A phosphite-pyridine/iridium complex library as highly selective catalysts for the hydrogenation of minimally functionalized olefins

Article abstract of DOI:10.1002/adsc.201201017

A modular library of readily available phosphite-pyridine ligands has been successfully applied for the first time in the iridium-catalyzed asymmetric hydrogenation of a broad range of minimally functionalized olefins. The modular ligand design has been shown to be crucial in finding highly selective catalytic systems for each substrate. Excellent enantioselectivities (ees up to 99%) have therefore been obtained in a wide range of E- and Z-trisubstituted alkenes, including more demanding triaryl-substituted olefins and dihydronaphthalenes. This good performance extends to the very challenging class of terminal disubstituted olefins, and to olefins containing neighbouring polar groups (ees up to 99%). Both enantiomers of the reduction product can be obtained in excellent enantioselectivities by simply changing the configuration of the carbon next to the phosphite moiety. The hydrogenations were also performed using propylene carbonate as solvent, which allowed the iridium catalyst to be reused and maintained the excellent Copyright

Full text of DOI:10.1002/adsc.201201017

FULL PAPERS
DOI: 10.1002/adsc.201201017
A Phosphite-Pyridine/Iridium Complex Library as Highly
Selective Catalysts for the Hydrogenation of Minimally
Functionalized Olefins
Javier Mazuela,a Oscar Pꢀmies,a,* and Montserrat Diꢁgueza,*
a
Departament de Quꢂmica Fꢂsica i Inorgꢀnica, Universitat Rovira i Virgili, C/Marcel·lꢂ Domingo, s/n, 43007 Tarragona,
Spain
Fax : (+34)-97-755-9563; phone: (+34)-97-755-8780; e-mail: oscar.pamies@urv.cat or montserrat.dieguez@urv.cat
Received: December 3, 2012; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201201017.
Abstract: A modular library of readily available minal disubstituted olefins, and to olefins containing
phosphite-pyridine ligands has been successfully ap- neighbouring polar groups (ees up to 99%). Both
plied for the first time in the iridium-catalyzed asym- enantiomers of the reduction product can be ob-
metric hydrogenation of a broad range of minimally tained in excellent enantioselectivities by simply
functionalized olefins. The modular ligand design has changing the configuration of the carbon next to the
been shown to be crucial in finding highly selective phosphite moiety. The hydrogenations were also per-
catalytic systems for each substrate. Excellent enan- formed using propylene carbonate as solvent, which
tioselectivities (ees up to 99%) have therefore been allowed the iridium catalyst to be reused and main-
obtained in a wide range of E- and Z-trisubstituted tained the excellent enantioselectivities.
alkenes, including more demanding triaryl-substitut-
ed olefins and dihydronaphthalenes. This good per- Keywords: asymmetric catalysis; heterodonor P,N li-
formance extends to the very challenging class of ter- gands; hydrogenation; iridium; olefins
Introduction
text, Pfaltz introduced a new class of hydrogenation
catalysts, iridium complexes with chiral P,N ligands,
The major progress in the field of asymmetric cataly- which mimic the Crabtree catalyst[3] and overcome
sis has been driven by the growing demand for enan- these limitations.[2,4,5] The first successful P,N ligands[6]
tiomerically pure pharmaceuticals, agrochemicals, fla- contained a phosphine or phosphinite moiety as a P-
vours and other fine chemicals. Asymmetric hydroge- donor group and either an oxazoline,[6b,g,j] oxazole,[6d]
nation utilizing molecular hydrogen to reduce prochi- thiazole[6i] or pyridine[6c,h,t] as an N-donor group.
ral olefins has become one of the most sustainable Among these, the phosphorus/oxazoline ligands have
and reliable catalytic methods for the preparation of played a dominant role. In recent years, research has
optically active compounds, mainly because of its high focused on the design of ligands containing more
efficiency, atom economy, and operational simplici- robust N-donor groups than oxazolines. In this re-
ty.[1] Over many years the scope of this reaction has spect, the use of pyridine-containing ligands as an al-
gradually been extended in terms of reactant struc- ternative to oxazolines is of interest because of the ro-
ture and catalyst efficiency. Today, an impressive bustness and the easy incorporation of the pyridine
range of chiral phosphorus ligands (mainly diphos- group. Soon after the successful application of phos-
phines) has been developed and successfully applied phinite-oxazoline ligands,[6b] Pfaltz and co-workers de-
in Rh- and Ru-catalyzed hydrogenation. However, veloped the first generation of phosphinite-pyridine
the range of olefins that can be hydrogenated with ligands (Figure 1),[6h,7] which was successfully used in
high enantiomeric excess is limited to substrates with a limited range of alkenes. The performance was sub-
a coordinating group next to the C=C bond, because sequently further improved by introducing a more
substrate chelation to the metal plays a pivotal role in rigid chiral bicyclic ligand backbone (2nd generation,
stereodiscrimination.[1] With minimally functionalized Figure 1).[6c,8] Although the number of substrates that
olefins, these catalysts generally show low reactivity can be successfully reduced was increased with this
and unsatisfactory enantioselectivity.[1,2] In this con- 2nd generation, there is still a problem of substrate
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1
ÞÞ
These are not the final page numbers!

Javier Mazuela et al.
FULL PAPERS
moiety with a biaryl phosphite group to provide li-
gands L1–L12a–g (Figure 2).[12]
These ligands a priori combine the advantages of
both types of successful ligands for this process (phos-
phite and pyridine). They are therefore less sensitive
to air and other oxidizing agents than phosphines and
phosphinites, easy to synthesize from readily available
alcohols, and more stable than their oxazoline coun-
terparts.[13] The modular construction of these ligands
Figure 1. Phosphinite-pyridine ligand libraries developed by
Pfaltz and co-workers.
range limitation, since high enantioselectivities are allows sufficient flexibility to fine-tune the steric and
mainly limited to trisubstituted substrates.[9]
electronic properties of both the ligand backbone and
Some years ago, we discovered that the presence of the biaryl moiety in order to explore how they affect
biaryl phosphite moieties in ligand design is highly ad- catalytic performance (activity and selectivity). We
vantageous.[10] Ir/phosphite-oxazoline catalytic systems thereby studied the effect of systematically varying
provide greater substrate versatility than previous Ir the substituents in the ligand backbone (R1 and R2, li-
systems based on phosphine/phosphinite-oxazoline li- gands L1–L8), the configuration of the ligand back-
gands. However, the use of ligands that combine the bone (ligands L1–L7 vs L9–L12), and the substituents
phosphite moiety with other nitrogen donor groups and configurations in the biaryl phosphite moiety (a–
rather than oxazoline has been limited.[10d] In this con- g). As a result, the optimal combination for maximum
text, Ruffoꢄs group, together with our group, devel- activity and enantioselectivity for a wide range of E-
oped a family of pyranoside phosphite-pyridine li- and Z-trisubstituted and 1,1-disubstituted olefins was
gands for this process.[11] Nonetheless, the enantiose- obtained.
lectivities and substrate versatility were only moder-
ate. At this point it was unclear whether these unsatis-
factory results were due to the large chelate ring size Results and Discussion
(nine-membered) formed by the pyranoside ligands
or to the unsuccessful combination of phosphite and Synthesis of the Ir Catalyst Precursors
pyridine moieties in the ligand. To address this point
and in order to systematically study the possibilities The catalyst precursors were made by refluxing a di-
of phosphite-pyridine ligands in this process, we de- chloromethane solution of the appropriate ligand
cided to take the 1st generation of Pfaltzꢄs phosphin- (L1–L12a–g) in the presence of 0.5 equiv. of [Ir
(m-
À
ite-pyridine ligands and replace the phosphinite Cl)cod]2 for 1 h. The ClÀ/BArF counterion exchange
was then achieved by a reaction with sodium tetrakis-
A
(NaBArF)
(1 equiv.) in the presence of water (Scheme 1). All
complexes were isolated as air-stable orange solids in
pure form, and they were then used without further
purification.
The complexes were characterized by elemental
1
analysis and H, 13C, and 31P NMR spectroscopy. The
spectral assignments were based on information from
1H-1H and 13C-1H correlation measurements, and
were as anticipated for these C1 iridium complexes.
The VT-NMR (+408C to À708C) spectra indicate
that only one isomer is present in solution. One sin-
glet in the 31P-{1H} NMR spectra was obtained in all
cases.[14]
_
Scheme 1. Synthesis of the [IrACTHNUTRGNENUG(cod)ACHTUGNTREN(NUGN PN)]BArF catalyst pre-
_
cursors (PN=L1–L12a–g).
Figure 2. Phosphite-pyridine ligand library L1–L12a–g.
2
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

A Phosphite-Pyridine/Iridium Complex Library as Highly Selective Catalysts for the Hydrogenation
Table 1. Ir-catalyzed hydrogenation of S1 and S2 using li-
gands L1–L12a–g.[a]
Asymmetric Hydrogenation of Trisubstituted Olefins
Asymmetric Hydrogenation of Minimally
Functionalized Trisubstituted Olefins
Entry
Ligand
ee [%][b]
ee [%][b]
In a first set of experiments, we used the Ir-catalyzed
hydrogenation of substrates E-2-(4-methoxyphenyl)-
2-butene S1 and Z-2-(4-methoxyphenyl)-2-butene S2
to study the potential of ligands L1–L12a–g. Substrate
S1 was chosen as a model for the hydrogenation of E-
isomers because it has been reduced with a wide
range of ligands, which enable the efficiency of the
various ligand systems to be compared directly.[2] In
order to assess the potential of the ligand library L1–
L12a–g for the more demanding Z-isomers, which are
usually hydrogenated less enantioselectively than the
corresponding E-isomers, we chose substrate S2 as
a model. Excellent activities and enantioselectivities
(up to 98% for S1 and up to 91% for S2) were ob-
tained. The results, which are summarized in Table 1,
indicate that enantioselectivity is mainly affected by
the substituents at the ligand backbone (R1 and R2)
and by the substituents/configuration at the biaryl
phosphite moiety. However, the effect of these ligand
parameters on enantioselectivity depends on the sub-
strate type (E- or Z-isomers). While for the E-sub-
strate S1 the enantioselectivity was best with ligand
L2e [98% ee (S)], enantioselectivities for the more
demanding Z-substrate S2 were therefore best with
ligand L6c [91% ee (R)]. Interestingly, for both types
of substrates, the sense of enantioselectivity is con-
trolled by the configuration of the stereogenic carbon
next to the phosphite moiety. Ligands L1–L8 there-
fore provide the opposite enantiomer to ligands L9–
L12 (i.e., Table 1; entry 10 vs. 25, for substrate S1; and
entry 17 vs. 27 for substrate S2).
1
2
3
4
5
6
7
8
L1a
L1b
L1c
L1d
L1e
Lif
61 (S)
48 (S)
50 (S)
27 (S)
64 (S)
38 (S)
58 (S)
90 (S)
87 (S)
98 (S)
58 (S)
63 (S)
89 (S)
45 (S)
90 (S)
80 (S)
74 (S)
55 (S)
90 (S)
62 (S)
70 (S)
60 (R)
36 (R)
66 (R)
97 (R)
88 (R)
72 (R)
98 (S)
74 (S)
75 (R)
84 (R)
88 (R)
73 (R)
25 (R)
74 (R)
30 (R)
72 (R)
59 (R)
45 (R)
72 (R)
68 (R)
72 (R)
52 (R)
58 (R)
84 (R)
91 (R)
85 (R)
48 (R)
11 (R)
75 (R)
77 (S)
64 (S)
6 (S)
L1g
L2a
L2d
L2e
L3a
L4a
L5a
L5d
L5e
L6a
L6c
L6d
L6e
L7a
L8a
L9a
L9d
L9e
L10e
L11e
L12e
L12e
L6c
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28[c]
29[c]
38 (S)
38 (S)
90 (S)
44 (R)
91 (R)
[a]
Reactions carried out at room temperature by using
0.5 mmol of substrate and 1 mol% of Ir catalyst precur-
sor at 50 bar of H2 using dichloromethane (2 mL) as sol-
vent. Full conversions were achieved in all cases.
Enantiomeric excesses determined by GC.
The effect of the substituents of the ligand back-
bone (R1 and R2) was studied using ligands L1–L8.
While for substrate S1 the enantioselectivity is highly
affected by the substituents at both R1 and R2 posi-
tions of the ligand backbone, for substrate S2 the
enantioselectivity is mainly affected by the substituent
[b]
[c]
Reaction carried out with 0.25 mol% of Ir catalyst pre-
cursor for 3 h.
at R2, and is relatively insensitive to the substituents again, the effect of this moiety on enantioselectivity
at R1. For substrate S1, although high enantioselectiv- depends on the substrate type. Regarding the sub-
ities can be obtained by introducing either a methyl stituents in the tropoisomeric biphenyl phosphite
substituent at R1 (ligands L2) or a tert-butyl substitu- moiety, for substrate S1, the presence of tert-butyl
ent at R2 (ligands L5), ligands L2 provided somewhat substituents at para positions of the biphenyl phos-
higher enantioselectivities than L5 (i.e., Table 1, en- phite moiety provides higher enantioselectivities than
tries 10 and 15). However, the introduction of both when a methoxy group or hydrogen is present (i.e.,
substituents simultaneously at R1 and R2 positions (li- a>bꢀc; Table 1, entry 1 vs. 2 and 3). However, the
gands L7) led to lower enantioselectivities (Table 1, effect for substrate S2 is opposite. The highest enan-
entry 20 vs. 8 and 13). For substrate S2, the introduc- tioselectivity is therefore obtained using a non-para-
tion of a phenyl substituent at R2 position has a posi- substituted biphenyl phosphite moiety (Table 1,
tive effect on enantioselectivities (Table 1, entry 16 vs. entry 3 vs. 2 and 1). Regarding the configuration of
1).
the biaryl phosphite, while for substrate S1 the enan-
The effect of the phosphite moieties was studied tioselectivity is higher using the enantiopure R-biaryl
using ligands L1a–g (Table 1, entries 1–7). Once phosphite moiety, for substrate S2 the presence of the
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3
ÞÞ
These are not the final page numbers!

Javier Mazuela et al.
FULL PAPERS
S-biaryl phosphite moiety provides higher enantiose- those observed for substrates S1 and S2. For E-sub-
lectivities (Table 1, entries 4–7). strates S3–S5, the enantioselectivities were therefore
In summary, by the correct choice of the substitu- best with ligands L2e and L10e, while ligands L6c and
ents at R1 and R2 of the ligand backbone, the configu- L12c afforded the highest ees for Z-substrate S6. We
ration of the stereogenic carbon next to the phosphite also found that enantioselectivity (ee values up to
moiety and the substituents/configuration at the 99%) is relatively insensitive to the electronic nature
biaryl phosphite moiety, we were able to obtain both of the substrate phenyl ring (i.e., substrates S1, S2
enantiomers of the reduction product in high enantio- and S4 vs. S3, S6 and S5, respectively). It should be
selectivities for both E- and Z-trisubstituted model noted that if the ligands are appropriately tuned, high
substrates (for substrate S1, ees up to 98% were ob- enantioselectivities can also be obtained for a wide
tained using ligands L2e and L10e; and for substrate range of the more demanding dihydronaphthalenes
S2, ees up to 91% were obtained using ligands L6c (S7–S10) and triaryl-substituted substrates (S11 and
and L12c). In addition, the excellent enantioselectivi- S12). For dihydronaphthalene substrates (S7–S10),
ties and activities were maintained at a low catalyst high enantioselectivities (95–98% ee) were obtained
loading (0.25 mol%; Table 1, entries 28 and 29).
with Ir-L2e and Ir-L10e catalysts. Although the corre-
We then studied the asymmetric hydrogenation of sponding chiral tetraline motif can be found in numer-
other E- and Z-trisubstituted olefins (S3–S12) by ous natural products [i.e., natural antitumor agent
using the phosphite-pyridine ligand library L1–L12a– (R)-(+)-7-demethyl-2-methoxycalamenene],[15] very
g. The most noteworthy results are shown in few catalytic systems are able to hydrogenate this sub-
Scheme 2 (see the Supporting Information for a com- strate class at high levels of enantioselectivities.[8b,15]
plete set of results). The enantioselectivities are Another important class of substrates that have also
among the best observed for these substrates.[2,6] We been scarcely studied is the triaryl-substituted
first studied the hydrogenation of substrates S3–S6, group.[10e,16] This substrate class provides an easy entry
related to S1 and S2 that differ in the substituents in point to diarylmethine chiral centers, which are pres-
both the aryl ring and the substituents trans to the ent in several important drugs and natural products.[17]
aryl group. The results followed the same trends as We were again pleased to find that this substrate class
could also be reduced in high enantioselectivity but in
this case using the Ir-L4a catalytic system (Scheme 2,
ees ranging from 97% to 98%).
Asymmetric Hydrogenation of Trisubstituted Olefins
Containing a Neighbouring Polar Group
The reduction of substrates bearing a neighbouring
polar group is of great importance because they are
important intermediates for the synthesis of high-
value chemicals and they enable further functionaliza-
tion. We therefore decided to study the potential of
our phosphite-pyridine ligand library L1–L12a–g for
the reduction of a wide range of trisubstituted alkenes
containing several types of polar groups in greater
depth. The results are summarized in Scheme 3 (for
a full set of results, see Table SI.2 in Supporting Infor-
mation). Once again, excellent enantioselectivities in
both enantiomers of the reduction products (ee values
up to 99%) for a range of substrates were obtained
under mild reaction conditions by suitable tuning of
the ligand parameters.
The reduction of several a,b-unsaturated esters
(S13–S15) followed different trends to those observed
for the previous E-trisubstituted substrates. Enantio-
selectivities were therefore best using ligands L5a,
L5e, L11a and L11e (ees ranging from 96% to 99%).
It should be noted that ees are highly independent on
the electronic nature of the substrate phenyl ring. We
also found that the hydrogenation of allylic alcohol
Scheme 2. Selected hydrogenation results of E- and Z-tri-
substituted olefins using [IrACHTNUTRGENNUG(cod)(L1–L12a–g)]BArF catalyst
precursors. Reaction conditions: 1 mol% catalyst precursor,
CH2Cl2 as solvent, 50 bar H2, room temperature, 2 h. Full
conversions were achieved in all cases.
4
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

A Phosphite-Pyridine/Iridium Complex Library as Highly Selective Catalysts for the Hydrogenation
Asymmetric Hydrogenation of 1,1-Disubstituted
Terminal Olefins
We next studied the the asymmetric hydrogenation of
more demanding terminal olefins. The lower enantio-
selectivity obtained with 1,1-disubstituted terminal
olefins compared with trisubstituted olefins is attrib-
uted to two main factors.[2d,e] The first is that the two
substituents in the substrate can easily exchange posi-
tions in the chiral environment formed by the cata-
lysts, thus reversing the face selectivity. The second
reason is that the terminal double bond can isomerize
to form the more stable internal alkene, which usually
leads to the predominant formation of the opposite
enantiomer of the hydrogenated product. Few known
catalytic systems provide high enantioselectivities for
these substrates, and those that do are usually limited
in substrate scope.[2e,19,20] Unlike the hydrogenation of
trisubstituted olefins, the enantioselectivity in the re-
duction of terminal alkenes is highly pressure-depen-
dent. Hydrogenation at an atmospheric pressure of
H2 therefore generally gave significantly higher ee
values than at higher pressures.[19]
Scheme 3. Selected hydrogenation results of trisubstituted
olefins bearing neighbouring polar group using
[Ir(cod)(L1–L12a–g)]BArF catalyst precursors. Reaction con-
a
ACHTUNGTRENNUNG
ditions: 1 mol% catalyst precursor, CH2Cl2 as solvent, 50 bar
H2, room temperature, 2 h. Full conversions were achieved
in all cases.
Asymmetric Hydrogenation of Minimally
Functionalized 1,1-Disubstituted Terminal Olefins
S16 and allylic acetate S17 followed the same trend. In an initial set of experiments, we used the Ir-cata-
High enantioselectivities were therefore also obtained lyzed asymmetric hydrogenation of 2-(4-methoxyphe-
with catalyst systems containing the ligands L5a, L5e,
L11a and L11e (ees up to 98%). As observed for the
E-trisubstituted substrate S1, the highest enantioselec-
tivities in the hydrogenation of vinylsilane S18 were
obtained using ligands L2e and L10e (ees up to 78%).
Ligand tuning was also essential to achieve the high-
est levels of enantioselectivity in the reduction of a,b-
unsaturated ketone S19 and several vinylboronates
S20–S22. For substrate S19, enantioselectivities are
therefore best when using Ir-L2a and Ir-L10a catalysts
(ees up to 99%), while for substrates S20–S22, Ir-L1a
and Ir-L9a catalytic systems provided the highest
enantioselectivities (ees up to 99%). The hydrogena-
tion of vinylboronates provides easy access to chiral
borane compounds, which are useful building blocks
Table 2. Selected results for the Ir-catalyzed hydrogenation
of S23 using the ligands L1–L12a–g.[a]
Entry
Ligand
ee [%][b]
Entry
Ligand
ee [%][b]
1
2
3
4
5
6
7
8
L1a
L1b
L1c
L1d
L1e
L1f
L1g
L2a
L2d
L2e
L3a
L4a
L5a
48 (R)
49 (R)
50 (R)
40 (S)
58 (R)
36 (S)
58 (R)
72 (R)
8 (S)
96 (R)
42 (R)
19 (R)
64 (R)
14
15
16
17
18
19
20
21
L5d
L5e
L6a
L6d
L6e
L7a
L8a
L9a
L9d
L9e
L10e
L2e
L10e
77 (R)
30 (S)
63 (R)
62 (R)
42 (S)
33 (S)
60 (R)
49 (S)
56 (R)
43 (S)
95 (S)
96 (R)
95 (S)
À
in organic synthesis because the C B bond can be
À
À
À
readily converted to C O, C N and C C bonds with
retention of the chirality. For vinylboronates, our re-
sults show that ees are again highly independent of
the electronic properties of the phenyl substrate ring.
It should be pointed out that these results surpass
the ees achieved using related 1st generation phos-
phinite-pyridine analogues.[18] This is therefore one of
the few catalytic systems that can hydrogenate a wide
range of trisubstituted olefins in high activities and
enantioselectivities.[2,6]
9
22
23
10
11
12
13
24
25[c]
26[c]
[a]
Reactions carried out using 0.5 mmol of S21 and 1 mol%
of Ir catalyst precursor at 1 bar of H2. Full conversions
after 2 h were achieved in all cases.
Enantiomeric excesses determined by chiral GC.
Reaction carried out at 0.25 mol% of Ir catalyst precur-
sor for 3 h.
[b]
[c]
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
5
ÞÞ
These are not the final page numbers!

Javier Mazuela et al.
FULL PAPERS
Table 3. Selected results for the Ir-catalyzed hydrogenation
of minimally functionalized 1,1-disubstituted terminal ole-
fins using ligands L1–L12a–g.[a]
nyl)but-1-ene S23. The results obtained using the
ligand library L1–L12a–g under optimized conditions
are shown in Table 2. We were again able to fine-tune
the ligand parameters to produce high activities and
enantioselectivities (ees up to 96%) in the hydrogena-
tion of this substrate using ligands L2e and L10e at
low catalyst loadings (0.25 mol%) and hydrogen pres-
sures (1 bar). Once again, it was possible to obtain
both enantiomers of the hydrogenated product by
simply changing the configuration of the stereogenic
carbon next to the phosphite moiety (see Table 2,
entry 10 vs. 24). Enantioselectivity is also affected by
the substituents at the ligand backbone (R1 and R2)
and by the substituents/configuration in the biaryl
phosphite moiety. Regarding the effect of the sub-
stituents at the ligand backbone, we found that enan-
tioselectivities are best with ligands that contain
a methyl substituent at R1 and a hydrogen substituent
at R2 positions (ligands L2 and L10).
As far as the effect of the substituents/configuration
of the phosphite moiety is concerned, enantioselectiv-
ity is mainly affected by the configuration of the
biaryl phosphite moiety, and is relatively insensitive
to the substituents at both ortho and para positions of
the biaryl phosphite group. The best enantioselectivi-
ties are therefore obtained using ligands containing
an enantiopure R-biaryl phosphite moiety (see
Table 2, entry 10 vs. 9).
We then studied the asymmetric hydrogenation of
other 1,1-disubstituted aryl-alkyl substrates (S24–
S31), 1,1-disubstituted pyridyl-alkyl olefins (S32 and
S33) and 1,1-diaryl terminal alkenes (S34–S36) using
the phosphite-pyridine ligand library L1–L12a–g. The
most noteworthy results are shown in Table 3 (for
a complete set of results, see Table SI.3 in Supporting
Information). The results follow the same trends as
the hydrogenation of S23 for all substrates. The cata-
lyst precursors containing the phosphite-pyridine li-
gands L2e and L10e therefore provided the best
enantioselectivities in both enantiomers of the reduc-
tion product. These results are again among the best
reported for these substrates.[2e]
Our results with several 1,1-disubstituted aryl-alkyl
substrates (S24–S31) indicated that enantioselectivity
is not affected by the electronic nature of the sub-
strate aryl ring (Table 2, entry 10; and Table 3, en-
tries 1 and 3), but it is slightly affected by the nature
of the alkyl chain (ees ranging from 92% to 97%;
Table 3, entries 1, 5–16). Enantioselectivities therefore
[a]
Reactions carried out using 0.5 mmol of substrate and
0.25 mol% of Ir catalyst precursor at 1 bar of H2. Full
conversions were achieved in all cases.
Enantiomeric excesses determined by chiral GC (except
for entries 22–24 that were measured by HPLC).
[b]
[c]
Reaction carried out under 50 bar of H2.
decrease from 97–96% to 92% by increasing the selectivity as those obtained using substrates S29 and
steric bulk of the alkyl substituent. This can be attrib- S30, which are more prone to isomerization and also
uted to the restrictions imposed by the Ir catalysts contain bulky alkyl substituents (Table 3, entry 15 vs.
themselves rather than to the presence of an isomeri- 11 and 13).
zation process under hydrogenation conditions. This is
Due to the interest of heterocycles for industry and
supported by the fact that the hydrogenation of sub- because the heterocyclic part can be modified post-
strate S31 bearing a tert-butyl group, for which iso- hydrogenation, we decided to test the scope of our
merization cannot occur, provides the same enantio- ligand library by performing the hydrogenation of
6
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

A Phosphite-Pyridine/Iridium Complex Library as Highly Selective Catalysts for the Hydrogenation
pyridyl-alkyl substrates S32 and S33. We were pleased We then turned our attention to the asymmetric re-
to see that we also obtained high activities and enan- duction of the trifluoromethyl olefin S39 and allylic
tioselectivities under mild reaction conditions silane S40. The hydrogenation of these compounds
(Table 3, entries 17–20).
gave rise to important organic intermediates and
Finally, we studied the hydrogenation of several a number of innovative new organofluorine[24] and or-
diaryl terminal alkenes (S34–S36; Table 3, entries 21– ganosilicon[25] drugs are now being developed. For
24). Enantiopure diarylalkanes are important inter- substrate S39, an unprecedented high enantioselectivi-
mediates for the preparation of drugs and research ty (ee up to 99%) has been obtained with Ir-L1c and
materials.[21] They have traditionally been prepared Ir-L9c catalytic systems. However, for substrate S40,
using rather laborious approaches.[21,22] It has recently we also obtained high enantioselectivities but with li-
been shown that they can be prepared more efficient- gands L2e and L10e. Once again, these results clearly
ly using enantioselective hydrogenation.[10c] Substrates show the efficiency of using highly modular scaffolds
differing sterically (S35 and S36) were also hydrogen- in the ligand design.
ated with high enantioselectivities (ees up to 82%;
Table 3, entries 22–24) using the Ir-L2e catalytic
system. However, as anticipated, the control of enan- Recycling Experiments using Propylene Carbonate as
tioselectivity in substrate S34, for which the aryl Solvent
groups only differ electronically, was less effective
(Table 3, entry 21).
Encouraged by the excellent results obtained, we de-
cided to go one step further and study the hydrogena-
tion using propylene carbonate (PC) as an environ-
mentally friendly alternative solvent. PC has recently
emerged as a sustainable alternative to standard or-
ganic solvents because of its high boiling point, low
toxicity and environmentally friendly synthesis.[26]
Asymmetric Hydrogenation of 1,1-Disubstituted
Terminal Olefins Containing a Neighbouring Polar
Group
We next examined the asymmetric hydrogenation of Moreover, Bçrnerꢄs group has demonstrated that PC
1,1-disubstituted terminal olefins containing a polar allows Ir catalysts to be repeatedly recycled by
neighbouring group (S37–S40). The results are sum- a simple two-phase extraction with an apolar sol-
marized in Scheme 4 (for a complete set of results, vent,[27] which for a practical industrial application is
see Table SI.3 in Supporting Information). In all of great importance because of the high price of iridi-
cases, both enantiomers of the hydrogenated product um.
can be obtained in high enantioselectivities by simply
changing the configuration of the carbon next to the idine catalytic systems can be used in combination
phosphite moiety. with PC (Table 4). However, higher pressures are re-
Our results indicated that the new Ir-phosphite-pyr-
We initially tested the ligand library in the hydroge- quired to match the performance achieved using di-
nation of the allylic alcohol S37 and allylic acetate chlororomethane as solvent (i.e., 50 bar of H2 are re-
S38. Derivatives of the hydrogenation of these prod- quired in the reduction of terminal substrates). Thus,
ucts are important intermediates for the synthesis of we were able to recycle Ir-L2e catalyst up to 3 times
high-value cosmetics, natural products and drugs.[23] in the hydrogenation of terminal olefins S23 and S31
Enantioselectivities followed a different trend to that without significant losses in enantioselectivities, al-
observed with the previous 1,1,-disubstituted terminal though reaction time increased after each run.[28]
olefins S23–S36, and the best enantioselectivities (up
to 84%) were obtained using ligands L5e and L11e.
Table 4. Recycling experiments with the catalyst precursor
(L2e)]BArF and S23 and S31 as substrates in PC.[a]
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
Cycle
Substrate
Conv. [%] (h)[b]
ee [%][c]
1
2
3
1
2
3
S23
S23
S23
S31
S31
S31
100 (4)
98 (6)
57 (10)
100 (4)
92 (6)
95 (R)
94 (R)
94 (R)
91 (R)
91 (R)
90 (R)
Scheme 4. Selected hydrogenation results of 1,1-disubstitut-
ed terminal olefins containing a neighbouring polar group
58 (10)
[a]
using [Ir
N
Reactions carried out using 0.5 mmol of substrate and
1 mol% of Ir catalyst precursor using 50 bar of H2.
Conversion measured by GC.
tion conditions: 0.5 mol% catalyst precursor, CH2Cl2 as sol-
vent, 50 bar H2, room temperature, 2 h. Full conversions
were achieved in all cases.
[b]
[c]
Enantiomeric excesses determined by chiral GC.
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
7
ÞÞ
These are not the final page numbers!

Javier Mazuela et al.
FULL PAPERS
Conclusions
Experimental Section
We have reported the first successful application of General Considerations
phosphite-pyridine ligands in the Ir-catalyzed asym-
All reactions were carried out using standard Schlenk tech-
niques under an atmosphere of argon. Solvents were puri-
fied and dried by standard procedures. Phosphorochloridites
were easily prepared in one step from the corresponding
biaryls. Enantiopure phosphite-pyridine ligands L1–L12a–g
were prepared as previously described.[12] 1H, 13C-{1H}, and
31P-{1H} NMR spectra were recorded using a 400 MHz spec-
trometer. Chemical shifts are relative to that of SiMe4 (1H
and 13C) as internal standard or H3PO4 (31P) as external
metric hydrogenation of minimally functionalized ole-
fins. These ligands combine the advantages of both
types of successful ligands for this process (phosphite
and pyridine). They are therefore more robust than
their oxazoline and phosphine/phosphinite counter-
parts, and the incorporation of the desired diversity is
easier to achieve in both the pyridine and the phos-
phite moieties. The modular ligand design has been
shown to be crucial in finding highly selective catalyt-
ic systems for each substrate. By carefully selecting
the ligand components, we obtained excellent enan-
tioselectivities (ees up to 99%) in a wide range of E-
and Z-trisubstituted alkenes, including more demand-
ing triaryl-substituted olefins, and dihydronaphtha-
lenes. The good performance extends to the very chal-
lenging class of terminal disubstituted olefins (ees up
to 99%). These catalysts are also very tolerant to the
presence of a neighbouring polar group. A range of
allylic alcohols, acetates, a,b-unsaturated esters and
ketones, allylic silanes, vinylboronates and trifluoro-
methyl olefins were thus hydrogenated with high
enantioselectivities. Note that both enantiomers of
1
standard. H and 13C assignments were made on the basis of
1
1H-1H gCOSY and H-13C gHSQC experiments.
Typical Procedure for the Preparation of
[IrACTHNURTGNEUGN(cod)(L)]BArF (L=L1–L12a–g)
The corresponding ligand (0.074 mmol) was dissolved in
CH2Cl2 (2 mL) and [Ir(m-Cl)(cod)]2 (25 mg, 0.037 mmol) was
A
ACHTUNGTRENNUNG
added. The reaction was refluxed at 508C for 1 hour. After
5 min at room temperature, NaBArF (77.1 mg, 0.082 mmol)
and water (2 mL) were added and the reaction mixture was
stirred vigorously for 30 min at room temperature. The
phases were separated and the aqueous phase was extracted
twice with CH2Cl2. The combined organic phases were fil-
tered through a celite plug, dried with MgSO4 and the sol-
the reduction product can be obtained in excellent vent was evaporated to give the product as an orange solid.
(L1a)]BArF:Yield: 118 mg (93%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
enantioselectivities by simply changing the configura-
tion of the carbon next to the phosphite moiety. The
new Ir-phosphite-pyridine catalyst library not only
performs well in traditional organic solvents but also
in propylene carbonate, an alternative environmental-
ly friendly solvent, which allowed the catalyst to be
reused while maintaining the excellent enantioselec-
tivities. We also demonstrated that the introduction of
a biaryl phosphite moiety into the ligand design is
(CDCl3): d=06.0 (s); 1H NMR (CDCl3): d=1.29 (s, 9H,
CH3, t-Bu), 1.33 (s, 18H, CH3, t-Bu), 1.51 (s, 9H, CH3, t-Bu),
1.87 (b, 2H, CH2, cod), 2.13 (b, 3H, CH3), 2.18 (b, 4H, CH2,
cod), 2.36 (b, 2H, CH2, cod), 3.94 (b, 1H, CH=, cod), 4.29
(b, 1H, CH=, cod), 4.71 (b, 1H, CH=, cod), 5.35 (b, 1H,
CH=, cod), 6.12 (m, 1H, CHO), 7.1–8.6 (m, 20H, CH=);
13C NMR (CDCl3): d=25.3 (b, CH2, cod), 29.0 (b, CH2,
cod), 30.9 (CH3), 31.1 (CH3, t-Bu), 31.2 (CH3, t-Bu), 31.3
(CH3, t-Bu), 31.9 (CH3, t-Bu), 33.0 (b, CH2, cod), 34.8 (C, t-
highly advantageous in terms of substrate versatility. Bu), 35.4 (C, t-Bu), 35.5 (C, t-Bu), 36.3 (b, CH2, cod), 65.8
(b, CH=, cod), 69.9 (b, CH=, cod), 77.2 (CHO), 100.7 (d,
CH=, cod, C,P =20.9 Hz), 104.5 (d, CH=, cod, JC,P
12.5 Hz), 117.7 (b, CH=, BArF), 119–131 (aromatic carbons),
The efficiency of this ligand design is therefore also
corroborated by the fact that these Ir-phosphite-pyri-
dine catalysts provided higher enantioselectivity and
broader substrate versatility than their phosphinite-
pyridine analogues.[18] In addition the results of our
phosphite-pyridine catalyst library compare very well
with the ones achieved using the second generation of
phosphinite-pyridine ligands (Figure 1),[29] which can
be considered as the state of the art for this transfor-
J
=
135.0 (b, CH=, BArF), 139–159 (aromatic carbons), 161.9 (q,
À
C B,
BArF,
1J=49 Hz);
anal.
calcd.
(%)
for
C75H72BF24IrNO3P: C 52.21, H 4.21, N 0.81; found: C 52.16,
H 4.17, N 0.78.
(L1b)]BArF: Yield: 117 mg (95%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=109.0 (s); 1H NMR (CDCl3): d=1.21 (s, 9H,
CH3, t-Bu), 1.41 (s, 9H, CH3, t-Bu), 1.76 (b, 2H, CH2, cod),
mation, with the added advantatge that our Ir-phos- 2.02 (b, 3H, CH3), 2.05 (b, 4H, CH2, cod), 2.29 (b, 2H, CH2,
cod), 3.73 (s, 6H, CH3, CH3O), 4.13 (b, 1H, CH=, cod), 4.30
(b, 1H, CH=, cod), 4.59 (b, 1H, CH=, cod), 5.22 (b, 1H,
CH=, cod), 6.03 (m, 1H, CHO), 6.5–8.5 (m, 20H, CH=);
13C NMR (CDCl3): d=25.5 (b, CH2, cod), 29.1 (b, CH2,
cod), 31.0 (CH3, t-Bu), 31.2 (CH3), 31.8 (CH3, t-Bu), 33.5 (b,
CH2, cod), 35.6 (C, t-Bu), 35.7 (C, t-Bu), 36.7 (b, CH2, cod),
55.8 (CH3, CH3O), 55.9 (CH3, CH3O), 66.3 (b, CH=, cod),
phite-pyridine systems are able to expand the scope
to a broad range of disubstituted substrates. These re-
sults open up a new class of Ir catalysts for the highly
enantioselective hydrogenation of minimally function-
alized olefins, including those with a neighbouring
polar group, which is of great practical interest.
70.2 (b, CH=, cod), 77.4 (CHO), 100.4 (d, CH=, cod, JC,P
=
21.7 Hz), 104.7 (d, CH=, cod, JC,P =11.7 Hz), 113–116 (aro-
matic carbons), 117.7 (b, CH=, BArF), 120–133 (aromatic
carbons), 135.0 (b, CH=, BArF), 139–159 (aromatic carbons),
8
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

A Phosphite-Pyridine/Iridium Complex Library as Highly Selective Catalysts for the Hydrogenation
161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%) for
C69H60BF24IrNO5P: C 49.53, H 3.61, N 0.84; found: C 49.46,
H 3.57, N 0.79.
13C NMR (C6D6): d=0.0 (CH3, SiMe3), 1.1 (CH3, SiMe3),
À
17.5 (d, CH3, JC,P =10.9 Hz), 25.0 (b, CH2, cod), 28.4 (b,
CH2, cod), 34.1 (b, CH2, cod), 37.1 (b, CH2, cod), 66.3 (b,
CH=, cod), 71.2 (b, CH=, cod), 76.8 (d, CH, JC,P =7 Hz),
100.5 (d, CH=, cod, JC,P =22.5 Hz), 105.6 (d, CH=, cod,
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L1c)]BArF: Yield: 112 mg (92%). 31P NMR
(CDCl3); d=109.1 (s); 1H NMR (CDCl3): d=0.20 (s, 9H,
CH3, SiMe3), 0.48 (s, 9H, CH3, SiMe3), 1.78 (b, 2H, CH2,
cod), 1.89 (b, 3H, CH3), 2.19 (b, 4H, CH2, cod), 2.40 (b, 2H,
CH2, cod), 4.16 (b, 1H, CH=, cod), 4.20 (b, 1H, CH=, cod),
4.73 (b, 1H, CH=, cod), 5.38 (b, 1H, CH=, cod), 6.19 (m,
1H, CHO), 7.2–8.7 (m, 22H, CH=); 13C NMR (CDCl3): d=
0.8 (CH3, SiMe3), 1.5 (CH3, SiMe3), 26.2 (b, CH2, cod), 29.6
(b, CH2, cod), 31.9 (CH3), 34.4 (b, CH2, cod), 37.5 (b, CH2,
cod), 67.9 (b, CH=, cod), 71.6 (b, CH=, cod), 78.2 (CHO),
J
C,P =11.6 Hz), 117.7 (b, CH=, BArF), 121–135 (aromatic car-
bons), 135.0 (b, CH=, BArF), 137–159 (aromatic carbons),
161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%) for
À
C73H60BF24IrNO3PSi2: C 50.23, H 3.46, N 0.80; found: C
50.20, H 3.44, N 0.76.
(L1g)]BArF: Yield: 123 mg (95%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUNG
1
(C6D6): d=107.6 (s); H NMR (C6D6): d=0.05 (s, 9H, CH3,
SiMe3), 0.48 (s, 9H, CH3, SiMe3), 1.40 (b, 2H, CH2, cod),
1.71 (b, 3H, CH2, cod), 1.85 (b, 3H, CH2, cod), 1.9 (d, 3H,
CH3, 3 JH,H =6.8 Hz), 2.99 (b, 1H, CH=, cod), 3.70 (b, 1H,
CH=, cod), 4.61 (b, 1H, CH=, cod), 4.63 (m, 1H, CHO),
4.80 (b, 1H, CH=, cod), 6.1–8.4 (m, 26H, CH=); 13C NMR
(C6D6): d=0.9 (CH3, SiMe3), 1.1 (CH3, SiMe3), 24.9 (b, CH2,
cod), 25.9 (d, CH3, JC,P =3.9 Hz), 28.3 (b, CH2, cod), 33.0 (b,
CH2, cod), 37.1 (b, CH2, cod), 65.1 (b, CH=, cod), 68.6 (b,
CH=, cod), 81.0 (s, CHO), 104.6 (s, CH=, cod), 104.8 (d,
CH=, cod, JC,P =7 Hz), 117.7 (b, CH=, BArF), 121–135 (aro-
matic carbons), 135.0 (b, CH=, BArF), 137–159 (aromatic
101.2 (d, CH=, cod, JC,P =21 Hz), 106.0 (d, CH=, cod, JC,P
11.6 Hz), 117.7 (b, CH=, BArF), 120–135 (aromatic carbons),
135.0 (b, CH=, BArF), 137–159 (aromatic carbons), 161.9 (q,
=
À
C B,
BArF,
1J=49 Hz);
anal.
calcd.
(%)
for
C65H56BF24IrNO3PSi2: C 47.45, H 3.43, N 0.85; found: C
47.38, H 3.38, N 0.81.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L1d)]BArF: Yield: 118 mg (96%). 31P NMR
(CDCl3): d=103.0 (s); 1H NMR (CDCl3): d=1.28 (s, 9H,
CH3, t-Bu), 1.50 (s, 9H, CH3, t-Bu), 1.77 (b, 6H, CH3-Ar),
1.78 (b, 3H, CH3), 2.15 (b, 2H, CH2, cod), 2.26 (b, 6H, CH3-
Ar), 2.28 (b, 4H, CH2, cod), 2.37 (b, 2H, CH2, cod), 3.82 (b,
1H, CH=, cod), 4.43 (b, 1H, CH=, cod), 4.60 (b, 1H, CH=,
cod), 5.23 (b, 1H, CH=, cod), 6.09 (m, 1H, CHO), 7.2–8.6
(m, 18H, CH=); 13C NMR (CDCl3): d=16.6 (CH3-Ar), 16.7
(CH3-Ar), 17.4 (CH3-Ar), 17.5 (CH3-Ar), 20.4 (CH3), 25.0
(b, CH2, cod), 28.6 (b, CH2, cod), 31.2 (CH3, t-Bu), 32.4
(CH3, t-Bu), 33.6 (b, CH2, cod), 34.8 (C, t-Bu), 34.9 (C, t-
Bu), 36.7 (b, CH2, cod), 65.8 (b, CH=, cod), 70.7 (b, CH=,
cod), 77.2 (CHO), 99.6 (d, CH=, cod, J=24.4 Hz), 104.0 (d,
CH=, cod, J=12.3 Hz), 117.7 (b, CH=, BArF), 120–134 (aro-
matic carbons), 135.0 (b, CH=, BArF), 136–159 (aromatic
carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%)
À
for C73H60BF24IrNO3PSi2: C 50.23, H 3.46, N 0.80; found: C
50.18, H 3.42, N 0.76.
(L2a)]BArF: Yield: 124 mg (96%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=110.7 (s); 1H NMR (CDCl3): d=1.31 (s, 9H,
CH3, t-Bu), 1.35 (s, 9H, CH3, t-Bu), 1.36 (s, 9H, CH3, t-Bu),
1.58 (s, 9H, CH3, t-Bu), 1.73 (b, 3H, CH3), 1.98–2.53 (b, 8H,
CH2, cod), 3.16 (b, 3H, CH3-Py), 3.95 (b, 1H, CH=, cod),
4.59 (b, 1H, CH=, cod), 5.05 (b, 1H, CH=, cod), 5.25 (b,
1H, CH=, cod), 6.24 (m, 1H, CHO), 7.0–8.0 (m, 19H, CH=
); 13C NMR (CDCl3): d=17.9 (b, CH3), 23.9 (b, CH2, cod),
27.8 (b, CH2, cod), 29.1 (CH3-Py), 30.4 (CH3, t-Bu), 30.9 (C,
t-Bu), 31.2 (C, t-Bu), 31.3 (CH3, t-Bu), 31.4 (CH3, t-Bu), 34.7
(b, CH2, cod), 35.2 (C, t-Bu), 35.4 (C, t-Bu), 37.5 (b, CH2,
cod), 70.4 (b, CH=, cod), 72.9 (b, CH=, cod), 75.4 (CHO),
88.6 (d, CH=, cod, JC,P =26 Hz), 104.1 (b, CH=, cod), 117.7
(b, CH=, BArF), 120–131 (aromatic carbons), 135.0 (b, CH=,
carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%)
À
for C71H64BF24IrNO3P: C 51.09, H 3.86, N 0.84; found: C
51.04, H 3.84, N 0.81.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L1e)]BArF: Yield: 120 mg (97%). 31P NMR
(CDCl3): d=102.3 (s); 1H NMR (CDCl3): d=1.18 (s, 9H,
CH3, t-Bu), 1.50 (s, 9H, CH3, t-Bu), 1.72 (b, 6H, CH3-Ar),
1.79 (b, 3H, CH3), 2.13 (b, 2H, CH2, cod), 2.24 (s, 3H, CH3-
Ar), 2.25 (s, 3H CH3-Ar), 2.27 (b, 4H, CH2, cod), 2.43 (b,
2H, CH2, cod), 3.49 (b, 1H, CH=, cod), 4.12 (b, 1H, CH=,
cod), 4.77 (b, 1H, CH=, cod), 5.33 (b, 1H, CH=, cod), 5.46
(m, 1H, CHO), 7.2–8.6 (m, 18H, CH=); 13C NMR (CDCl3):
d=16.5 (CH3-Ar), 16.6 (CH3-Ar), 20.3 (CH3-Ar), 20.4 (CH3-
Ar), 24.8 (b, CH2, cod), 25.2 (CH3), 28.5 (b, CH2, cod), 31.9
(CH3, t-Bu), 32.3 (CH3, t-Bu), 32.9 (b, CH2, cod), 34.9 (C, t-
Bu), 35.0 (C, t-Bu), 36.8 (b, CH2, cod), 63.7 (b, CH=, cod),
67.6 (b, CH=, cod), 80.8 (CHO), 102.5 (b, CH=, cod), 102.7
(b, CH=, cod), 117.7 (b, CH=, BArF), 120–134 (aromatic car-
bons), 135.0 (b, CH=, BArF), 136–158 (aromatic carbons),
À
BArF), 139–158 (aromatic carbons), 161.9 (q, C B, BArF,
1J=49 Hz); anal. calcd. (%) for C76H74BF24IrNO3P: C 52.48,
H 4.29, N 0.80 found: C 52.43, H 4.26, N 0.77.
(L2d)]BArF: Yield: 118 mg (95%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=103.1 (s); 1H NMR (CDCl3): d=1.26 (s, 9H,
CH3, t-Bu), 1.44 (s, 9H, CH3, t-Bu), 1.65 (s, 3H, CH3-Ar),
1.68 (s, 3H, CH3-Ar), 1.74 (b, 3H, CH3), 2.15 (b, 2H, CH2,
cod), 2.19 (s, 3H, CH3-Ar), 2.24 (s, 3H, CH3-Ar), 2.28 (b,
4H, CH2, cod), 2.37 (b, 2H, CH2, cod), 3.04 (s, 3H, CH3-
Py), 3.80 (b, 1H, CH=, cod), 4.42 (b, 1H, CH=, cod), 4.57
(b, 1H, CH=, cod), 5.21 (b, 1H, CH=, cod), 6.06 (m, 1H,
CHO), 7.2–8.6 (m, 17H, CH=); 13C NMR (CDCl3): d=16.5
(CH3-Ar), 16.8 (CH3-Ar), 17.1 (CH3-Ar), 17.4 (CH3-Ar),
20.2 (CH3), 25.1 (b, CH2, cod), 28.5 (b, CH2, cod), 29.3
(CH3-Py), 31.2 (CH3, t-Bu), 31.9 (CH3, t-Bu), 33.6 (b, CH2,
cod), 34.8 (C, t-Bu), 34.9 (C, t-Bu), 36.2 (b, CH2, cod), 65.9
(b, CH=, cod), 70.3 (b, CH=, cod), 77.7 (CHO), 99.8 (d,
CH=, cod, J=24.4 Hz), 103.6 (d, CH=, cod, J=12.0 Hz),
117.7 (b, CH=, BArF), 120–134 (aromatic carbons), 135.0 (b,
161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%) for
À
C71H64BF24IrNO3P: C 51.09, H 3.86, N 0.84; found: C 51.02,
H 3.83, N 0.82.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L1f)]BArF: Yield: 119 mg (92%). 31P NMR
1
(C6D6): d=112.1 (s); H NMR (C6D6): d=0.17 (s, 9H, CH3,
SiMe3), 0.48 (s, 9H, CH3, SiMe3), 1.09 (b, 3H, CH3), 1.29 (b,
2H, CH2, cod), 1.67 (b, 2H, CH2, cod), 1.82 (b, 2H, CH2,
cod), 1.93 (b, 2H, CH2, cod), 3.64 (b, 1H, CH=, cod), 4.06
(b, 1H, CH=, cod), 4.12 (b, 1H, CH=, cod), 4.80 (b, 1H,
CH=, cod), 5.76 (m, 1H, CHO), 6.6–8.5 (m, 26H, CH=);
À
CH=, BArF), 136–159 (aromatic carbons), 161.9 (q, C B,
BArF, 1J=49 Hz); anal. calcd. (%) for C72H66BF24IrNO3P: C
51.37, H 3.95, N 0.83; found. C 51.33, H 3.92, N 0.79.
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
9
ÞÞ
These are not the final page numbers!

Javier Mazuela et al.
FULL PAPERS
[Ir
(cod)
E
t-Bu), 30.9 (CH3, t-Bu), 31.0 (CH3, t-Bu), 31.2 (CH3, t-Bu),
31.3 (CH3, t-Bu), 31.5 (C, t-Bu), 34.7 (b, CH2, cod), 34.8 (C,
t-Bu), 35.0 (C, t-Bu), 35.4 (C, t-Bu), 36.4 (b, CH2, cod), 63.5
(b, CH=, cod), 65.9 (b, CH=, cod), 89.7 (CHO), 101.1 (d,
CH=, cod,
JC,P =17.6 Hz), 104.3 (d, CH=, cod, JC,P =
16.8 Hz), 117.7 (b, CH=, BArF), 120–131 (aromatic carbons),
135.0 (b, CH=, BArF), 138–155 (aromatic carbons), 161.9 (q,
1J=49 Hz);
anal.
calcd.
(%)
for
À
1H, CH=, cod), 5.39 (m, 1H, CHO), 7.2–8.6 (m, 17H, CH= C B,
BArF,
); 13C NMR (CDCl3): d=16.8 (CH3-Ar), 16.9 (CH3-Ar), 20.5
(CH3-Ar), 20.8 (CH3-Ar), 24.8 (b, CH2, cod), 25.1 (CH3),
28.8 (b, CH2, cod), 29.8 (CH3-Py), 31.7 (CH3, t-Bu), 32.2
(CH3, t-Bu), 32.8 (b, CH2, cod), 34.6 (C, t-Bu), 34.8 (C, t-
Bu), 36.5 (b, CH2, cod), 64.9 (b, CH=, cod), 69.3 (b, CH=,
cod), 80.1 (CHO), 102.3 (b, CH=, cod), 102.9 (b, CH=, cod),
117.7 (b, CH=, BArF), 120–134 (aromatic carbons), 135.0 (b,
C78H78BF24IrNO3P: C 53.01, H 4.45, N 0.79; found: C 52.99,
H 4.43, N 0.77.
(L5d)]BArF: Yield: 122 mg (96%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=106.4 (s); 1H NMR (CDCl3): d=1.04 (s, 9H,
CH3, t-Bu), 1.21 (s, 9H, CH3, t-Bu), 1.47 (s, 9H, CH3, t-Bu),
1.73 (s, 3H, CH3-Ar), 1.79 (s, 3H, CH3-Ar), 2.14 (b, 2H,
CH2, cod), 2.22 (s, 3H, CH3-Ar), 2.27 (s, 3H, CH3-Ar), 2.29
(b, 4H, CH2, cod), 2.33 (b, 2H, CH2, cod), 3.86 (b, 1H, CH=
, cod), 4.41 (b, 1H, CH=, cod), 4.73 (b, 1H, CH=, cod), 5.19
(b, 1H, CH=, cod), 6.01 (m, 1H, CHO), 7.2–8.6 (m, 18H,
CH=); 13C NMR (CDCl3): d=16.2 (CH3-Ar), 16.5 (CH3-
Ar), 17.2 (CH3-Ar), 17.5 (CH3-Ar), 25.0 (b, CH2, cod), 27.8
(b, CH2, cod), 30.5 (C, t-Bu), 31.1 (CH3, t-Bu), 31.5 (CH3, t-
Bu), 32.2 (CH3, t-Bu), 33.4 (b, CH2, cod), 34.3 (C, t-Bu), 34.6
(C, t-Bu), 36.1 (b, CH2, cod), 66.9 (b, CH=, cod), 70.9 (b,
CH=, cod), 79.5 (CHO), 99.1 (d, CH=, cod, J=24.8 Hz),
103.4 (d, CH=, cod, J=11.6 Hz), 117.7 (b, CH=, BArF), 120–
134 (aromatic carbons), 135.0 (b, CH=, BArF), 136–159 (aro-
CH=, BArF), 136–158 (aromatic carbons), 161.9 (q, C B,
BArF, 1J=49 Hz); anal. calcd. (%) for C72H66BF24IrNO3P: C
51.37, H 3.95, N 0.83; found. C 51.35, H 3.93, N 0.80.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L3a)]BArF: Yield: 128 mg (96%). 31P NMR
(CDCl3): d=108.4 (s); 1H NMR (CDCl3): d=1.31 (s, 9H,
CH3, t-Bu), 1.37 (s, 9H, CH3, t-Bu), 1.38 (s, 9H, CH3, t-Bu),
1.58 (s, 9H, CH3, t-Bu), 1.60 (b, 3H, CH3), 1.79 (b, 2H, CH2,
cod), 2.29 (b, 4H, CH2, cod), 2.53 (b, 2H, CH2, cod), 4.31 (b,
1H, CH=, cod), 4.75 (b, 1H, CH=, cod), 5.16 (b, 1H, CH=,
cod), 5.30 (b, 1H, CH=, cod), 6.11 (m, 1H, CHO), 7.0–7.7
(m, 19H, CH=); 13C NMR (CDCl3): d=17.8 (b, CH3), 23.8
(b, CH2, cod), 28.0 (b, CH2, cod), 30.7 (C, t-Bu), 31.2 (C, t-
Bu), 31.5 (CH3, t-Bu), 31.7 (CH3, t-Bu), 34.9 (C, t-Bu), 35.0
(C, t-Bu), 35.4 (b, CH2, cod), 37.6 (b, CH2, cod), 72.3 (b,
CH=, cod), 74.9 (b, CH=, cod), 75.0 (CHO), 89.0 (d, CH=,
cod, JC,P =26.7 Hz), 102.8 (d, CH=, cod, JC,P =8.4 Hz), 117.7
(b, CH=, BArF), 120–132 (aromatic carbons), 135.0 (b, CH=,
matic carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd.
À
(%) for C74H70BF24IrNO3P: C 51.94, H 4.12, N 0.82; found.
C 51.91, H 4.10, N 0.81.
(L5e)]BArF: Yield: 119 mg (94%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=105.2 (s); 1H NMR (CDCl3): d=1.02 (s, 9H,
CH3, t-Bu), 1.25 (s, 9H, CH3, t-Bu), 1.44 (s, 9H, CH3, t-Bu),
1.71 (s, 3H, CH3-Ar), 1.76 (s, 3H, CH3-Ar), 2.11 (b, 2H,
CH2, cod), 2.27 (s, 6H, CH3-Ar), 2.29 (b, 4H, CH2, cod),
2.37 (b, 2H, CH2, cod), 3.63 (b, 1H, CH=, cod), 4.26 (b, 1H,
CH=, cod), 4.83 (b, 1H, CH=, cod), 5.29 (b, 1H, CH=, cod),
5.51 (m, 1H, CHO), 7.2–8.6 (m, 18H, CH=); 13C NMR
(CDCl3): d=16.5 (CH3-Ar), 16.6 (CH3-Ar), 20.1 (CH3-Ar),
20.4 (CH3-Ar), 24.9 (b, CH2, cod), 28.7 (b, CH2, cod), 30.3
(C, t-Bu), 31.1 (CH3, t-Bu), 32.3 (CH3, t-Bu), 32.4 (CH3, t-
Bu), 32.6 (b, CH2, cod), 33.9 (C, t-Bu), 34.2 (C, t-Bu), 35.9
(b, CH2, cod), 64.2 (b, CH=, cod), 69.8 (b, CH=, cod), 81.2
(CHO), 102.2 (b, CH=, cod), 104.2 (b, CH=, cod), 117.7 (b,
CH=, BArF), 120–134 (aromatic carbons), 135.0 (b, CH=,
BArF), 139–150 (aromatic carbons), 161.9 (q, C B, BArF,
1J=49 Hz); anal. calcd. (%) for C75H71BBrF24IrNO3P: C
49.93, H 3.97, N 0.78; found: C 49.88, H 3.94, N 0.75.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L4a)]BArF: Yield: 125 mg (94%). 31P NMR
(CDCl3): d=98.2 (s); 1H NMR (CDCl3), d=1.33 (s, 9H,
CH3, t-Bu), 1.34 (s, 9H, CH3, t-Bu), 1.38 (s, 9H, CH3, t-Bu),
1.54 (b, 3H, CH3), 1.59 (s, 9H, CH3, t-Bu), 1.89 (b, 2H, CH2,
cod), 2.19 (b, 4H, CH2, cod), 2.63 (b, 2H, CH2, cod), 4.62 (b,
1H, CH=, cod), 4.68 (b, 1H, CH=, cod), 4.79 (b, 1H, CH=,
cod), 5.29 (b, 1H, CH=, cod), 6.07 (m, 1H, CHO), 7.1–8.2
(m, 24H, CH=); 13C NMR (CDCl3): d=17.2 (d, CH3, JC,P
10.8), 23.2 (b, CH2, cod), 28.4 (b, CH2, cod), 30.2 (CH3, t-
Bu), 30.5 (CH3, t-Bu), 30.9 (C, t-Bu), 31.3 (CH3, t-Bu), 31.4
(CH3, t-Bu), 34.7 (b, CH2, cod), 35.0 (C, t-Bu), 35.3 (C, t-
Bu), 35.6 (C, t-Bu), 35.7 (b, CH2, cod), 70.6 (b, CH=, cod),
À
BArF), 136–158 (aromatic carbons), 161.9 (q, C B, BArF,
1J=49 Hz); anal. calcd. (%) for C74H70BF24IrNO3P: C 51.94,
H 4.12, N 0.82; found. C 51.90, H 4.11, N 0.80.
73.1 (b, CH=, cod), 74.6 (CHO), 83.2 (d, CH=, cod, JC,P
(L6a)]BArF: Yield: 123 mg (93%). 31P NMR
[IrACTHNGUTRENNU(G cod)ACHTGNUTRENNUNG
29.4 Hz), 97.6 (d, CH=, cod, JC,P =7 Hz), 117.7 (b, CH=,
BArF), 120–133 (aromatic carbons), 135.0 (b, CH=, BArF),
(CDCl3): d=103.6 (s); 1H NMR (CDCl3): d=1.13 (s, 9H,
CH3, t-Bu), 1.15 (s, 9H, CH3, t-Bu), 1.20 (s, 9H, CH3, t-Bu),
1.23 (s, 9H, CH3, t-Bu), 1.43 (b, 2H, CH2, cod), 1.62 (b, 2H,
CH2, cod), 1.96 (b, 2H, CH2, cod), 2.39 (b, 2H, CH2, cod),
3.70 (b, 1H, CH=, cod), 4.24 (b, 1H, CH=, cod), 4.74 (b,
1H, CH=, cod), 5.30 (b, 1H, CH=, cod), 6.91 (m, 1H,
CHO), 7.0–8.5 (m, 25H, CH=); 13C NMR (CDCl3): d=25.1
(b, CH2, cod), 28.6 (b, CH2, cod), 30.9 (CH3, t-Bu), 31.3
(CH3, t-Bu), 31.5 (CH3, t-Bu), 32.1 (CH3, t-Bu), 33.2 (b,
CH2, cod), 34.7 (C, t-Bu), 34.8 (C, t-Bu), 35.2 (C, t-Bu), 35.6
(C, t-Bu), 36.7 (b, CH2, cod), 65.2 (b, CH=, cod), 70.6 (b,
CH=, cod), 81.9 (d, CH, JC,P =10.1 Hz), 101.7 (d, CH=, cod,
137–159 (aromatic carbons), 161.9 (q, C B, BArF, 1J=
À
49 Hz); anal. calcd. (%) for C81H76BF24IrNO3P: C 54.00, H
4.25, N 0.78; found: C 53.96, H 4.22, N 0.76.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L5a)]BArF: Yield: 123 mg (94%). 31P NMR
(CDCl3): d=108.8 (s); 1H NMR (CDCl3): d=1.06 (s, 9H,
CH3, t-Bu), 1.18 (s, 9H, CH3, t-Bu), 1.33 (s, 9H, CH3, t-Bu),
1.34 (s, 9H, CH3, t-Bu), 1.40 (s, 9H, CH3, t-Bu), 2.02 (b, 2H,
CH2, cod), 2.21 (b, 4H, CH2, cod), 2.36 (b, 2H, CH2, cod),
4.22 (b, 1H, CH=, cod), 4.36 (b, 1H, CH=, cod), 5.16 (b,
1H, CH=, cod), 5.17 (b, 1H, CH=, cod), 5.20 (m, 1H,
CHO), 7.1–8.7 (m, 20H, CH=); 13C NMR (CDCl3): d=24.9
(b, CH2, cod), 26.9 (CH3, t-Bu), 29.8 (b, CH2, cod), 30.6 (C,
J
C,P =21 Hz), 105.0 (d, CH=, cod, JC,P =12.4 Hz), 117.7 (b,
CH=, BArF), 120–133 (aromatic carbons), 135.0 (b, CH=,
10
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

A Phosphite-Pyridine/Iridium Complex Library as Highly Selective Catalysts for the Hydrogenation
À
BArF), 139–160 (aromatic carbons), 161.9 (q, C B, BArF,
1J=49 Hz); anal. calcd. (%) for C80H74BF24IrNO3P: C 53.76,
H 4.17, N 0.78; found: C 53.73, H 4.15, N 0.76.
1H, CH=, cod), 4.38 (b, 1H, CH=, cod), 4.99 (b, 1H, CH=,
cod), 5.38 (b, 1H, CH=, cod), 5.73 (d, 1H, CHO, JC,P
=
6.4 Hz), 7.0–7.8 (m, 19H, CH=); 13C NMR (CDCl3): d=23.9
(b, CH2, cod), 27.2 (b, CH2, cod), 28.2 (C, t-Bu), 30.0 (CH3,
t-Bu), 30.1 (CH3, MePy), 30.9 (CH3, t-Bu), 31.0 (CH3, t-Bu),
31.2 (CH3, t-Bu), 31.3 (CH3, t-Bu), 34.6 (C, t-Bu), 34.8 (b,
CH2, cod), 34.9 (C, t-Bu), 35.0 (C, t-Bu), 35.4 (C, t-Bu), 35.8
(b, CH2, cod), 37.3 (b, CH2, cod), 67.4 (b, CH=, cod), 73.8
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L6c)]BArF: Yield: 116 mg (92%). 31P NMR
(CDCl3): d=103.2 (s); 1H NMR (CDCl3): d=0.20 (s, 9H,
CH3, SiMe3), 0.24 (s, 9H, CH3, SiMe3), 1.75 (b, 2H, CH2,
cod), 1.91 (b, 2H, CH2, cod), 2.19 (b, 2H, CH2, cod), 2.53 (b,
2H, CH2, cod), 4.18 (b, 1H, CH=, cod), 4.44 (b, 1H, CH=,
cod), 4.80 (b, 1H, CH=, cod), 5.54 (b, 1H, CH=, cod), 7.03
(m, 1H, CHO), 7.1–8.7 (m, 27H, CH=); 13C NMR (CDCl3):
d=0.2 (CH3, SiMe3), 1.3 (CH3, SiMe3), 25.5 (b, CH2, cod),
28.9 (b, CH2, cod), 34.4 (b, CH2, cod), 37.4 (d, CH2, cod,
(b, CH=, cod), 87.6 (s, CHO), 87.9 (d, CH=, cod, JC,P
=
26.4 Hz), 103.8 (d, CH=, cod, JC,P =9.3 Hz), 117.7 (b, CH=,
BArF), 120–131 (aromatic carbons), 135.0 (b, CH=, BArF),
138–157 (aromatic carbons), 161.9 (q, C B, BArF, 1J=
À
J
C,P =6.2 Hz), 67.3 (b, CH=, cod), 72.1 (b, CH=, cod), 82.7
49 Hz); anal. calcd. (%) for C79H80BF24IrNO3P: C 53.26, H
4.53, N 0.79; found: C 53.23, H 4.51, N 0.76.
(d, CH, JC,P =9.3 Hz), 101.4 (d, CH=, cod, JC,P =21.7 Hz),
106.0 (d, CH=, cod, JC,P =11.7 Hz), 117.7 (b, CH=, BArF),
120–134 (aromatic carbons), 135.0 (b, CH=, BArF), 136–160
(L8a)]BArF: Yield: 126 mg (96%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=111.1 (s); 1H NMR (CDCl3): d=1.01 (s, 9H,
CH3, t-Bu), 1.22 (s, 9H, CH3, t-Bu), 1.29 (s, 9H, CH3, t-Bu),
1.53 (s, 9H, CH3, t-Bu), 1.70 (b, 2H, CH2, cod), 1.77 (d, 3H,
CH3, 3JH,H =6.8 Hz), 2.22 (b, 4H, CH2, cod), 2.58 (b, 2H,
CH2, cod), 4.18 (b, 1H, CH=, cod), 4.57 (b, 1H, CH=, cod),
5.04 (b, 1H, CH=, cod), 5.16 (b, 1H, CH=, cod), 6.29 (m,
1H, CHO), 6.9–9.0 (m, 22H, CH=); 13C NMR (CDCl3): d=
18.3 (CH3), 24.0 (b, CH2, cod), 27.8 (b, CH2, cod), 30.5
(CH3, t-Bu), 31.0 (CH3, t-Bu), 31.1 (CH3, t-Bu), 31.2 (CH3, t-
Bu), 31.3 (C, t-Bu), 34.7 (b, CH2, cod), 35.0 (C, t-Bu), 35.1
(C, t-Bu), 35.3 (C, t-Bu), 37.6 (b, CH2, cod), 70.5 (b, CH=,
cod), 72.0 (b, CH=, cod), 77.2 (CHO), 91.0 (d, CH=, cod,
(aromatic carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal.
À
calcd. (%) for C70H58BF24IrNO3PSi2: C 49.24, H 3.42, N 0.82
found: C 49.21, H 3.40, N 0.79.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L6d)]BArF: Yield: 116 mg (92%). 31P NMR
(CDCl3): d=102.3 (s); 1H NMR (CDCl3): d=1.28 (s, 9H,
CH3, t-Bu), 1.39 (s, 9H, CH3, t-Bu), 1.68 (s, 3H, CH3-Ar),
1.73 (s, 3H, CH3-Ar), 2.12 (b, 2H, CH2, cod), 2.13 (s, 3H,
CH3-Ar), 2.19 (s, 3H, CH3-Ar), 2.28 (b, 4H, CH2, cod), 2.34
(b, 2H, CH2, cod), 3.92 (b, 1H, CH=, cod), 4.41 (b, 1H,
CH=, cod), 4.54 (b, 1H, CH=, cod), 5.33 (b, 1H, CH=, cod),
6.02 (m, 1H, CHO), 7.2–8.6 (m, 23H, CH=); 13C NMR
(CDCl3); d=16.2 (CH3-Ar), 16.4 (CH3-Ar), 17.2 (CH3-Ar),
17.5 (CH3-Ar), 20.9 (CH3), 25.1 (b, CH2, cod), 27.9 (b, CH2,
cod), 31.9 (CH3, t-Bu), 32.2 (CH3, t-Bu), 34.2 (b, CH2, cod),
34.9 (C, t-Bu), 35.1 (C, t-Bu), 36.7 (b, CH2, cod), 68.2 (b,
CH=, cod), 70.2 (b, CH=, cod), 77.2 (CHO), 101.2 (d, CH=,
cod, J=23.8 Hz), 104.1 (d, CH=, cod, J=16.0 Hz), 117.7 (b,
CH=, BArF), 120–134 (aromatic carbons), 135.0 (b, CH=,
J
C,P =24 Hz), 104.5 (d, CH=, cod, JC,P =9.3 Hz), 117.7 (b,
CH=, BArF), 119–132 (aromatic carbons), 135.0 (b, CH=,
À
BArF), 138–161 (aromatic carbons), 161.9 (q, C B, BArF,
1J=49 Hz); anal. calcd. (%) for C79H74BF24IrNO3P: C 53.44,
H 4.20, N 0.79; found: C 53.41, H 4.17, N 0.76.
(L9a)]BArF: Yield: 116 mg (92%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=106.0 (s); 1H NMR (CDCl3): d=1.29 (s, 9H,
CH3, t-Bu), 1.34 (s, 18H, CH3, t-Bu), 1.51 (s, 9H, CH3, t-Bu),
1.87 (b, 2H, CH2, cod), 2.13 (b, 3H, CH3), 2.21 (b, 4H, CH2,
cod), 2.36 (b, 2H, CH2, cod), 3.94 (b, 1H, CH=, cod), 4.29
(b, 1H, CH=, cod), 4.71 (b, 1H, CH=, cod), 5.24 (b, 1H,
CH=, cod), 6.12 (m, 1H, CHO), 7.1–8.6 (m, 20H, CH=);
13C NMR (CDCl3): d=25.3 (b, CH2, cod), 29.0 (b, CH2,
cod), 30.7 (C, t-Bu), 30.9 (CH3), 31.1 (CH3, t-Bu), 31.2 (CH3,
t-Bu), 31.3 (CH3, t-Bu), 31.9 (CH3, t-Bu), 33.0 (b, CH2, cod),
34.8 (C, t-Bu), 35.4 (C, t-Bu), 35.5 (C, t-Bu), 36.3 (b, CH2,
cod), 65.8 (b, CH=, cod), 69.9 (b, CH=, cod), 77.2 (CHO),
100.7 (d, CH=, cod, JC,P =20.9 Hz), 104.5 (d, CH=, cod,
À
BArF), 136–159 (aromatic carbons), 161.9 (q, C B, BArF,
1J=49 Hz); anal. calcd. (%) for C76H66BF24IrNO3P: C 52.72,
H 3.84, N 0.81; found. C 52.71, H 3.83, N 0.80.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L6e)]BArF: Yield: 119 mg (93%). 31P NMR
(CDCl3): d=102.1 (s); 1H NMR (CDCl3): d=1.21 (s, 9H,
CH3, t-Bu), 1.44 (s, 9H, CH3, t-Bu), 1.63 (s, 6H, CH3-Ar),
1.69 (s, 3H, CH3-Ar), 1.72 (s, 3H, CH3-Ar), 1.77 (s, 3H,
CH3), 2.11 (b, 2H, CH2, cod), 2.17 (s, 3H, CH3-Ar), 2.24 (b,
4H, CH2, cod), 2.31 (b, 2H, CH2, cod), 3.98 (b, 1H, CH=,
cod), 4.37 (b, 1H, CH=, cod), 4.47 (b, 1H, CH=, cod), 5.26
(b, 1H, CH=, cod), 6.06 (m, 1H, CHO), 7.2–8.6 (m, 23H,
CH=); 13C NMR (CDCl3): d=16.1 (CH3-Ar), 16.2 (CH3-
Ar), 17.0 (CH3-Ar), 17.3 (CH3-Ar), 20.7 (CH3), 25.1 (b,
CH2, cod), 27.9 (b, CH2, cod), 31.9 (CH3, t-Bu), 32.2 (CH3, t-
Bu), 34.2 (b, CH2, cod), 34.8 (C, t-Bu), 35.2 (C, t-Bu), 36.3
(b, CH2, cod), 71.1 (b, CH=, cod), 72.6 (b, CH=, cod), 79.2
(CHO), 100.2 (d, CH=, cod, J=24.8 Hz), 102.6 (d, CH=,
cod, J=12.0 Hz), 117.7 (b, CH=, BArF), 120–134 (aromatic
carbons), 135.0 (b, CH=, BArF), 136–159 (aromatic carbons),
J
C,P =12.5 Hz), 117.7 (b, CH=, BArF), 119–131 (aromatic car-
bons), 135.0 (b, CH=, BArF), 139–159 (aromatic carbons),
161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%) for
À
C75H72BF24IrNO3P: C 52.21, H 4.21, N 0.81; found: C 52.18,
H 4.19, N 0.78.
(L9d)]BArF: Yield: 118 mg (96%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=102.9 (s); 1H NMR (CDCl3): d=1.19 (s, 9H,
CH3, t-Bu), 1.42 (s, 9H, CH3, t-Bu), 1.69 (b, 6H, CH3, Ar-
Me), 1.73 (b, 3H, CH3), 2.02 (b, 2H, CH2, cod), 2.18 (b, 6H,
CH3, Ar-Me), 2.29 (b, 4H, CH2, cod), 2.52 (b, 2H, CH2,
cod), 3.73 (b, 1H, CH=, cod), 4.27 (b, 1H, CH=, cod), 4.52
(b, 1H, CH=, cod), 5.15 (b, 1H, CH=, cod), 6.00 (m, 1H,
CHO), 7.1–8.5 (m, 18H, CH=); 13C NMR (CDCl3); d=16.6
(CH3, Ar-Me), 16.7 (CH3, Ar-Me), 17.3 (CH3, Ar-Me), 17.4
(CH3, Ar-Me), 20.3 (CH3), 25.0 (b, CH2, cod), 28.5 (b, CH2,
cod), 31.2 (CH3, t-Bu), 32.3 (CH3, t-Bu), 33.5 (b, CH2, cod),
34.8 (C, t-Bu), 34.9 (C, t-Bu), 36.7 (b, CH2, cod), 65.8 (b,
161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%) for
À
C76H66BF24IrNO3P: C 52.72, H 3.84, N 0.81; found. C 52.68,
H 3.81, N 0.78.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L7a)]BArF: Yield: 128 mg (97%). 31P NMR
(CDCl3); d=105.1 (s); 1H NMR (CDCl3): d=1.01 (s, 9H,
CH3, t-Bu), 1.13 (s, 9H, CH3, t-Bu), 1.28 (s, 9H, CH3, t-Bu),
1.38 (s, 9H, CH3, t-Bu), 1.53 (s, 9H, CH3, t-Bu), 1.80 (b, 2H,
CH2, cod), 2.04 (b, 2H, CH2, cod), 2.25 (b, 2H, CH2, cod),
2.43 (b, 2H, CH2, cod), 3.19 (s, 3H, CH3, MePy), 3.90 (b,
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
11
ÞÞ
These are not the final page numbers!

Javier Mazuela et al.
FULL PAPERS
CH=, cod), 70.7 (b, CH=, cod), 77.2 (s, CHO), 99.6 (d, CH=,
cod, JC,P =20.9 Hz), 104.0 (d, CH=, cod, JC,P =11.6 Hz), 117.7
(b, CH=, BArF), 120–135 (aromatic carbons), 135.0 (b, CH=,
for C72H66BF24IrNO3P: C 51.37, H 3.95, N 0.83; found: C
51.34, H 3.92, N 0.80.
(L11a)]BArF: Yield: 123 mg (94%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=108.4 (s); 1H NMR (CDCl3): d=1.08 (s, 9H,
CH3, t-Bu), 1.16 (s, 9H, CH3, t-Bu), 1.32 (s, 9H, CH3, t-Bu),
1.37 (s, 9H, CH3, t-Bu), 1.41 (s, 9H, CH3, t-Bu), 2.01 (b, 2H,
CH2, cod), 2.21 (b, 4H, CH2, cod), 2.36 (b, 2H, CH2, cod),
4.24 (b, 1H, CH=, cod), 4.34 (b, 1H, CH=, cod), 5.20 (b,
2H, CH=, cod), 5.27 (m, 1H, CHO), 7.1–8.7 (m, 20H, CH=
); 13C NMR (CDCl3): d=24.8 (b, CH2, cod), 26.8 (CH3, t-
Bu), 29.9 (b, CH2, cod), 30.5 (C, t-Bu), 30.7 (CH3, t-Bu), 31.1
(CH3, t-Bu), 31.2 (CH3, t-Bu), 31.4 (C, t-Bu), 34.6 (b, CH2,
cod), 34.7 (C, t-Bu), 35.0 (C, t-Bu), 35.4 (C, t-Bu), 36.4 (b,
CH2, cod), 63.5 (b, CH=, cod), 66.2 (b, CH=, cod), 89.5
(CHO), 101.0 (d, CH=, cod, JC,P =16.4 Hz), 104.1 (d, CH=,
cod, JC,P =18.2 Hz), 117.7 (b, CH=, BArF), 120–131 (aromat-
ic carbons), 135.0 (b, CH=, BArF), 138–155 (aromatic car-
À
BArF), 136–159 (aromatic carbons), 161.9 (q, C B, BArF,
1J=49 Hz); anal. calcd. (%) for C71H64BF24IrNO3P: C 51.09,
H 3.86, N 0.84; found: C 51.06, H 3.84, N 0.81.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L9e)]BArF: Yield: 113 mg (94%). 31P NMR
(CDCl3): d=102.2 (s); 1H NMR (CDCl3): d=1.12 (s, 9H,
CH3, t-Bu), 1.43 (s, 9H, CH3, t-Bu), 1.65 (b, 6H, CH3, Ar-
Me), 1.72 (b, 3H, CH3), 2.05 (b, 2H, CH2, cod), 2.17 (b, 6H,
CH3, Ar-Me), 2.19 (b, 4H, CH2, cod), 2.36 (b, 2H, CH2,
cod), 3.42 (b, 1H, CH=, cod), 4.05 (b, 1H, CH=, cod), 4.70
(b, 1H, CH=, cod), 5.33 (b, 1H, CH=, cod), 5.41 (m, 1H,
CHO), 7.0–8.5 (m, 18H, CH=); 13C NMR (CDCl3): d=16.7
(CH3, Ar-Me), 16.8 (CH3, Ar-Me), 20.4 (CH3, Ar-Me), 20.5
(CH3, Ar-Me), 25.1 (b, CH2, cod), 25.4 (CH3), 28.7 (b, CH2,
cod), 32.2 (CH3, t-Bu), 32.5 (CH3, t-Bu), 33.1 (b, CH2, cod),
35.2 (C, t-Bu), 35.3 (C, t-Bu), 37.1 (b, CH2, cod), 64.0 (b,
CH=, cod), 67.8 (b, CH=, cod), 81.1 (CHO), 102.7 (b, CH=,
cod), 102.9 (b, CH=, cod), 117.7 (b, CH=, BArF), 120–135
(aromatic carbons), 135.0 (b, CH=, BArF), 135–159 (aromat-
bons), 161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%) for
À
C78H78BF24IrNO3P: C 53.01, H 4.45, N 0.79; found. C 52.97,
H 4.43, N 0.76.
(L11e)]BArF: Yield: 114 mg (92%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=106.5 (s); 1H NMR (CDCl3): d=1.05 (s, 9H,
CH3, t-Bu), 1.09 (s, 9H, CH3, t-Bu), 1.37 (s, 9H, CH3, t-Bu),
1.55 (s, 3H, CH3, Ar-Me), 1.74 (s, 3H, CH3, Ar-Me), 1.95 (b,
2H, CH2, cod), 2.05 (b, 3H, CH2, cod), 2.08 (s, 3H, CH3, Ar-
Me), 2.13 (s, 3H, CH3, Ar-Me), 2.33 (b, 2H, CH2, cod), 2.58
(b, 1H, CH2, cod), 4.31 (b, 1H, CH=, cod), 4.32 (b, 1H,
CH=, cod), 4.40 (b, 1H, CH=, cod), 5.36 (b, 1H, CH=, cod),
5.38 (m, 1H, CHO), 7.0–8.7 (m, 18H, CH=); 13C NMR
(CDCl3); d=16.4 (CH3, Ar-Me), 16.5 (CH3, Ar-Me), 20.2
(CH3, Ar-Me), 20.4 (CH3, Ar-Me), 24.7 (b, CH2, cod), 27.7
(CH3, t-Bu), 28.3 (b, CH2, cod), 29.7 (C, t-Bu), 31.5 (CH3, t-
Bu), 31.6 (CH3, t-Bu), 34.4 (b, CH2, cod), 34.5 (C, t-Bu), 35.0
(C, t-Bu), 36.9 (b, CH2, cod), 67.6 (b, CH=, cod), 69.6 (b,
CH=, cod), 88.2 (CHO), 97.4 (d, CH=, cod, JC,P =23.2 Hz),
102.9 (d, CH=, cod, JC,P =11.7 Hz), 117.7 (b, CH=, BArF),
120–134 (aromatic carbons), 135.0 (b, CH=, BArF), 135–157
ic carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd.
À
(%) for C71H64BF24IrNO3P: C 51.09, H 3.86, N 0.84; found:
C 51.02, H 3.81, N 0.80.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L10a)]BArF: Yield: 124 mg (96%). 31P NMR
(CDCl3): d=109.9 (s); 1H NMR (CDCl3): d=1.32 (s, 9H,
CH3, t-Bu), 1.35 (s, 9H, CH3, t-Bu), 1.39 (s, 9H, CH3, t-Bu),
1.57 (s, 9H, CH3, t-Bu), 1.72 (b, 3H, CH3), 1.97 (b, 3H, CH2,
cod), 2.18 (b, 1H, CH2, cod), 2.40 (b, 2H, CH2, cod), 2.53 (b,
2H, CH2, cod), 3.19 (b, 3H, CH3-Py), 3.98 (b, 1H, CH=,
cod), 4.61 (b, 1H, CH=, cod), 5.03 (b, 1H, CH=, cod), 5.22
(b, 1H, CH=, cod), 6.21 (m, 1H, CHO), 7.0–8.0 (m, 19H,
CH=); 13C NMR (CDCl3): d=17.8 (b, CH3), 23.8 (b, CH2,
cod), 27.8 (b, CH2, cod), 29.1 (CH3-Py), 30.4 (CH3, t-Bu),
30.9 (C, t-Bu), 31.2 (C, t-Bu), 31.3 (CH3, t-Bu), 31.4 (CH3, t-
Bu), 34.6 (b, CH2, cod), 35.2 (C, t-Bu), 35.4 (C, t-Bu), 37.7
(b, CH2, cod), 70.3 (b, CH=, cod), 72.8 (b, CH=, cod), 75.4
(CHO), 89.2 (d, CH=, cod, JC,P =22.4 Hz), 104.2 (b, CH=,
cod), 117.7 (b, CH=, BArF), 120–131 (aromatic carbons),
135.0 (b, CH=, BArF), 139–158 (aromatic carbons), 161.9 (q,
À
(aromatic carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal.
À
calcd- (%) for C74H70BF24IrNO3P: C 51.94, H 4.12, N 0.82;
found: C 51.90, H 4.09, N 0.79.
(L12c)]BArF: Yield: 114 mg (91%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
1J=49 Hz);
anal.
calcd.
(%)
for
(CDCl3): d=103.2 (s); 1H NMR (CDCl3): d=0.21 (s, 9H,
CH3, SiMe3), 0.24 (s, 9H, CH3, SiMe3), 1.74 (b, 2H, CH2,
cod), 1.90 (b, 2H, CH2, cod), 2.17 (b, 2H, CH2, cod), 2.49 (b,
2H, CH2, cod), 4.17 (b, 1H, CH=, cod), 4.37 (b, 1H, CH=,
cod), 4.77 (b, 1H, CH=, cod), 5.52 (b, 1H, CH=, cod), 7.02
(m, 1H, CHO), 7.1–8.7 (m, 27H, CH=); 13C NMR (CDCl3):
d=0.2 (CH3, SiMe3), 1.1 (CH3, SiMe3), 25.6 (b, CH2, cod),
28.9 (b, CH2, cod), 34.9 (b, CH2, cod), 36.8 (d, CH2, cod,
C B,
BArF,
C76H74BF24IrNO3P: C 52.48, H 4.29, N 0.81; found. C 52.42,
H 4.25, N 0.78.
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L10e)]BArF: Yield: 116 mg (94%). 31P NMR
(CDCl3): d=105.2 (s); 1H NMR (CDCl3): d=1.27 (s, 9H,
CH3, t-Bu), 1.46 (s, 9H, CH3, t-Bu), 1.61 (b, 6H, CH3, Ar-
Me), 1.76 (b, 3H, CH3), 1.95 (b, 2H, CH2, cod), 2.07 (b, 2H,
CH2, cod), 2.16 (s, 3H, CH3, Ar-Me), 2.19 (s, 3H, CH3, Ar-
Me), 2.28 (b, 2H, CH2, cod), 2.37 (b, 2H, CH2, cod), 3.04 (s,
3H, CH3, MePy), 3.77 (b, 1H, CH=, cod), 4.50 (b, 1H, CH=,
cod), 4.80 (b, 1H, CH=, cod), 5.10 (b, 1H, CH=, cod), 6.11
(m, 1H, CHO), 7.0–7.7 (m, 17H, CH=); 13C NMR (CDCl3):
d=16.5 (CH3, Ar-Me), 16.7 (CH3, Ar-Me), 20.3 (CH3, Ar-
Me), 20.4 (CH3, Ar-Me), 23.8 (b, CH2, cod), 27.7 (CH3,
MePy), 29.4 (CH3), 29.7 (b, CH2, cod), 30.7 (CH3, t-Bu), 31.9
(CH3, t-Bu), 34.6 (C, t-Bu), 34.7 (C, t-Bu), 35.5 (b, CH2,
cod), 37.4 (b, CH2, cod), 71.4 (b, CH=, cod), 72.7 (b, CH=,
cod), 75.0 (CHO), 88.2 (d, CH=, cod, JC,P =27.1), 103.4 (d,
CH=, cod, JC,P =8.6 Hz), 117.7 (b, CH=, BArF), 120–135 (ar-
omatic carbons), 135.0 (b, CH=, BArF), 135–158 (aromatic
J
C,P =6.2 Hz), 67.6 (b, CH=, cod), 72.3 (b, CH=, cod), 82.3
(d, CH, JC,P =7.2 Hz), 101.2 (d, CH=, cod, JC,P =20.4 Hz),
105.4 (d, CH=, cod, JC,P =12.0 Hz), 117.7 (b, CH=, BArF),
120–134 (aromatic carbons), 135.0 (b, CH=, BArF), 136–160
(aromatic carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal.
À
calcd. (%) for C70H58BF24IrNO3PSi2: C 49.24, H 3.24, N
0.82; found. C 49.21, H 3.22, N 0.80.
(L12e)]BArF: Yield: 122 mg (94%). 31P NMR
[IrACTHNUGRTENNUG(cod)ACHTUGNTRENNUGN
(CDCl3): d=101.0 (s); 1H NMR (CDCl3): d=1.53 (s, 9H,
CH3, t-Bu), 1.60 (s, 9H, CH3, t-Bu), 2.08 (s, 3H, CH3, Ar-
Me), 2.15 (s, 3H, CH3, Ar-Me), 2.02 (b, 2H, CH2, cod), 2.39
(b, 4H, CH2, cod), 2.49 (b, 2H, CH2, cod), 2.59 (s, 3H, CH3,
Ar-Me), 2.63 (s, 3H, CH3, Ar-Me), 3.63 (b, 1H, CH=, cod),
carbons), 161.9 (q, C B, BArF, 1J=49 Hz); anal. calcd. (%)
À
12
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

A Phosphite-Pyridine/Iridium Complex Library as Highly Selective Catalysts for the Hydrogenation
4.29 (b, 1H, CH=, cod), 5.32 (b, 1H, CH=, cod), 5.48 (b,
1H, CH=, cod), 6.75 (m, 1H, CHO), 7.5–8.9 (m, 23H, CH=
); 13C NMR (CDCl3): d=16.7 (b, CH3, Ar-Me), 20.4 (CH3,
Ar-Me), 20.5 (CH3, Ar-Me), 25.2 (b, CH2, cod), 28.9 (b,
CH2, cod), 31.3 (b, CH2, cod), 31.7 (CH3, t-Bu), 32.5 (CH3, t-
Bu), 35.0 (C, t-Bu), 35.2 (C, t-Bu), 36.9 (b, CH2, cod), 62.8
(b, CH=, cod), 66.5 (b, CH=, cod), 85.8 (CHO), 103.2 (d,
CH=, cod, JC,P =14 Hz), 105.8 (d, CH=, cod, JC,P =18.6 Hz),
117.7 (b, CH=, BArF), 120–135 (aromatic carbons), 135.0 (b,
[2] For recent reviews, see: a) K. Kꢅllstrçm, I. Munslow,
P. G. Andersson, Chem. Eur. J. 2006, 12, 3194; b) S. J.
Roseblade, A. Pfaltz, Acc. Chem. Res. 2007, 40, 1402;
c) T. L. Church, P. G. Andersson, Coord. Chem. Rev.
2008, 252, 513; d) X. Cui, K. Burgess, Chem. Rev. 2005,
105, 3272; e) O. Pꢀmies, P. G. Andersson, M. Diꢁguez,
Chem. Eur. J. 2010, 16, 14232; f) D. H. Woodmansee,
A. Pfaltz, Chem. Commun. 2011, 47, 7912.
[3] R. H. Crabtree, Acc. Chem. Res. 1979, 12, 331.
[4] Chelating oxazoline-carbene ligands, mainly developed
by Burgess and co.workers, have also been successful
used and also to a less extent chiral diphosphines. See,
for instance: a) M. C. Perry, X. Cui, M. T. Powell, D. R.
Hou, J. H. Reibenspies, K. Burgess, J. Am. Chem. Soc.
2003, 125, 113; b) X. Cui, K. Burgess, J. Am. Chem.
Soc. 2003, 125, 14212; c) X. Cui, J. W. Ogle, K. Burgess,
Chem. Commun. 2005, 672; d) J. Zhao, K. Burgess, J.
Am. Chem. Soc. 2009, 131, 13236; e) T. T. Co, T. J. Kim,
Chem. Commun. 2006, 3537; f) G. S. Forman, T.
Ohkuma, W. P. Hems, R. Noyori, Tetrahedron Lett.
2000, 41, 9471.
[5] Very recently, the ligand scope has been extended to
the use of other non-nitrogen-containing heterodonor
ligands like P,O and P,S; see: a) D. Rageot, D. H.
Woodmansee, B. Pugin, A. Pfaltz, Angew. Chem. 2011,
123, 9772; Angew. Chem. Int. Ed. 2011, 50, 9598; b) M.
Coll, O. Pꢀmies, M. Diꢁguez, Chem. Commun. 2011,
47, 9215; c) M. Coll, O. Pꢀmies, M. Diꢁguez, Adv.
Synth. Catal. 2013, 355, 143–160.
À
CH=, BArF), 135–157 (aromatic carbons), 161.9 (q, C B,
BArF, 1J=49 Hz); anal. calcd. (%) for C76H66BF24IrNO3P: C
52.72, H 3.84, N 0.81; found: C 52.69, H 3.82, N 0.78.
Typical Procedure for the Hydrogenation of Olefins
The alkene (0.5 mmol) and the corresponding Ir complex
(1 mol%) were dissolved in CH2Cl2 (1 mL) in a high-pres-
sure autoclave. The autoclave was purged four times with
hydrogen. Then, it was pressurized at the desired pressure.
After the desired reaction time, the autoclave was depres-
surized and the solvent evaporated off. The residue was dis-
solved in Et2O (1 mL) and filtered through a short plug of
1
celite. The conversions were determined by H NMR or GC
and enantiomeric excess was determined by chiral GC or
chiral HPLC. The enantiomeric excesses of hydrogenated
products from S1, S2,[6d] S3,[30a] S4,[6d] S5,[10e] S6[30a] S7, S8,[6d]
S9, S10,[8b] S11, S12,[16] S13,[6d] S14, S15,[6r] S16, S17,[6d]
S18,[30b] S19,[6q] S20–S22,[6s] S23,[19a] S24,[6d] S25,[19a] S26,
S27,[30c] S28,[10c] S29,[6d] S30,[30c] S31–S35,[6d] S36,[10c] S37,[30d]
S38,[6d] S39[10c] and S40[30b] were determined using the condi-
tions previously described.
[6] See, for instance: a) M. C. Perry, X. Cui, M. T. Powell,
D. R. Hou, J. H. Reibenspies, K. Burgess, J. Am. Chem.
Soc. 2003, 125, 5391; b) J. Blankestein, J.; A. Pfaltz,
Angew. Chem. 2001, 113, 4577; Angew. Chem. Int. Ed.
2001, 40, 4445; c) S. Kaiser, S. P. Smidt, A. Pfaltz,
Angew. Chem. 2006, 118, 5318; Angew. Chem. Int. Ed.
2006, 45, 5194; d) K. Kꢅllstrçm, C. Hedberg, P. Brandt,
P. Bayer, P. G. Andersson, J. Am. Chem. Soc. 2004, 126,
14308; e) M. Engman, J. S. Diesen, A. Paptchikhine,
P. G. Andersson, J. Am. Chem. Soc. 2007, 129, 4536;
f) A. Trifonova, J. S. Diesen, P. G. Andersson, Chem.
Eur. J. 2006, 12, 2318; g) G. Menges, A. Pfaltz, Adv.
Synth. Catal. 2002, 344, 4044; h) W. J. Drury III, N.
Zimmermann, M. Keenan, M. Hayashi, S. Kaiser, R.
Goddard, A. Pfaltz, Angew. Chem. 2004, 116, 72;
Angew. Chem. Int. Ed. 2004, 43, 70; i) C. Hedberg, K.
Kꢅllstrçm, P. Brandt, L. K. Hansen, P. G. Andersson, J.
Am. Chem. Soc. 2006, 128, 2995; j) A. Franzke, A.
Pfaltz Chem. Eur. J. 2011, 17, 4131; k) W. Tang, W.
Wang, X. Zhang, Angew. Chem. 2003, 115, 973; Angew.
Chem. Int. Ed. 2003, 42, 943; l) D.-R. Hou, J. Reibens-
pies, T. J. Colacot, K. Burgess, Chem. Eur. J. 2001, 7,
5391; m) P. G. Cozzi, F. Menges, S. Kaiser, Synlett 2003,
833; n) A. Lightfoot, P. Schnider, A. Pfaltz, Angew.
Chem. 1998, 110, 3047; Angew. Chem. Int. Ed. 1998, 37,
2897; o) F. Menges, M. Neuburger, A. Pfaltz, Org. Lett.
2002, 4, 4713; p) D. Liu, W. Tang, X. Zhang, Org. Lett.
2004, 6, 513; q) S.-M. Lu, C. Bolm, Angew. Chem. 2008,
120, 9052; Angew. Chem. Int. Ed. 2008, 47, 8920; r) W.-
J. Lu, Y.-W. Chen, X.-L. Hou, Adv. Synth. Catal. 2010,
352, 103; s) A. Paptchikhine, P. Cheruku, M. Engman,
P. G. Andersson, Chem. Commun. 2009, 5996; t) T.
Bunlaksananusorn, K. Polborn, P. Knochel, Angew.
Typical Procedure for Catalyst Recycling
After each catalytic run, the autoclave was depressurized.
The colourless propylene carbonate solution was then ex-
tracted with dry/deoxygenated hexane under argon atmos-
phere in order to remove the substrate and the hydrogenat-
ed product. Upon extractions, the corresponding amount of
substrate was then added for starting a new run.
Acknowledgements
We would like to thank the Spanish Government for provid-
ing grant CTQ2010-15835, the Catalan Government for grant
2009SGR116, and the ICREA Foundation for providing M.
Diꢀguez and O. Pꢁmies with financial support through the
ICREA Academia awards.
References
[1] a) Catalytic Asymmetric Synthesis, 2nd edn., (Ed.: I.
Ojima), Wiley-VCH, New York, 2000; b) Asymmetric
Catalysis in Organic Synthesis, (Ed.: R. Noyori), Wiley,
New York, 1994; c) Asymmetric Catalysis on Industrial
Scale, (Eds.: H.-U. Blaser, E. Schmidt), Wiley, New
York, 2004; d) J. M. Brown, in: Comprehensive Asym-
metric Catalysis, (Eds.: E. N. Jacobsen, A. Pfaltz, H. Ya-
mamoto), Springer-Verlag, Berlin, 1999, Vol. 1.
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
13
ÞÞ
These are not the final page numbers!

Javier Mazuela et al.
FULL PAPERS
Chem. 2003, 115, 4071; Angew. Chem. Int. Ed. 2003, 42,
3941; u) Y. Zhang, Z. Han, F. Li, K. Ding, A. Zhang,
Chem. Commun. 2010, 46, 156; v) J. Shang, Z. Han, Y.
Li, Z. Wang, K. Ding, Chem. Commun. 2012, 48, 5172;
w) X. Wang, Z. Han, Z. Wang, K. Ding, Angew. Chem.
2012, 124, 960; Angew. Chem. Int. Ed. 2012, 51, 936.
[7] R. Zalubovskis, E. Hçrmann, A. Pfaltz, C. Moberg,
ARKIVOK 2008, 58.
[8] a) S. Bell, B. Wꢆstenberg, S. Kaiser, F. Menges, T.
Netscher, A. Pflatz, Science 2006, 311, 642; b) D. H.
Woodmansee, M.-A. Mꢆller, M. Neuburger, A. Pfaltz,
Chem. Sci. 2010, 1, 72; c) D. H. Woodmansee, M.-A.
Mꢆller, L. Trçndlin, E. Hçrmann, A. Pfaltz, Chem. Eur.
Diꢁguez, O. Pꢀmies, A. Ruiz, C. Claver, S. Castillꢇn,
Chem. Eur. J. 2001, 7, 3086; c) O. Pꢀmies, M. Diꢁguez,
G. Net, A. Ruiz, C. Claver, Organometallics 2000, 19,
1488; d) O. Pꢀmies, M. Diꢁguez, G. Net, A. Ruiz, C.
Claver, J. Org. Chem. 2001, 66, 8364; e) O. Pꢀmies, M.
Diꢁguez, Chem. Eur. J. 2008, 14, 944.
[15] M. G. Schrems, A. Pfaltz, Chem. Commun. 2009, 6210.
[16] P. Tolstoy, M. Engman, A. Paptchikhine, J. Bergquist,
T. L. Church, A. W.-M Leung, P. G. Andersson, J. Am.
Chem. Soc. 2009, 131, 8855.
[17] a) E. S. Rovner, A. J. Wein, Eur. Urol. 2002, 41, 6; b) J.
Wefer, M. C. Truss, U. Jonas, World J. Urol. 2001, 19,
312; c) C. J. Hills, S. A. Winter, J. A. Balfour, Drugs
1998, 55, 813; d) A. L. McRae, K. T. Brady, Expert
Opin. Pharmacother. 2001, 2, 883.
´
J. 2012, 18, 13780; d) A. Gacnic, A. Pfaltz, Chem. Eur.
J. 2012, 18, 6724.
[9] For applications of other phosphine/phosphinite-pyri-
dine ligands in this process, see: a) Q.-B. Liu, Y-G.
Zhou, Tetrahedron Lett. 2007, 48, 2101; b) Q.-B Liu, C.-
B. Yu, Y.-G. Zhou, Tetrahedron Lett. 2006, 47, 4733;
c) J. J. Verendel, P. G. Andersson, Dalton Trans. 2007,
5603; d) X. Meng, X. Li, D. Xu, Tetrahedron: Asymme-
try 2009, 20, 1402; e) G. Chelucci, M. Marchetti, A. V.
Malkov, F. Friscourt, M. E. Swarbrick, P. Kocovsky, Tet-
rahedron 2011, 67, 5421; f) X. Li, L. Kong, Y. Gao, X.
Wang, Tetrahedron Lett. 2007, 48, 3915; g) Z. Han, Z.
Wang, X. Zhan, K. Ding, Tetrahedron: Asymmetry
2010, 21, 1529; h) ref.[6t]
[10] a) M. Diꢁguez, J. Mazuela, O. Pꢀmies, J. J. Verendel,
P. G. Andersson, J. Am. Chem. Soc. 2008, 130, 7208;
b) M. Diꢁguez, J. Mazuela, O. Pꢀmies, J. J. Verendel,
P. G. Andersson, Chem. Commun. 2008, 3888; c) J. Ma-
zuela, J. J. Verendel, M. Coll, B. Schꢅffner, A. Bçrner,
P. G. Andersson, O. Pꢀmies, M. Diꢁguez, J. Am. Chem.
Soc. 2009, 131, 12344; d) J. Mazuela, A. Paptchikhine,
O. Pꢀmies, P. G. Andersson, M. Diꢁguez, Chem. Eur. J.
2010, 16, 4567; e) J. Mazuela, P.-O. Norrby, P. G. Ander-
sson, O. Pꢀmies, M. Diꢁguez, J. Am. Chem. Soc. 2011,
133, 13634.
[18] The related first generation of phosphinite-pyridine li-
gands afforded 87% ee for S1, 90% ee for S2, 97% ee
for S4, 78% ee for S8,[7] 95% ee for S13and 96% ee for
S16. There are no data reported for the rest of sub-
strates.
[19] For successful application of Ir catalysts, see: a) S.
McIntyre, E. Hçrmann, F. Menges, S. P. Smidt, A.
Pfaltz, Adv. Synth. Catal. 2005, 347, 282; b) ref.[6b]
[20] For successful applications of Sm, Ru and Rh com-
plexes, see: a) V. P. Conticello, L. Brard, M. A. Giardel-
lo, Y. Tsuji, M. Sabat, C. L. Stern, T. J. Marks, J. Am.
Chem. Soc. 1992, 114, 2761; b) M. A. Giardello, V. P.
Conticello, L. Brard, M. R. Gagnꢁ, T. J. Marks, J. Am.
Chem. Soc. 1994, 116, 10241; c) T. T. Co, T. J. Kim,
Chem. Commun. 2006, 3537; d) G. S. Forman, T.
Ohkuma, W. P. Hems, R. Noyori, Tetrahedron Lett.
2000, 41, 9471.
[21] a) T. C. Fessard, S. P. Andrews, H. Motoyohsi, E. Car-
reira, Angew. Chem. 2007, 119, 9492; Angew. Chem.
Int. Ed. 2007, 46, 9331; b) L. Prat, G. Dupas, J. Duflos,
G. Quꢁguiner, J. Bourguignon, V. Levacher, Tetrahe-
dron Lett. 2001, 42, 4515; c) J. A. Wilkinson, S. B. Ros-
sington, S. Ducki, J. Leonard, N. Hussain, Tetrahedron
2006, 62, 1833.
[22] a) K. Okamoto, Y. Nishibayashi, S. Uemura, A. Toshi-
mitsu, Angew. Chem. 2005, 117, 3654; Angew. Chem.
Int. Ed. 2005, 44, 3588; b) Y. Hatanaka, T. Hiyama, J.
Am. Chem. Soc. 1990, 112, 7793.
[23] See for instance: a) A. Abate, E. Brenna, C. Fuganti,
G. G. Gatti, T. Givenzana, L. Malpezzi, S. Serra, J. Org.
Chem. 2005, 70, 1281; b) K. Drescher, A. Haupt, L.
Unger, S. C. Rutner, W. Braje, R. Grandel, C. Henry,
G. Backfisch, A. Beyerbach, W. Bisch, WO Patent
2006/040182A1, 2006.
[24] See for instance: a) M. Schlosser, Angew. Chem. 1998,
110, 1538; Angew. Chem. Int. Ed. 1998, 37, 1496;
b) B. E. Smart, J. Fluorine Chem. 2001, 109, 3; c) Asym-
metric Fluoroorganic Chemistry: Synthesis Application
and Future Direction, (Ed.: P. V. Ramachandran),
American Chemical Society, Washington DC, 2000;
d) A special issue has been devoted to “Fluorine in the
Life Sciences” ChemBioChem 2004, 5, 559.
[11] J. Margalef, M. Lega, F. Ruffo, O. Pꢀmies, M. Diꢁguez,
Tetrahedron: Asymmetry 2012, 23, 945.
[12] These ligands have recently been succesfully applied in
the asymmetric Pd-allylic substitution reaction of
a wide range of mono-, di- and trisubstituted substrates
using several C-, N- and O-nucleophiles. See: J. Mazue-
la, O. Pꢀmies, M. Diꢁguez, Chem. Eur. J. 2013, 19,
2461. Although half of the chiral pyridine-alcohols are
commercially available, we have easily prepared them
all from the corresponding pyridyl-aldehydes and 6-
bromopyridines in few steps, see: J. Uenishi, T. Hirao-
ka, S. Hata, K. Nishiwaki, O. Yonemitsu, J. Org. Chem.
1998, 63, 2481.
[13] See, for instance: a) P. W. N. M. van Leeuwen, P. C. J.
Kamer, C. Claver, O. Pꢀmies, M. Diꢁguez, Chem. Rev.
2011, 111, 2077; b) Heterocyclic Chemistry, 4th edn.,
(Eds.; J. A. Joule, K. Mills), Blackwell Science Ltd,
Oxford, 2000.
[14] The rapid ring inversions (tropoisomerization) in the
biaryl phosphite moiety are usually stopped upon coor-
dination to the metal center. See, for example:
a) G. J. H. Buisman, L. A. van der Veen, A. Klootwijk,
W. G. J. de Lange, P. C. J. Kamer, P. W. N. M. van Leeu-
wen, D. Vogt, Organometallics 1997, 16, 2929; b) M.
[25] See, for instance: a) I. Fleming, A. Barbero, D. Walter,
Chem. Rev. 1997, 97, 2063; b) G. R. Jones, Y. Landais,
Tetrahedron 1996, 52, 7599; c) W. Bains, R. Tacke, Curr.
Opin. Drug Discovery Dev. 2003, 6, 526.
14
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

A Phosphite-Pyridine/Iridium Complex Library as Highly Selective Catalysts for the Hydrogenation
[26] B. Schꢅffner, F. Schꢅffner, S. P. Verevkin, A. Bçrner,
Chem. Rev. 2010, 110, 4554.
S4, 99% ee for S8, 98% ee for S9, 97% ee for S10,
>99% ee for S13, 97% ee for S16 and 98% ee for S20.
For disubstituted substrate S23, ees up to 80% were
achieved.
[27] J. Bayardon, J. Holz, B. Schꢅffner, V. Andrushko, S.
Verevkin, A. Preetz, A. Bçrner, Angew. Chem. 2007,
119, 6075; Angew. Chem. Int. Ed. 2007, 46, 5971.
[28] This is probably due to the iridium catalyst partially
passing into the hexane phase (see, ref.[27]) and/or the
formation of inactive triiridium hydride clusters; see:
a) S. P. Smidt, A. Pfaltz, E. Martinez-Viviente, P. S. Pre-
gosin, A. Albinati, Organometallics 2003, 22, 1000;
b) ref.[3]
[30] a) T. Ohta, H. Ikegami, T. Miyake, H. Takaya, J. Orga-
nomet. Chem. 1995, 502, 169; b) K. Kꢅllstrçm, I. J.
Munslow, C. Hedberg, P. G. Andersson, Adv. Synth.
Catal. 2006, 348, 2575; c) K. Inagaki, T. Ohta, K.
Nozaki, H. Takaya, J. Organomet. Chem. 1997, 531,
159; d) S. Deerenberg, P. C. J. Kamer, P. W. N. M. van
Leeuwen, Organometallics 2000, 19, 2065.
[29] The second generation of phosphinite-pyridine ligands
afforded >99% ee for S1, 98% ee for S2, >99% ee for
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
15
ÞÞ
These are not the final page numbers!

FULL PAPERS
16 A Phosphite-Pyridine/Iridium Complex Library as Highly
Selective Catalysts for the Hydrogenation of Minimally
Functionalized Olefins
Adv. Synth. Catal. 2013, 355, 1 – 16
Javier Mazuela, Oscar Pꢀmies,* Montserrat Diꢁguez*
16
asc.wiley-vch.de
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!