et O (1.5
2
ml) and filtered through a short Celite plug. The enantiomeric excess was determined by
1
chiral GC or chiral HPLC and conversions were determined by H NMR. The
10a
37
10a
o
enantiomeric excesses of hydrogenated products from S1-S5, S6, S7, S8-S9,5
3
8
o
39
40
i
v
26a
27b
28a
41
10a
S10, S11,5 S12, S13, S14,5 S15-S16,5 S17, S18, S19-S23, S24, S25,
4
2
29a
28a
S26-S32, S33, S34, were determined using the conditions described previously.
2
3

ACCEPTED MANUSCRIPT
Acknowledgements
We thank the Spanish Government for providing grant CTQ2013-40568, the Catalan
Government for grant 2014SGR670, and the ICREA Foundation for providing M.
Diéguez and O. Pàmies with financial support through the ICREA Academia awards.
We also thank the Centre National de la Recherche Scientifique, the Institut
Universitaire de France, and the Laboratoire Européen Associé “Laboratoire Trans-
Pyrénéen: de la Molécule aux Matériaux” for additional support.
References
1
a) Comprehensive Asymmetric Catalysis; Eds.: Jacobsen, E. N.; Pfaltz, A.; Yamamoto;
H.; Springer-Verlag: Berlin, 1999; b) Catalytic Asymmetric Synthesis; 3rd Edition; Ed.:
Ojima, I.; John Wiley & Sons, Inc.: Hoboken, 2010; c) Asymmetric Catalysis in
Industrial Scale: Challenges, Approaches and Solutions; 2nd Ed; Eds.: Blaser, H. U.;
Federsel, H.-J.; Wiley: Weinheim, Germany, 2010; d) Asymmetric Catalysis in Organic
Synthesis; Ed.: Noyori; R.: Wiley: New York, 1994; e) Busacca, C. A.; Fandrick, D. R.;
Song, J. J.; Senanayakl, C. H. Adv. Synth. Catal. 2011, 353, 1825.
2
a) Brown, J. M. in Comprehensive Asymmetric Catalysis; Eds.: Jacobsen, E. N.; Pfaltz,
A.; Yamamoto, H.; Springer-Verlag: Berlin, 1999; Vol. I, pp 121-182. b) Wang, D.-S.;
Chen, Q.-A.; Lu, S.-M.; Zhou, Y.-G. Chem. Rev. 2012, 112, 2557. d) Knowles, W. S.;
Noyori, R. Acc. Chem. Res. 2007, 40, 1238.
3
For reviews, see: a) Cui, X.; Burgess, K. Chem. Rev. 2005, 105, 3272. b) Källström,
K.; Munslow, I.; Andersson, P. G. Chem. Eur. J. 2006, 12, 3194. c) Roseblade, S. J.;
Pfaltz, A. Acc. Chem. Res. 2007, 40, 1402. d) Church, T. L.; Andersson, P. G. Coord.
Chem. Rev. 2008, 252, 513. e) Pàmies, O.; Andersson, P. G.; Diéguez, M. Chem. Eur. J.
2
010, 16, 14232. f) Woodmansee, D. H.; Pfaltz, A. Chem. Commun. 2011, 47, 7912. g)
Zhu, Y.; Burgess, K. Acc. Chem. Res. 2012, 45, 1623. h) Verendel, J. J.; Pàmies, O.;
Diéguez, M.; Andersson, P. G. Chem. Rev. 2014, 114, 2130.
4
Lightfoot, A.; Schnider, P.; Pfaltz, A. Angew. Chem. Int. Ed. 1998, 37, 2897.
2
4

ACCEPTED MANUSCRIPT
5
See, for instance: a) Blankenstein, J.; Pfaltz, A. Angew. Chem. Int. Ed. 2001, 40, 4445.
b) Hou, D.-R.; Reibenspies, J.; Colacot, T. J.; Burgess, K. Chem. Eur. J. 2001, 7, 5391.
c) Menges, F.; Pfaltz, A. Adv. Synth. Catal. 2002, 344, 40. d) Perry, M. C.; Cui, X.;
Powell, M. T.; Hou, D.-R.; Reibenspies, J. H.; Burgess, K. J. Am. Chem. Soc. 2003,
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These ligands have been applied in allylic substitution reactions,
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Fesulphos ligand 10 has been successfully used in several asymmetric metal-
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See for example: a) Judge, T. M.; Phillips, G.; Morris, J. K.; Lovasz, K. D.; Romines,
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(
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