A modular furanoside thioether-phosphite/phosphinite/ phosphine ligand library for asymmetric iridium-catalyzed hydrogenation of minimally functionalized olefins: Scope and limitations

Article abstract of DOI:10.1002/adsc.201200711

A highly modular furanoside thioether-phosphite/phosphinite/phosphine ligand library has been synthesized for the iridium-catalyzed asymmetric hydrogenation of minimally functionalized olefins. These ligands can be prepared efficiently from easily accessible D-(+)-xylose. We found that their effectiveness at transferring the chiral information in the product can be tuned by correctly choosing the ligand components. Enantioselectivities were therefore excellent (ees up to 99%) in a wide range of E- and Z-trisubstituted alkenes using 5-deoxyribofuranoside thioether-phosphite ligands. It should be pointed out that these catalysts are also very tolerant to the presence of a neighbouring polar group. For 1,1-disubstituted substrates, both enantiomers of the hydrogenation product can be obtained in high enantioselectivities simply by changing the configuration of the biaryl phosphite moiety. The asymmetric hydrogenation was also performed using propylene carbonate as solvent, which allowed the iridium catalysts to be reused while maintaining the excellent enantioselectivities. Copyright

Full text of DOI:10.1002/adsc.201200711

FULL PAPERS
DOI: 10.1002/adsc.201200711
A Modular Furanoside Thioether-Phosphite/Phosphinite/
Phosphine Ligand Library for Asymmetric Iridium-Catalyzed
Hydrogenation of Minimally Functionalized Olefins: Scope and
Limitations
Mercedes Coll,a Oscar Pꢀmies,a,* and Montserrat Diꢁgueza,*
a
Departament de Quꢂmica Fꢂsica i Inorgꢀnica, Universitat Rovira i Virgili, C/Marcel·li Domingo, s/n. 43007 Tarragona,
Spain
Fax : (+34)-9-7755-9563; phone: (+34)-9-7755-8780; e-mail: oscar.pamies@urv.cat or montserrat.dieguez@urv.cat
Received: August 9, 2012; Published online: December 7, 2012
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200711.
Abstract: A highly modular furanoside thioether- to the presence of a neighbouring polar group. For
phosphite/phosphinite/phosphine ligand library has 1,1-disubstituted substrates, both enantiomers of the
been synthesized for the iridium-catalyzed asymmet- hydrogenation product can be obtained in high enan-
ric hydrogenation of minimally functionalized ole- tioselectivities simply by changing the configuration
fins. These ligands can be prepared efficiently from of the biaryl phosphite moiety. The asymmetric hy-
easily accessible d-(+)-xylose. We found that their drogenation was also performed using propylene car-
effectiveness at transferring the chiral information in bonate as solvent, which allowed the iridium cata-
the product can be tuned by correctly choosing the lysts to be reused while maintaining the excellent
ligand components. Enantioselectivities were there- enantioselectivities.
fore excellent (ees up to 99%) in a wide range of E-
and Z-trisubstituted alkenes using 5-deoxyribofura-
noside thioether-phosphite ligands. It should be Keywords: asymmetric catalysis; heterodonor P,S li-
pointed out that these catalysts are also very tolerant gands; hydrogenation; iridium; olefins
Introduction
less developed because these substrates have no adja-
cent polar group to direct the reaction.[1] In the last
The development of efficient methods for the synthe- decade, Ir complexes containing chiral P,N ligands
sis of enantiomerically enriched compounds remains have emerged as powerful tools in the asymmetric hy-
at the center of modern-day organic chemistry, as drogenation of minimally functionalized olefins.[2]
these methods have a wide range of important appli- They are essentially complementary to Rh- and Ru-
cations, from the total synthesis of natural products to diphosphine catalysts. Because of the early success of
the preparation of analogues of lead compounds in Pfaltz[3a] and others[3b–e] in developing chiral heterodo-
the pharmaceutical industry. Because of its high effi- nor phosphine-oxazoline ligands as chiral mimics of
(PCy3)]PF6,[4] research
ciency, atom economy and operational simplicity, the Crabtreeꢃs catalyst [IrACTHUNRTGENNUG(cod)(py)ACHTUNGTRENNUGN
asymmetric hydrogenation of properly selected pro- in this field has focused on maximizing the efficiency
chiral starting materials could be a sustainable and of these ligands by: (i) modifying the structure of the
direct synthetic tool for preparing these compounds.[1] chiral ligandꢃs backbone, (ii) replacing the phosphine
The early success of Rh- and Ru-diphosphine cata- moiety with a phosphinite, phosphite or carbene
lysts in the hydrogenation of functionalized olefins group, and (iii) changing the oxazoline moiety for
and ketones inspired the design of many chiral li- other N-donor groups (such as oxazole, pyridine or
gands.[1] Nowadays several homodonor ligands thiazole).[5] Although the number of substrates that
(mainly diphosphines) and heterodonor ligands (such can be successfully reduced increased, there is still im-
as P, N, P, P ’ and P,S) have therefore been developed portant substrate classes that give unsatisfactory re-
and successfully applied. The asymmetric hydrogena- sults with known catalysts. More research is therefore
tion of minimally functionalized olefins, however, is needed to find more versatile ligand systems that can
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Mercedes Coll et al.
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Figure 1. Thioether-phosphite/phosphinite/phosphine ligands L1–L15a–l.
be synthesized in an efficient and modular synthetic and (b) the thioether group is more stable than the
route using simple starting materials. In this respect, oxazoline moiety.[9] The modular nature of this ligand
research focus on the possibility of changing the library (Figure 1) allowed us to investigate the effect
nature of the N-donor atom in these heterodonor li- of systematically varying the position of the thioether
gands has not been contemplated until very recently. group at either C-5 (ligands L1–L11) or C-3 (ligands
In this context, we have recently communicated the L12–L15) of the furanoside backbone and the effect
first successful application of non-N-donor heterodo- of the configuration at C-3 of the furanoside back-
nor ligands – thioether-phosphite – for asymmetric Ir- bone on catalytic performance. We also studied the
catalyzed hydrogenation of model trisubstituted and effect of the substituents in the thioether group (L1–
terminal minimally functionalized olefins.[6,7] Despite L7), the effect of the substituents and configurations
this success, the use of other thioether-phosphite li- in the biaryl phosphite moiety (a–h) and replacing the
gands has not yet been reported and a systematic phosphite moiety by a phosphinite group (i–k) or
study of the possibilities offered by thioether-phos- a phosphine group (l). In this paper, we have also ex-
phorus as new ligands for this process is still needed. tended the scope of these new catalytic systems by
For this purpose, in this paper we extend our prelimi- using propylene carbonate as alternative environmen-
nary study to other furanoside thioether-phosphite li- tally friendly solvent, which allows the catalyst recy-
gands (Figure 1) and other more challenging sub- cling.
strates. We have therefore extended the Ir-P,S catalyst
library by adding furanoside ligands with new sub-
stituents in the thioether and biaryl phosphite group Results and Discussion
(b, d, e and f). We also compare the effectiveness of
these thioether-phosphite ligands with their related Synthesis of Ligands
thioether-phosphinites (L1–L15i–k) and thioether-
phosphines (L1–L15l). This library of potentially 180 Synthesis of the thioether-phosphite/phosphinite/phos-
ligands is derived from natural d-xylose so they have phine
ligands
L1–L15a–l
is
straightforward
the advantages of carbohydrates (e.g., they are cheap (Scheme 1).[10] They were efficiently synthesized from
and have a facile modular construction).[8] Moreover, the corresponding easily accessible sugar-derived al-
the addition of a thioether moiety to the ligand cohols 1–4.[11] These compounds are easily made in
design may be beneficial because: (a) the S atoms a few steps from inexpensive d-(+)-xylose. Com-
become a stereogenic center when coordinated to the pounds 1–4 were chosen as intermediates for the
metal, which moves the chirality closer to the metal, preparation of ligands because they make it easy to
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A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
Scheme 1. Synthesis of thioether-phosphite/phosphinite/phosphine ligands L1–L15a–l. Reaction conditions: (a) Tf2O, Py,
CH2Cl2, À158C; (b) NaSR, THF, room temperature; (c) NH4OH/MeOH; (d) ClP(OR)2, Py, toluene, 808C or ClPR2, Py,
THF, room temperature; (e) KPPh2/THF/À788C to room temperature.
incorporate the various elements that enable the posi- 21 and 23 [Scheme 1, step (c)]. The last step of the
tion of the thioether (at either C-5 or C-3) and the ligand synthesis is the reaction of the corresponding
configuration of C-3 to be studied.
sugar thioether-hydroxy compound (5–15, 17, 19, 21
For the synthesis of thioether/phosphite and thio- and 23) in the presence of pyridine with 1 equivalent
ether-phosphinite ligands (L1–L15a–k), compounds of either the corresponding biaryl phosphorochlori-
1–4 were treated with one equivalent of triflic anhy- dite [ClP(OR)2; P(OR)2 =a–h] to achieve thioether-
dride to produce the desired monotriflates. Subse- phosphite ligands (L1–L15a–h) or the desired chloro-
quent reaction with the corresponding NaSR provided diarylphosphine (ClPR2; PR2 =i–k) to provide thio-
direct access to the corresponding thioether-hydroxy ether-phosphinite ligands (L1–L15i–k) [Scheme 1,
species 5–15[12] and thioether-benzoyl intermediates step (d)].
16, 18, 20 and 22 [Scheme 1, steps (a, b)]. Therefore,
For the synthesis of thioether-phosphine ligands L1l
this step also provided the desired diversity in elec- and L7l, thioether-hydroxy compounds 12 and 15
tronic and steric properties of the thioether moiety. were treated with one equivalent of triflic anhydride
The benzoyl protecting group of compounds 16, 18, to produce the desired thioether-triflates (Scheme 1).
20 and 22 was removed under basic standard condi- Subsequent reaction with potassium diphenylphos-
tions to achieve thioether-hydroxy compoundss 17, 19,
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Mercedes Coll et al.
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phine in THF provided easy access to the desired copy. The spectral assignments were based on infor-
1
thio
G
mation from H-1H and 13C-1H correlation measure-
All the ligands were stable during purification on ments and were as expected for these C1 iridium com-
neutral alumina under an atmosphere of argon and plexes.
were generally isolated in good yields as white solids
or colourless oils. They were stable at room tempera- the presence of a single isomer in all cases except for
ture. Thioether-phosphite/phosphinite ligands were [Ir(cod)(L1–L7a, c, g–h)]BArF in which there are two
VT-NMR (+408C to À708C) experiments indicate
AHCTUNGTRENNUNG
very stable to hydrolysis and the thioether-phosphine isomers. These isomers may be attributed to the two
ligands were stable in air in the solid state. For all li- possible diastereoisomers formed when the thioether
gands, the elemental analyses were in agreement with coordinates to the metal atom (note that the coordi-
the assigned structures. The 1H, 13C and 31P NMR nated S atom is a stereogenic center), to the different
spectra were as expected for these C1 ligands.
tropoisomers of the biphenyl moieties, or to both.
However, if compound Ir/L1a is compared with relat-
ed compounds Ir/L1g and Ir/L1h, which contain enan-
tiomerically pure binaphthyl moieties, the presence of
two isomers in them all suggests that these isomers
Synthesis of the Ir-Catalyst Precursors
The catalyst precursors were made by refluxing a di- are due to the different configurations of the sulfur
chloromethane solution of the appropriate ligand stereocenter. From this we can also conclude that
(L1–L15a–l) in the presence of 0.5 equivalent of ligand backbones L8–L15 effectively control the thio-
[Ir
terion with sodium tetrakis
phenyl]borate (NaBArF) (1 equiv.) in the presence of diastereoisomer
water at room temperature (Scheme 2).[13] All com- [Ir
(cod)(L)]BArF (L=L1e, f, I, j, l and L7e, f, I, j, l),
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
plexes were isolated as air-stable red-orange solids in which indicates that thioether coordination can also
pure form and they were then used without further be controlled in 5-deoxyxylofuranoside ligands L1–L7
purification. The complexes were characterized by el- either by introducing bulky enantiopure biaryl phos-
1
emental analysis and H, 13C, and 31P NMR spectros- phite moieties (e and f) or incorporating a phosphinite
(i and j) or a phosphine (l) rather than a phosphite
group.
We were able to obtain [Ir
ACHUTGTNNERNUG(cod)HCATUNGTRNEN(UGN L1a)]BArF,
[Ir(cod)(L7i)]BArF and [Ir(cod)(L12i)]BArF crystals
A
E
N
ACHTUNGTRENNUNG
that were suitable for X-ray analysis (Figure 2). The
crystal structures confirmed the equatorial position of
the thioether substituent in all cases. However, while
for [Ir
ring adopted a boat conformation, it adopted twist-
boat conformations for [Ir(cod)(L7i)]BArF and [Ir-
(cod)(L12i)]BArF. This results in a different spatial
disposition of the thioether substituent. Thus, while
for [Ir(cod)(L1a)]BArF the thioether moiety occupies
ACHUTGTNRENNUG(cod)ACHTUNGTREN(NNGU L1a)]BArF the seven-membered chelate
A
ACHTUNGTRENNUNG
E
ACHTUNGTRENNUNG
_
Scheme 2. Synthesis of catalyst precursors [IrACTHNUTRGENN(UG cod)CAHTUNGTRNE(NUGN PS)]
_
BArF (PS=L1–L15a–l).
N
ACHTUNGTRENNUNG
Figure 2. Structures of (a) [IrACHTUNGRTENNUG(cod)ACHTUGNTERN(NUNG L1a)]BArF, (b) [IrCAHUTNGTREN(NUG cod)AHTCUNGTERN(NUNG L7i)]BArF and (c) [IrACHTUNGRTEGN(NUN cod)ACHTNUGERTN(NUNG L12i)]BArF in the crystal (H atoms,
BArF ion and cyclooctadiene ligand have been omitted for clarity). CCDC 905001, CCDC 905002 and CCDC 905003 contain
the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crys-
tallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
the lower left quadrant, for [Ir
[Ir(cod)(L12i)]BArF the thioether substituents occupy ent, the substituents/configuration in the biaryl phos-
the upper left quadrant. In addition, the [Ir(cod)- phite moiety (a–h) and the replacement of the phos-
(L1a)]BArF structure also showed that the biphenyl phite moiety by a phosphinite (i–k) or a phosphine (l)
phosphite moiety adopts an R-configuration when co- group.
ACHUTGTNRNE(UNG cod)ACHUTNGTREN(NUGN L7i)]BArF and bone, the configuration of C-3, the thioether substitu-
N
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
ordinated to the iridium center.
The results indicate a cooperative effect between
the position of the thioether group and the configura-
tion of carbon atom C-3 of the furanoside backbone
(Table 1, entries 1, 8, 21 and 23). The matched combi-
nation is therefore achieved with 5-deoxyribofurano-
side-derived ligands L8–L11, which have the thioether
moiety attached to C-5 and an R configuration of
carbon atom C-3.
Asymmetric Hydrogenation of Trisubstituted Olefins
Asymmetric Hydrogenation of Minimally
Functionalized Trisubstituted Olefins
In the first set of experiments, we used the Ir-cata-
The effect of the thioether substituent was studied
lyzed hydrogenation of (E)-2-(4-methoxyphenyl)-2- using ligands L1–L7a (Table 1, entries 1–7). Results
butene S1 to study the potential of ligands L1–L15a–l. showed that enantioselectivity is mainly dependent on
Butene S1 was chosen as the substrate because it has the steric properties of the substituents in the thioeth-
been hydrogenated by a wide range of catalysts, er moiety. Enantioselectivity increases by increasing
which enabled the efficiency of the various ligand sys- the steric bulk of the thioether substituent (2,6-
tems to be compared directly.[2] The results are sum- Me2C6H3 >t-Buꢀi-Pr>Phꢀ4-X-C6H4 ꢀMe). Bulky
marized in Table 1. We found that enantioselectivities aryl substituents are therefore needed if enantioselec-
were highly affected by the position of the thioether tivities are to be high. Similar behaviour was observed
group at either C-5 or C-3 of the furanoside back- for the other ligand backbones (Table 1). Enantiose-
Table 1. Selected results for the Ir-catalyzed hydrogenation of S1 using the furanoside P,S-ligand library L1–L15a–l.[a]
Entry
Ligand
% Conversion[b]
% ee[b]
Entry
Ligand
% Conversion[b]
% ee[]b]
1
2
3
4
5
6
7
8
L1a
L2a
L3a
L4a
L5a
L6a
L7a
L8a
L8b
L8c
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
13 (R)
15 (R)
23 (R)
24 (R)
14 (R)
13 (R)
30 (R)
87 (R)
85 (R)
87 (R)
21 (R)
82 (R)
27 (S)
26 (R)
24 (R)
45 (R)
72 (R)
99 (R)
99 (R)
50 (S)
68 (R)
21 (R)
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
L14a
L15a
L1i
L2i
L3i
L4i
L5i
L6i
L7i
L8i
L8j
L11j
L11j
L12i
L14i
L1l
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
82
68 (S)
24 (S)
17 (R)
8 (R)
14 (R)
10 (R)
16 (R)
17 (R)
45 (R)
69 (R)
85 (R)
77 (R)
95 (R)
76 (R)
40 (S)
10 (R)
7 (R)
9
10
11
12
13
14
15
16
17
18
19
29
21
22
L8d
L8e
L8f
L8g
L8h
L9a
L10a
L11a
L11e
L11f
L12a
L13a
39
L7l
40[c]
41[c]
42[d]
43[e]
44[e]
L11a
L11e
L11a
L11a
L11e
98 (R)
98.5 (R)
96 (R)
99 (R)
99 (R)
81
[a]
Reactions carried out using 0.5 mmol of S1 and 2 mol% of Ir catalyst precursor.
Conversion and enantiomeric excesses determined by chiral GC.
Reaction carried out at 75 bar H2.
Reaction carried out at 50 bar H2.
Reaction carried out with 0.5 mol% of Ir catalyst precursor.
[b]
[c]
[d]
[e]
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lectivities up to 99% were therefore obtained using
the 5-deoxyribofuranoside ligand containing the 2,6-
Me2C6H3 thioether group (L11a, entry 18).
The effects of the phosphite moiety were studied
using 5-deoxyribofuranoside ligands L8a–h (Table 1,
entries 8–15). We found that bulky substituents need
to be present in the biaryl phosphite moieties if enan-
tioselectivities are to be high (i.e., Table 1, entries 8–
10 vs. 11). The results also show a cooperative effect
between the configuration of the bulky biphenyl
moiety and the configuration of the ligand backbone
on enantioselectivity. This led to a matched combina-
tion for ligand L8e, which contains an R-biaryl moiety
(Table 1, entry 12). In addition, a comparison of the
absolute stereochemistry obtained by using ligands
with bulky tropoisomeric biphenyl moieties (L8a–c;
entries 8–10) with those obtained upon using the re-
lated enantiopure biphenyl ligands L8e and L8f (en-
tries 12 and 13) shows that the tropoisomeric biphenyl
moiety in ligands L8a–c adopts an R-configuration
upon forming a complex with iridium. In contrast, the
biaryl-configuration of ligands containing less sterical-
ly hindered binaphthyl substituents (g, h) has little
effect on the enantioselectivity (entries 14 and 15).
The same trends were observed for the other ligand
Scheme 3. Selected hydrogenation results of trisubstituted
olefins using [IrACTHNUTRGNE(UNG cod)(L1–L15a–l)]BArF catalyst precursors.
Reaction conditions: 2 mol% catalyst precursor, CH2Cl2 as
solvent, 100 bar H2, 4 h.
backbones (see Table SI.1 in the Supporting Informa- enantioselectivities are among the best observed for
tion).
these substrates.[2,5] The hydrogenation of both E- and
Finally, we studied the effect on catalytic perfor- Z-trisubstituted olefins followed the same trends as
mance of introducing either a phosphinite or a phos- the reduction in S1. The best enantioselectivities (ees
phine moiety. In general, the results of using ligands up to 99%) were therefore obtained using Ir-L11a
L1–L15i–l indicated that replacing the phosphite and Ir-L11e catalytic systems. Interestingly, Z-trisub-
moiety by a phosphinite or a phosphine group in the stituted isomers (S4–S7), which are usually hydrogen-
ligands had a negative effect on enantioselectivity ated less enantioselectively than the corresponding E-
(Table 1, entries 25–39). However, this negative effect isomers, were also hydrogenated in high enantioselec-
is less pronounced if bulky ortho-tolyl phosphinites tivities using the [Ir
N
ACHTUNGTERN(NUNG P-S)]BArF (P-S=L11a and
are used (ees up to 95%, entry 35).
In summary, excellent enantioselectivities (ees up to
99%) were obtained with thioether-phosphite ligands enantioselectivity (ee values up to 99%) is relatively
L11a and L11e (Table 1, entries 18 and 19), which insensitive to the electronic nature of the substrate
contain the optimal combination of ligand parameters. phenyl ring (substrates S1 and S4 vs. S2 and S5, re-
Not only can the effect of the structural parameters spectively). This contrasts with the positive effect on
on catalytic performance be controlled, but also the enantioselectivity observed for cyclic substrates when
reaction parameters. Therefore, we next studied the a methoxy substituent is introduced into the phenyl
effect of the hydrogen pressure on the catalytic out- ring (Scheme 3, substrate S6 vs. S7). It should be
come. The results show a small decrease in enantiose- pointed out that the enantioselectivities obtained in
lectivity when the hydrogen pressure is lowered the reduction of triaryl-substituted substrates S8 and
(Table 1, entries 18, 40–42). We also performed the re- S9 were excellent (ees up to 99%). This latter sub-
action at low catalyst loading (0.5 mol%) using Ir- strate class provides an easy entry point to diarylme-
L11a and Ir-L11e catalysts (Table 1, entries 43 and thine chiral centers, which are present in several im-
44). The excellent enantioselectivities (99% (R) ee) portant drugs and natural products.[14] Despite this,
were maintained.
only two catalytic systems have recently been able to
We then studied the asymmetric hydrogenation of hydrogenate this type of substrate with high enantio-
other E- and Z-trisubstituted olefins (S2–S9) by using selectivities.[15]
the thioether-phosphite/phosphinite/phosphine ligand
library L1–L15a–l. The most noteworthy results are
shown in Scheme 3 (for a full set of results, see Tables
SI.2 to Table SI.4 in the Supporting Information). The
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A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
retention of the chirality.[16] Despite this there are few
reports on the highly enantioselective Ir-reduction of
this substrate class.[15b,17]
Asymmetric Hydrogenation of 1,1-Disubstituted
Terminal Olefins
We next applied thioether-phosphite/phosphinite/
phosphine ligands L1–L15a–l in the asymmetric hy-
drogenation of a more demanding class of substrates:
1,1-disubstituted terminal olefins. Enantioselectivity is
more difficult to control in these substrates than in
trisubstituted olefins,[2d–f] because: (i) the terminal
double bond can isomerize to form the more stable
internal alkene, which leads to the predominant for-
mation of the opposite enantiomer of the hydrogenat-
ed product [Scheme 5, (a)] and (ii) face selectivity is
more difficult to control because there are only two
substituents in the substrate [Scheme 5, (b)].[2d–f] Few
known catalytic systems provide high enantioselectivi-
ties for these substrates, and those that do are usually
limited in substrate scope.[2e,18,19] In contrast to the hy-
drogenation of trisubstituted olefins, the enantioselec-
Scheme 4. Selected hydrogenation results of trisubstituted
olefins containing neighbouring polar group using
[Ir(cod)(L1–L15a–l)]BArF catalyst precursors. Reaction con-
ditions: 2 mol% catalyst precursor, CH2Cl2 as solvent,
100 bar H2, 4 h.
a
ACHTUNGTRENNUNG
Asymmetric Hydrogenation of Trisubstituted Olefins
Containing a Neighbouring Polar Group
To further study the potential of the furanoside thio- tivity in the reduction of terminal alkenes is highly
ether-phosphite/phosphinite/phosphine ligand library pressure dependent. Therefore, hydrogenation at an
L1–L15a–l in the reduction of minimally functional- atmospheric pressure of H2 generally gave significant-
ized trisubstituted olefins, we screened it in the Ir-cat- ly higher ee values than at higher pressures.[18a]
alyzed hydrogenation of trisubstituted alkenes con-
In an initial set of experiments we used the Ir-cata-
taining a neighbouring polar group. These substrates lyzed asymmetric hydrogenation of 3,3-dimethyl-2-
are interesting because they easily allow for further phenyl-1-butene S18. The results obtained using the
functionalization and they are therefore important ligand library L1-L15a–l are summarized in Table 2.
synthons for the synthesis of more complex chiral We were again able to fine-tune the ligand parame-
molecules. The results are summarized in Scheme 4 ters to produce high activities and enantioselectivities
(for a full set of results, see Table SI.5 in the Support- (ees up to 98%) in the hydrogenation of this substrate
ing Information). The reduction of substrates S10–S17 using low hydrogen pressures (1 bar). Enantioselectiv-
followed the same trends as those observed for the ities were again affected by the position of the thio-
previous E- and Z-trisubstituted substrates. Again, ether group at either C-5 or C-3 of the furanoside
high-to-excellent enantioselectivities (ee values up to backbone, the configuration of C-3, the thioether sub-
99%) were obtained for a range of substrates using stituent, the substituents/configuration in the biaryl
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG(L11a)]BArF and [IrAHCNUTGERTN(GNNU cod)ACHTNUGTNER(NUGN L11e)]BArF cata- phosphite moiety (a–h) and the replacement of the
lyst precursors. The reduction of several a,b-unsatu- phosphite moiety by a phosphinite (i–k) or a phos-
rated esters (S10–S12) is highly independent of the phine (l) group. In general the effect of these ligand
electronic nature of the substrate phenyl ring (ees parameters on enantioselectivity followed the same
ranging from 98% to 99%). High enantioselectivities trend as for the reduction of trisubstituted olefins.
were also obtained in the asymmetric reduction of al-
lylic alcohol S13 and allylic acetate S14. On the other
hand, the presence of trimethylsilyl groups in the sub-
strate has a negative effect on enantioselectivity. The
reduction of enol silane S15 therefore proceeds with
moderate enantiocontrol. Finally, high enantioselec-
tivities (up to 91%) were obtained in the hydrogena-
tion of vinylboronates S16 and S17. The hydrogena-
tion of vinylboronates provides easy access to chiral
borane compounds, which are useful building blocks
À
in organic synthesis because the C B bond can be
readily converted to C O, C N and C C bonds with Scheme 5.
À
À
À
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149

Mercedes Coll et al.
Table 2. Selected results for the Ir-catalyzed hydrogenation of S18 using the furanoside P,S-ligand library L1–L15a–l.[a]
FULL PAPERS
Entry
Ligand
% Conversion[b]
% ee[b]
Entry
Ligand
% Conversion[b]
% ee[b]
1
2
3
4
5
6
7
8
L1a
L1c
L1f
L2a
L3a
L4a
L5a
L6a
L7a
L7c
L7f
L8a
L8b
L8c
L8d
L8e
L8f
L8g
L8h
L9a
L10a
L11a
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
28 (R)
93 (S)
87 (R)
4 (R)
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43[c]
44[c]
L11e
L11f
L12a
L12c
L12f
L13a
L14a
L15a
L1i
L2i
L3i
L4i
L7i
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
99
98 (S)
97 (R)
45 (S)
96 (S)
86 (R)
13 (S)
6 (R)
3 (R)
4 (S)
31(R)
35 (R)
27 (R)
25 (R)
42 (R)
91 (S)
93 (R)
63 (S)
62 (S)
62 (S)
3 (S)
91 (S)
83 (R)
49 (S)
11 (R)
8 (S)
9
10
11
12
13
14
15
16
17
18
19
20
21
22
6 (S)
2 (S)
4 (S)
60 (S)
20 (S)
42 (S)
91 (S)
17 (S)
55 (S)
35 (R)
0
L8i
L11i
L11j
L12i
L12j
L14i
L7l
42 (S)
98 (S)
L11e
L11f
98 (S)
97 (R)
[a]
Reactions carried out using 0.5 mmol of S18 and 2 mol% of Ir catalyst precursor.
Conversion and enantiomeric excesses determined by chiral GC.
Reaction carried out at 0.5 mol% of Ir catalyst precursor.
[b]
[c]
However, the effect of the configuration of the biaryl library L1–L15a–l. The most noteworthy results are
phosphite moiety was different. Therefore, in contrast shown in Table 3 (see also Supporting Information,
to the previous cooperative effect observed for trisub- Table SI.6).
stituted olefins that led to higher ees with ligands con-
The results follow the same trends as the hydroge-
taining enantiopure bulky R-biaryl moieties (e), in nation of S18. Again, catalyst precursors containing
the reduction of S18 ligands containing enantiopure the thioether-phosphite ligands L11a L11e and L11f
bulky R- and S-biaryl moieties (e and f) acted as provided the best enantioselectivities (ees up to 99%).
pseudo-enantiomers (Table 2, entries 23 and 24). Both
Our results with several 1,1-disubstituted aryl-alkyl
enantiomers of the hydrogenation product can there- substrates (S18–S26) indicated that enantioselectivity
fore be obtained in high enantioselectivities (ees up to is highly affected by the nature of the alkyl chain (ees
98%) using Ir-L11e and Ir-L11f catalytic systems even ranging from 28% to 98%, Table 2, entry 22 and
at low catalyst loadings (Table 2, entries 43 and 44).
Table 3, entries 1 and 6–10) and less affected by the
In summary, enantioselectivities were best when electronic nature of the aryl ring (ees ranging from
the Ir-catalyst precursors used contained thioether- 79% to 81%, Table 3, entries 1 and 4, 5). One plausi-
phosphite ligands L11a, L11e and L11f. These results, ble explanation can be found in the competition be-
which again clearly show the efficiency of using mod- tween direct hydrogenation vs. isomerization for the
ular scaffolds in the ligand design are among the best different substrates. This is supported by the fact that
that have been reported for this demanding substra- the hydrogenation of substrate S18 bearing a tert-
te.[2e]
butyl group, for which isomerization cannot occur,
We then studied the asymmetric hydrogenation of provides high levels of enantioselectivity (ees up to
other 1,1-disubstituted aryl-alkyl substrates (S19– 98%; Table 2, entry 22), while the lowest enantiose-
S26), 1,1-disubstituted heteroaryl-alkyl olefins (S27– lectivities of the series (Table 3, entries 9 and 10) are
S29), 1,1-diaryl terminal alkenes (S30 and S31) and found for substrates S25 and S26, which form the
1,1-allylic alcohol and acetate (S32 and S33) by using most stable isomerized tetrasubstituted olefins.
the thioether-phosphite/phosphinite/phosphine ligand
150
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A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
Table 3. Selected results for the Ir-catalyzed hydrogenation of minimally functionalized 1,1-disubstituted terminal olefins
using ligands L1–L15a–l.[a]
Entry
Substrate
Ligand
% ee[b]
Entry
10
Substrate
Ligand
% ee[b]
40 (S)
1
2
3
L11a
L11e
L11f
78 (S)
79 (S)
77 (R)
L11a
4
5
6
L11a
L11a
L11a
73 (S)
81 (S)
62 (S)
11
12
L11a
L11a
55 (À)
61 (+)
13
14
15
L11a
L11e
L11f
99 (+)
99 (+)
98 (À)
7
8
L11a
65 (S)
16c
17c
L11a
L11a
43 (+)
L11a
L11a
43 (S)
28 (S)
18 (+)
18[c]
19[c]
L11a
L11a
83 (S)
81 (S)
9
[a]
Reactions carried out using 1 mmol of substrate and 2 mol% of Ir catalyst precursor at 1 bar of H2. Full conversions were
obtained in all cases.
Enantiomeric excesses determined by chiral GC (except for entry 16, which was measured by HPLC).
Reaction carried out at 50 bar H2.
[b]
[c]
We then decided to apply this ligand library in the rather laborious approaches.[20,21] Recently, it has been
asymmetric hydrogenation of 1,1-heteroaromatic al- shown that they can be prepared more efficiently
kenes (S27–S29) because heterocycles are used in in- using enantioselective hydrogenation.[5h] Substrates
dustry and the heterocyclic part can be modified post- differing sterically (S30) and electronically (S31) were
hydrogenation. Under standard conditions, our cata- hydrogenated with low-to-moderate enantioselectivi-
lyst systems were also able to hydrogenate this type ties (ees up to 40%) using the Ir-L11a catalytic
of substrate with excellent activities and moderate-to- system.
excellent enantioselectivities (ees up to 99%; Table 3,
Finally, we tested the ligand library in the hydroge-
entries 11–15). The results again suggest that the con- nation of the allylic alcohol S32 and allylic acetate
trol of isomerization is the key to achieving high ees S33. Derivatives of the hydrogenation of these prod-
for this substrate class. Therefore, the highest enantio- ucts are important intermediates for the synthesis of
selectivity was obtained in the hydrogenation of S29 high-value cosmetics, natural products and drugs.[22]
bearing a tert-butyl group (Table 3, entries 13–15).
Good enantioselectivities up to 83% were obtained
Next, we studied the hydrogenation of diaryl termi- using ligand L11a (Table 3, entries 18 and 19). These
nal alkenes S30 and S31 (Table 3, entries 16 and 17). results are among the best reported and again indi-
Enantiopure diarylalkanes are important intermedi- cate that the new Ir-P,S catalytic systems are also able
ates for the preparation of drugs and research materi- to efficiently hydrogenate substrates containing
als.[20] They have traditionally been prepared using a neighbouring polar group in terminal olefins.
Adv. Synth. Catal. 2013, 355, 143 – 160
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151

Mercedes Coll et al.
FULL PAPERS
Table 4. Recycling experiments with the catalyst precursor
C-3 of the furanoside backbone, the configuration of
C-3, the thioether substituent, the substituents/config-
uration in the biaryl phosphite moiety and the re-
placement of the phosphite moiety by a phosphinite
or a phosphine group). By carefully selecting the
ligand components we found that the best enantiose-
lectivities were obtained using thioether-phosphite li-
gands with a 5-deoxyribofuranoside backbone. These
ligands combine the advantages of sugar, phosphite
and thioether cores: that is to say, they are readily
available from cheap feedstocks, are highly resistant
to oxidation, have a straightforward modular con-
struction, and are more stable than oxazolines.[8,26] Ex-
cellent enantioselectivities were therefore obtained
[IrACHTUNGTRENNUNG(cod)ACHTUNGTRENNUNG
(L11a)]BArF and S1 and S18 as substrates in PC.[a]
Cycle
Substrate
% Conversion (h)[b]
% ee[c]
1[d]
2[d]
3[d]
4[d]
5[d]
100 (4)
95 (4)
87 (6)
94 (12)
73 (18)
99 (R)
98 (R)
96 (R)
96 (R)
95 (R)
1[e]
2[e]
3[e]
4[e]
5[e]
100 (4)
98 (4)
92 (6)
95 (12)
79 (18)
98 (S)
98 (S)
96 (S)
95 (S)
94 (S)
[a]
Reactions carried out using 0.5 mmol of substrate and (ees up to 99%) in a wide range of E- and Z-trisubsti-
2 mol% of Ir catalyst precursor.
tuted alkenes. It should be pointed out that these cat-
alysts are also very tolerant to the presence of a neigh-
bouring polar group. Thus, a range of allylic alcohols,
acetates, a,b-unsaturated esters and vinylboronates
were hydrogenated with high enantioselectivities. The
good performance extends to the very challenging
class of terminal disubstituted aryl/alkyl olefins. For
this substrate class, our results indicated that enantio-
selectivity is dependent on the nature of the alkyl sub-
strate substituent, which has been attributed to the
presence of an isomerization process under hydroge-
[b]
[c]
1
Conversion measured by H NMR for substrate S1 or by
GC for substrate S18.
Enantiomeric excesses determined by chiral HPLC (sub-
strate S1) or GC (substrate S18).
Reaction carried out at 125 bar.
Reaction carried out at 50 bar.
[d]
[e]
Recycling Experiments using Propylene Carbonate as
Solvent
Encouraged by the excellent results obtained, we de- nation conditions. Enantioselectivities were therefore
cided to go one step further and study the recycling best in the asymmetric reduction of aryl and heteroar-
of our catalyst systems. For a practical application, yl/tert-butyl substrates (ees up to 99%). Interestingly,
catalyst recycling is an extremely important topic be- for 1,1-disubstituted substrates, both enantiomers of
cause of the very high price of iridium. Propylene car- the hydrogenation product can be obtained in high
bonate (PC) allows catalysts to be repeatedly recycled enantioselectivity, simply by changing the configura-
by a simple two-phase extraction with an apolar sol- tion of the biaryl phosphite moiety. The asymmetric
vent.[23] Moreover, PC is an extremely attractive sol- hydrogenation was also performed using propylene
vent because of its high boiling point, low toxicity and carbonate as solvent, which allowed the Ir catalysts to
environmentally friendly synthesis.[23,24] To study be reused and maintained the excellent enantioselec-
whether the new Ir-P,S catalytic systems developed in tivities. These results provide a new class of ligands
this study can be efficiently recycled using PC, sub- for the highly enantioselective Ir-catalyzed hydroge-
strates S1 and S18 were hydrogenated with the cata- nation of a wide range of substrates and open up the
lyst precursor [IrACTHNUGRTENNUG(cod)ACHTUNGTRENN(UGN L11a)]BArF (Table 4). We enantioselective Ir-catalyzed hydrogenation of mini-
were pleased to see that this catalyst can be used in mally functionalized olefins to a type of ligand other
PC up to five times with no significant losses in enan- than N-donor heterodonor ligands.
tioselectivity, although the reaction time increased.
This is probably due to the iridium catalyst partially
passing into the hexane phase[23a] and/or the formation
Experimental Section
of inactive triiridium hydride clusters.[4,25]
General Considerations
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
are easily prepared in one step from the corresponding biar-
yls.[27] Phosphite-thioether ligands L1–L3a,[10] phosphinite-
thioether ligands L1–L7i[12a,28], thioether-hydroxy compounds
5–11[10,12a] and alcohols 1–4[11] were prepared as previously
described. 1H, 13C{1H}, 31P{1H} NMR spectra and NOESY
experiments were recorded using a 400 MHz spectrometer.
Conclusions
A thioether-phosphite/phosphinite/phosphine ligand
library, which contains a furanoside as a simple but ef-
fective backbone, was tested in the asymmetric Ir-cat-
alyzed hydrogenation of several minimally functional-
ized alkenes. Our results show that catalytic perfor-
mance depended strongly on the ligand parameters
(the position of the thioether group at either C-5 or Chemical shifts are relative to that of SiMe4 (1H and 13C) as
152
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Adv. Synth. Catal. 2013, 355, 143 – 160

A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
internal standard or H3PO4 (31P) as external standard. 1H
and 13C assignments were made on the basis of 1H-1H
gCOSY and 1H-13C gHSQC experiments.
JC,P =16 Hz), 78.7 (C-4), 84.5 (C-2), 105.0 (C-1), 111.7
(CMe2), 121.4 (CH=), 121.7 (CH=), 123.0 (C), 124.4 (C),
124.9 (d, CH=, JC,P =7.1 Hz), 126.0 (CH=), 126.3 (CH=),
127.1 (CH=), 128.3 (CH=), 128.4 (CH=), 19.3 (CH=), 130.0
(CH=), 130.5 (CH=), 131.2 (C), 131.7 (C), 132.8 (C), 132.9
(C), 135.6 (C), 147.3 (C), 148.2 (d, C, JC,P =5.3 Hz); anal.
calcd. (%) for C34H29O6PS: C 68.45, H 4.90, S 5.37; found: C
68.54, H 4.86, S 5.24.
Typical Procedure for the Preparation of Thioether-
Phosphite Ligands L1–L15a–h
The corresponding phosphorochloridite (1.1 mmol) pro-
duced in situ was dissolved in toluene (5 mL) and pyridine
(0.3 mL, 3.9 mmol) was added. The corresponding thioether-
hydroxy compound (1 mmol) was azeotropically dried with
toluene (3ꢅ2 mL) and then dissolved in toluene (5 mL) to
which pyridine (0.3 mL, 3.9 mmol) was added. The alcohol
solution was transferred slowly to the solution of phosphor-
ochloridite. The reaction mixture was stirred at 808C for
90 min, and the pyridine salts were removed by filtration.
Evaporation of the solvent gave a white foam, which was
purified by flash chromatography in alumina (toluene/
NEt3 =100/1) to produce the corresponding ligand as
a white solid.
L1h: Yield: 393 mg (66%). 31P NMR (400 MHz, C6D6):
d=145.7 (s); 1H NMR (400 MHz, C6D6): d= 0.89 (s, 3H,
2
CH3), 1.16 (s, 3H, CH3), 3.23 (dd, 1H, H-5’, J5’,5 =13.2 Hz,
3
3J5’,4 =5.6 Hz), 3.39 (dd, 1H, H-5, 2J5,5’ =13.2 Hz, J5,4
=
2
4.6 Hz), 4.39 (d, 1H, H-2, J2,1 =3.6 Hz), 4.41 (m, 1H, H-4),
3
4.89 (dd, 1H, H-3, J3,P =9.2 Hz, J3,4 =2.8 Hz), 5.68 (d, 1H,
H-1, 3J1,2 =3.6 Hz), 6.79–7.61 (m, 17H, CH=); 13C NMR
(400 MHz, C6D6): d=24.4 (CH3), 27.0 (CH3), 32.4 (C-5),
76.6 (d, C-3, JC,P =10.5 Hz), 79.4 (d, C-4, JC,P =5.3 Hz), 85.1
(C-2), 105.6 (C-1), 112.1 (CMe2), 122.2 (CH=), 122.3 (CH=),
123.5 (C), 125.1 (C), 125.6 (CH=), 125.7 (CH=), 126.7 (CH=
), 127.0 (d, CH=, JC,P =3.5 Hz), 127.7 (d, CH=, JC,P
=
14.7 Hz), 129.0 (d, CH=, JC,P =4.0 Hz), 129.6 (CH=), 130.3
(CH=), 130.9 (C), 131.3 (C), 131.8 (C), 132.4 (C), 133.4 (C),
133.7 (C), 135.1 (C), 147.9 (d, C, JC,P =4.0 Hz), 148.9 (d, C,
L1e: Yield: 458 mg (69%). 31P NMR (400 MHz, C6D6):
d=140.9 (s); 1H NMR (400 MHz, C6D6): d=0.98 (s, 3H,
CH3), 1.18 (s, 3H, CH3), 1.52 (s, 18H, CH3, t-Bu), 1.66 (s,
3H, CH3), 1.78 (s, 3H, CH3), 2.02 (s, 3H, CH3), 2.07 (s, 3H,
J
C,P =6.0 Hz); anal. calcd. (%) for C34H29O6PS: C 68.45, H
4.90, S 5.37; found: C 68.51, H 4.92, S 5.44.
2
3
CH3), 2.75 (dd, 1H, H-5’, J5’,5 =14.4 Hz, J5’,4 =6.8 Hz), 2.81
L4a: Yield: 442 mg (63%). 31P NMR (400 MHz, C6D6):
d=142.4 (s); 1H NMR (400 MHz, C6D6): d=1.01 (s, 3H,
CH3), 1.17 (s, 9H, CH3, t-Bu), 1.24 (s, 9H, CH3, t-Bu), 1.246
(s, 9H, CH3, t-Bu), 1.34 (s, 3H, CH3), 1.59 (s, 18H, CH3, t-
2
3
(dd, 1H, H-5, J5’-5 =14.4 Hz, J5,4 =6.4 Hz), 4.46 (m, 1H, H-
4), 4.61 (d, 1H, H-2, J2,1 =3.6 Hz), 4.82 (dd, 1H, H-3, J3,P
2
=
3
3
10.8 Hz, J3,4 =2.4 Hz), 5.85 (d, 1H, H-1, J1,2 =3.6 Hz), 6.82–
7.31 (m, 7H, CH=); 13C NMR (400 MHz, C6D6); d=16.1
(CH3-Ar), 16.5 (CH3-Ar), 20.0 (CH3-Ar), 20.1 (CH3-Ar),
25.9 (CH3), 26.4 (CH3), 30.5 (C-5), 31.3 (CH3, t-Bu), 31.5
(CH3, t-Bu), 34.5 (C, t-Bu), 34.7 (C, t-Bu), 76.5 (d, C-3,
2
3
Bu), 3.02 (dd, 1H, H-5’, J5’,5 =13.6 Hz, J5’,4 =6.8 Hz), 3.11
2
3
(dd, 1H, H-5, J5,5’ =13.6 Hz, J5,4 =2.8 Hz), 4.39 (m, 1H, H-
2), 4.60 (m, 1H, H-4), 5.07 (m, 1H, H-3), 5.78 (d, 1H, H-1,
3J1,2 =3.6 Hz), 7.32 (m, 2H, CH=), 7.60 (m, 2H, CH=);
13C NMR (400 MHz, C6D6): d=26.2 (CH3), 27.2 (CH3), 30.4
(CH3, t-Bu), 30.9 (CH3, t-Bu), 31.5 (CH3, t-Bu), 34.2 (C, t-
Bu), 35.8 (C, t-Bu), 42.0 (C-5), 77.1 (C-3), 80.2 (C-4), 84.5
(C-2), 104.6 (C-1), 111.4 (CMe2), 124.3 (CH=), 127.1 (CH=),
127.9 (CH=), 128.2 (CH=), 133.8 (C), 134.0 (C), 140.5 (C),
140.7 (C), 146.8 (C), 147.0 (C); anal. calcd. (%) for
C40H61O6PS: C 68.54, H 8.77, S 4.57; found: C 68.49, H 8.75,
S 4.53.
J
C,P =5.4 Hz), 79.4 (C-4), 84.2 (C-2), 105.0 (C-1), 111.7
(CMe2), 125.3 (CH=), 127.8 (CH=), 127.9 (CH=), 128.1
(CH=), 128.8 (CH=), 128.9 (C), 131.0 (C), 132.2 (C), 132.6
(C), 134.7 (C), 135.2 (C), 136.6 (C), 137.6 (C), 138.0 (C),
144.6 (C), 145.0 (C); anal. calcd. (%) for C38H49O6PS: C
68.65, H 7.43, S 4.82; found: C 68.61, H 7.41, S 4.79.
L1f: Yield: 405 mg (61%). 31P NMR (400 MHz, C6D6):
d=136.9 (s); 1H NMR (400 MHz, C6D6): d=0.86 (s, 3H,
CH3), 1.18 (s, 3H, CH3), 1.49 (s, 9H, CH3, t-Bu), 1.54 (s, 9H,
L5a: Yield: 595 mg (81%). 31P NMR (400 MHz, C6D6):
CH3, t-Bu), 1.65 (s, 3H, CH3), 1.76 (s, 3H, CH3), 2.00 (s, 6H,
1
2
d=143.2 (bs); H NMR (400 MHz, C6D6): d=1.14 (s, 3H,
CH3), 3.34 (m, 2H, H-5ꢃ and H-5), 3.89 (d, 1H, H-2, J2,1
=
CH3), 1.29 (s, 18H, CH3, t-Bu), 1.33 (s, 3H, CH3), 1.59 (s,
9H, CH3, t-Bu), 1.63 (s, 9H, CH3, t-Bu), 2.23 (s, 3H, CH3-
3.6 Hz), 4.48 (m, 1H, H-4), 5.02 (dd, 1H, H-3, J3,P =6.8 Hz,
3
3J3,4 =2.8 Hz), 5.66 (d, 1H, H-1, J1,2 =3.6 Hz), 6.80–7.30 (m,
2
Ph), 2.98 (dd, 1H, H-5’, J5’,5 =14.0 Hz, 3J5’,4 =6.4 Hz), 3.48
7H, CH=); 13C NMR (400 MHz, C6D6): d=16.1 (CH3-Ar),
16.4 (CH3-Ar), 19.9 (CH3-Ar), 20.0 (CH3-Ar), 25.5 (CH3),
26.2 (CH3), 31.2 (CH3, t-Bu), 31.4 (CH3, t-Bu), 31.5 (C-5),
34.5 (C, t-Bu), 34.7 (C, t-Bu), 77.0 (d, C-3, JC,P =2.0 Hz), 79.4
(d, C-4, JC,P =6.1 Hz), 84.0 (C-2), 105.0 (C-1), 110.8 (CMe2),
126.7 (CH=), 128.6 (CH=), 128.8 (CH=), 129.5 (CH=), 130.3
(CH=), 132.0 (C), 132.5 (C), 133.3 (C), 135.3 (C), 135.8 (C),
136.4 (C), 138.1 (C), 138.5 (C), 138.8 (C), 145.6 (C), 145.8
(C); anal. calcd. (%) for C38H49O6PS: C 68.65, H 7.43, S
4.82; found: C 68.62, H 7.41, S 4.80.
2
3
(dd, 1H, H-5, J5,5’ =14.0 Hz, J5,4 =3.2 Hz), 4.41 (d, 1H, H-2,
2J2,1 =3.6 Hz), 4.53 (m, 1H, H-4), 4.76 (m, 1H, H-3), 5.64 (d,
3
1H, H-1, J1,2 =4.0 Hz), 6.80–7.50 (m, 8H, CH=); 13C NMR
(400 MHz, C6D6): d=21.3 (CH3-Ph), 25.4 (CH3), 26.0 (CH3),
31.8 (CH3, t-Bu), 32.0 (CH3, t-Bu), 32.1 (CH3, t-Bu), 32.2
(CH3, t-Bu), 34.7 (C, t-Bu), 35.0 (C, t-Bu), 36.0 (C-5), 75.1
(C-3), 76.5 (C-4), 78.3 (C-2), 102.9 (C-1), 113.1 (CMe2),
124.9 (CH=), 125.1 (CH=), 125.8 (CH=), 126.9 (CH=), 127.0
(CH=), 127.2 (CH=), 131.8 (C). 133.8 (C), 134.0 (C), 134.2
(C), 141.1 (C), 141.4 (C) 141.5 (C), 145.8 (C), 146.2 (C),
146.3 (C); anal. calcd. (%) for C43H59O6PS: C 70.27, H 8.09,
S 4.36; found: C 70.25, H 8.10, S 4.38.
L1g: Yield: 435 mg (73%). 31P NMR (400 MHz, C6D6):
d=148.6 (s); 1H NMR (400 MHz, C6D6): d=0.97 (s, 3H,
CH3), 1.18 (s, 3H, CH3), 3.27 (m, 2H, H-5ꢃ and H-5), 4.49
L6a: Yield: 623 mg (79%). 31P NMR (400 MHz, C6D6):
2
(m, 1H, H-4), 4.68 (d, 1H, H-2, J2,1 =4.0 Hz), 4.97 (dd, 1H,
1
3
H-3, J3,P =5.6 Hz, 3J3,4 =2.0 Hz), 5.82 (d, 1H, H-1, J1,2
=
d=143.4 (bs); H NMR (400 MHz, C6D6): d=1.17 (s, 3H,
4.0 Hz), 6.80–7.60 (m, 17H, CH=); 13C NMR (400 MHz,
C6D6): d=26.0 (CH3), 26.5 (CH3), 30.9 (C-5), 78.0 (d, C-3,
CH3), 1.29 (s, 9H, CH3, t-Bu), 1.31 (s, 9H, CH3, t-Bu), 1.38
(s, 3H, CH3), 1.51 (s, 9H, CH3, t-Bu), 1.60 (s, 9H, CH3, t-
Adv. Synth. Catal. 2013, 355, 143 – 160
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
153

Mercedes Coll et al.
FULL PAPERS
2
3
Bu), 2.87 (dd, 1H, H-5’, J5’,5 =14.0 Hz, J5’,4 =6.4 Hz), 3.48
6.1 Hz), 84.1 (C-2), 104.8 (C-1), 111.8 (CMe2), 127.9 (CH=),
128.0 (CH=), 128.3 (CH=), 131.3 (C), 131.9 (C), 132.6 (C),
133.0 (C), 137.8 (C), 138.2 (C), 143.1(C), 145.0 (C), 145.1
(C); anal. calcd. (%) for C40H53O6PS: C 69.34, H 7.71, S
4.63; found: C 69.31, H 7.71, S 4.60.
2
3
(dd, 1H, H-5, J5,5’ =14.0 Hz, J5,4 =3.2 Hz), 4.52 (d, 1H, H-2,
2J2,1 =4.0 Hz), 4.64 (m, 1H, H-4), 4.69 (m, 1H, H-3), 5.59 (d,
1H, H-1, J1,2 =4.0 Hz), 6.80–7.50 (m, 8H, CH=); 13C NMR
3
(400 MHz, C6D6): d=26.0 (CH3), 26.3 (CH3), 31.9 (CH3, t-
Bu), 32.0 (CH3, t-Bu), 32.2 (CH3, t-Bu), 34.7 (C, t-Bu), 34.8
(C, t-Bu), 35.0 (C, t-Bu), 35.8 (C-5), 74.3 (C-3), 76.9 (C-4),
78.2 (C-2), 102.8 (C-1), 113.4 (CMe2), 124.8 (CH=), 125.6
(CH=), 125.9 (CH=), 126.8 (CH=), 126.9 (CH=), 127.2
(CH=), 131.4 (C). 132.8 (C), 133.4 (C), 133.6 (C), 141.4 (C),
141.8 (C), 145.9 (C), 146.1 (C), 146.2 (C), 146.4 (C); anal.
calcd. (%) for C43H56F3O6PS: C 65.46, H 7.15, S 4.06; found:
C 65.43, H 7.13, S 4.04.
L8a: Yield: 532 mg (73%). 31P NMR (400 MHz, C6D6):
d=143.1 (s); 1H NMR (400 MHz, C6D6): d=1.12 (s, 3H,
CH3), 1.25 (s, 9H, CH3, t-Bu), 1.27 (s, 9H, CH3, t-Bu), 1.44
(s, 3H, CH3), 1.57 (s, 9H, CH3, t-Bu), 1.59 (s, 9H, CH3, t-
2
3
Bu), 2.90 (dd, 1H, H-5’, J5’,5 =13.6 Hz, J5’,4 =5.2 Hz), 3.23
2
3
(dd, 1H, H-5, J5,5’ =13.6 Hz, J5,4 =3.2 Hz), 3.96 (m, 1H, H-
2), 4.41 (m, 1H, H-3), 4.48 (m, 1H, H-4), 5.41 (d, 1H, H-1,
3J1,2 =3.2 Hz), 6.80–7.60 (m, 9H, CH=); 13C NMR (400 MHz,
C6D6): d=26.4 (CH3), 26.6 (CH3), 31.0 (CH3, t-Bu), 31.1
(CH3, t-Bu), 31.2 (CH3, t-Bu), 34.3 (C, t-Bu), 35.2 (C, t-Bu),
35.3 (C-5), 76.2 (C-3), 77.5 (d, C-4, JC,P =3.1 Hz), 78.3 (C-2),
103.8 (C-1), 112.6 (CMe2), 123.9 (d, CH=, JC,P =25.9 Hz),
125.6 (CH=), 126.7 (CH=), 126.9 (CH=), 128.6 (CH=), 128.9
(CH=), 129.4 (CH=), 133.1 (C), 133.4 (C), 137.0 (C), 140.4
(C), 140.6 (C), 146.1 (C), 146.2 (C), 146.7 (C); anal. calcd.
(%) for C42H57O6PS: C 69.97, H 7.97, S 4.45; found: C 69.95,
H 8.01, S 4.41.
L7a: Yield: 520 mg (69%). 31P NMR (400 MHz, C6D6):
d=142.7 (bs); H NMR (400 MHz, C6D6): d=1.15 (s, 3H,
CH3), 1.25 (s, 9H, CH3, t-Bu), 1.31 (s, 9H, CH3, t-Bu), 1.43
(s, 3H, CH3), 1.52 (s, 9H, CH3, t-Bu), 1.60 (s, 9H, CH3, t-
Bu), 2.59 (s, 6H, CH3-Ar), 2.72 (dd, 1H, H-5’, J5’,5 =14 Hz,
1
2
3J5’,4 =7.2 Hz), 3.13 (dd, 1H, H-5, J5,5’ =14 Hz, J5,4 =3.2 Hz),
3.98 (m, 1H, H-2), 4.03 (m, 1H, H-4), 4.19 (m, 1H, H-3),
5.43 (d, 1H, H-1, 3J1,2 =3.6 Hz), 6.80–7.60 (m, 7H, CH=);
13C NMR (400 MHz, C6D6): d=22.1 (CH3-Ar), 26.4 (CH3),
27.0 (CH3), 31.0 (CH3, t-Bu) 31.2 (CH3, t-Bu), 34.3 (C, t-Bu),
35.2 (C, t-Bu), 35.4 (C-5), 75.4 (C-3), 76.5 (C-4), 78.3 (C-2),
104.0 (C-1), 112.8 (CMe2), 124.0 (d, CH=, JC,P =12 Hz),
126.7 (CH=), 126.8 (CH=), 128.1 (CH=), 128.2 (CH=), 129.2
(CH=), 133.6 (C), 137.8 (C), 140.4 (C), 141.3 (C), 143.2 (C),
146.8 (C); anal. calcd. (%) for C44H61O6PS: C 70.56, H 8.21,
S 4.28; found: C 70.62, H 8.25, S 4.21.
2
3
L8b: Yield: 408 mg (61%). 31P NMR (400 MHz, C6D6):
d=141.8 (s); 1H NMR (400 MHz, C6D6): d=1.18 (s, 3H,
CH3), 1.27 (s, 9H, CH3, t-Bu), 1.40 (s, 3H, CH3), 1.59 (s, 9H,
2
3
CH3, t-Bu), 2.97 (dd, 1H, H-5’, J5’,5 =13.2 Hz, J5’,4 =6.4 Hz),
2
3
3.23 (dd, 1H, H-5, J5,5’ =13.2 Hz, J5,4 =2.4 Hz), 3.28 (s, 3H,
CH3-O), 3.29 (s, 3H, CH3-O), 3.92 (m, 1H, H-2), 4.39 (m,
3
1H, H-3), 4.42 (m, 1H, H-4), 5.39 (d, 1H, H-1, J1,2
=
L7e: Yield: 471 mg (68%). 31P NMR (400 MHz, C6D6):
d=140.7 (s); 1H NMR (400 MHz, C6D6): d=1.02 (s, 3H,
CH3), 1.24 (s, 3H, CH3), 1.50 (s, 9H, CH3, t-Bu), 1.53 (s, 9H,
CH3, t-Bu), 1.70 (s, 3H, CH3), 1.84 (s, 3H, CH3), 2.05 (s, 3H,
3.6 Hz), 6.80–7.60 (m, 9H, CH=); 13C NMR (400 MHz,
C6D6): d=26.2 (CH3), 26.5 (CH3), 31.2 (CH3, t-Bu), 31.5
(CH3, t-Bu), 34.2 (C, t-Bu), 34.9 (C, t-Bu), 35.6 (C-5), 54.8
(CH3-O), 76.3 (C-3), 77.4 (b, C-4), 78.5 (C-2), 103.4 (C-1),
112.4 (CMe2), 123.8 (d, CH=, JC,P =24.2 Hz), 125.3 (CH=),
126.4 (CH=), 126.9 (CH=), 128.2 (CH=), 128.5 (CH=), 129.0
(CH=), 133.4 (C), 137.0 (C), 140.4 (C), 140.6 (C), 146.1 (C),
151.3 (C), 151.6 (C); anal. calcd. (%) for C36H45O8PS: C
64.65, H 6.78, S 4.79; found: C 64.64, H 6.77, S 4.77.
2
CH3), 2.19 (s, 3H, CH3), 2.45 (dd, 1H, H-5’, J5’,5 =14.0 Hz,
3J5’,4 =7.6 Hz), 2.49 (s, 6H, CH3), 2.66 (dd, 1H, H-5, J5’,5
=
2
3
14.0 Hz, J5,4 =2.4 Hz), 4.19 (m, 1H, H-4), 4.59 (d, 1H, H-2,
2J2,1 =3.6 Hz), 4.71 (dd, 1H, H-3,
J3,P =10.4 Hz, J3,4 =
3
3
2.4 Hz), 5.84 (d, 1H, H-1, J1,2 =3.6 Hz), 6.90–7.30 (m, 5H,
CH=); 13C NMR (400 MHz, C6D6): d=16.1 (CH3-Ar), 16.4
(CH3-Ar), 20.0 (CH3-Ar), 20.1 (CH3-Ar), 21.8 (CH3-Ar),
26.0 (CH3), 26.3 (CH3), 31.1 (CH3, t-Bu), 31.4 (CH3, t-Bu),
L8c: Yield: 397 mg (62%). 31P NMR (400 MHz, C6D6):
d=141.7 (s); 1H NMR (400 MHz, C6D6): d=0.37 (s, 9H,
CH3Si), 0.42 (s, 9H, CH3Si) 1.09 (s, 3H, CH3), 1.45 (s, 3H,
2
3
32.7 (C-5), 34.4 (C, t-Bu), 34.7 (C, t-Bu), 77.0 (d, C-3, JC,P
=
CH3), 2.84 (dd, 1H, H-5’, J5’,5 =14.0 Hz, J5’,4 =6.4 Hz), 3.20
2
3
6.2 Hz), 78.7 (C-4), 84.3 (d, C-2, JC,P =4.0 Hz), 104.8 (C-1),
111.5 (CMe2), 127.7 (CH=), 127.8 (CH=), 128.0 (CH=),
128.2 (CH=), 131.0 (C), 132.0 (C), 132.3 (C), 132.5 (C),
133.0 (C), 134.6 (C), 135.2 (C), 137.7 (C), 137.9 (C), 138.0
(C), 143.3 (C), 144.6 (C), 144.9 (C); anal. calcd. (%) for
C40H53O6PS: C 69.34, H 7.71, S 4.63; found: C 69.32, H 7.70,
S 4.62.
(dd, 1H, H-5, J5,5’ =14.0 Hz, J5,4 =3.2 Hz), 3.91 (m, 1H, H-
2), 4.29 (m, 1H, H-3), 4.46 (m, 1H, H-4), 5.32 (d, 1H, H-1,
3J1,2 =4.0 Hz), 6.80–7.60 (m, 11H, CH=); 13C NMR
(400 MHz, C6D6): d=0 (CH3Si), 0.1 (CH3Si), 26.6 (CH3),
26.7 (CH3), 35.9 (C-5), 76.3 (C-3), 77.8 (C-4), 78.5 (C-2),
104.0 (C-1), 112.7 (CMe2), 125.1 (CH=), 125.3 (CH=), 125.8
(C), 126.0 (CH=), 126.9 (C), 128.2 (CH=), 128.8 (CH=),
129.8 (CH=), 130.9 (C), 132.5 (CH=), 132.7 (CH=), 133.1
(C), 135.2 (CH=), 135.7 (CH=), 145.9 (C), 146.6 (C); anal.
calcd. (%) for C32H41O6PS: C 59.97, H 6.45, S 5.00; found: C
60.02, H 6.49, S 4.98.
L7f: Yield: 492 mg (71%). 31P NMR (400 MHz, C6D6):
d=137.7 (s); 1H NMR (400 MHz, C6D6): d=0.90 (s, 3H,
CH3), 1.25 (s, 3H, CH3), 1.52 (s, 9H, CH3, t-Bu), 1.57 (s, 9H,
CH3, t-Bu), 1.68 (s, 3H, CH3), 1.78 (s, 3H, CH3), 2.03 (s, 6H,
2
CH3), 2.56 (s, 6H, CH3), 3.08 (dd, 1H, H-5’, J5’,5 =13.2 Hz,
L8d: Yield: 243 mg (49%). 31P NMR (400 MHz, C6D6):
3
3J5’,4 =6.4 Hz), 3.24 (dd, 1H, H-5, 2J5’,5 =13.2 Hz, J5,4
=
d=141.8 (s). 1H NMR (400 MHz, C6D6): d=1.11 (s, 3H,
2
2
7.6 Hz), 4.01 (d, 1H, H-2, J2,1 =4.0 Hz), 4.40 (m, 1H, H-4),
CH3), 1.40 (s, 3H, CH3), 2.92 (dd, 1H, H-5’, J5’,5 =14.0 Hz,
3
3
4.92 (dd, 1H, H-3, J3,P =7.6 Hz, J3,4 =2.4 Hz), 5.66 (d, 1H,
3J5’,4 =6.4 Hz), 3.22 (dd, 1H, H-5, 2J5,5’ =14.0 Hz, J5,4
=
H-1, 3J1,2 =3.6 Hz), 6.90–7.30 (m, 5H, CH=); 13C NMR
(400 MHz, C6D6): d=16.1 (CH3-Ar), 16.4 (CH3-Ar), 19.9
(CH3-Ar), 20.0 (CH3-Ar), 21.9 (CH3-Ar), 25.5 (CH3), 26.2
(CH3), 31.2 (CH3, t-Bu), 31.4 (CH3, t-Bu), 33.0 (C-5), 34.6
4.4 Hz), 4.06 (m, 1H, H-2), 4.32 (m, 1H, H-3), 4.36 (m, 1H,
H-4), 5.25 (d, 1H, H-1, 3J1,2 =3.6 Hz), 6.80–7.60 (m, 13H,
CH=); 13C NMR (400 MHz, C6D6): d=26.1 (CH3), 26.4
(CH3), 34.8 (C-5), 76.2 (C-3), 77.9 (C-4), 79.1 (C-2), 103.2
(C-1), 113.1 (CMe2), 121.5 (CH=), 121.8 (CH=), 124.6 (CH=
(C, t-Bu), 34.7 (C, t-Bu), 77.5 (C-3), 79.2 (d, C-4, JC,P
=
154
asc.wiley-vch.de
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 143 – 160

A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
2
), 125.3 (CH=), 125.9 (CH=), 126.8 (CH=), 127.9 (CH=),
128.2 (CH=), 129.1 (CH=), 129.5 (CH=), 129.4 (CH=), 131.0
(C), 131.3 (C), 132.4 (C), 132.9 (C), 141.7 (C); anal. calcd.
(%) for C26H25O6PS: C 62.89, H 5.08, S 6.46; found: C 62.85,
H 5.06, S 6.43.
CH3), 1.46 (s, 3H, CH3), 3.00 (dd, 1H, H-5’, J5’,5 =14.0 Hz,
3J5’,4 =6.6 Hz), 3.31 (dd, 1H, H-5, 2J5,5’ =14.0 Hz, J5,4
=
3
3.6 Hz), 4.12 (m, 1H, H-2), 4.19 (m, 1H, H-3), 4.47 (m, 1H,
H-4), 5.17 (d, 1H, H-1, 3J1,2 =3.2 Hz), 6.80–7.60 (m, 17H,
CH=); 13C NMR (400 MHz, C6D6): d=27.1 (CH3), 35.7 (C-
5), 77.4 (d, C-3, JC,P =4.6 Hz), 77.8 (d, C-4, JC,P =3.9 Hz),
79.2 (C-2), 104.6 (C-1), 113.2 (CMe2), 122.4 (CH=), 122.8
(CH=), 123.4 (C), 125.2 (C), 125.6 (d, CH=, JC,P =12.2 Hz),
126.5 (CH=), 127.2 (CH=), 127.0 (d, CH=, JC,P =17.0 Hz),
129.0 (CH=), 129.5 (CH=), 129.9 (CH=), 130.6 (CH=), 131.3
L8e: Yield: 471 mg (72%). 31P NMR (400 MHz, C6D6):
d=136.6 (s); 1H NMR (400 MHz, C6D6): d=1.11 (s, 3H,
CH3), 1.44 (s, 3H, CH3), 1.58 (s, 9H, CH3, t-Bu), 1.60 (s, 9H,
CH3, t-Bu), 1.67 (s, 3H, CH3Ph), 1.74 (s, 3H, CH3Ph), 2.04
(s, 3H, CH3Ph), 2.11 (s, 3H, CH3Ph), 3.05 (dd, 1H, H-5’,
2
2J5’,5 =14.0 Hz, 3J5’,4 =4.8 Hz), 3.29 (dd, 1H, H-5, J5,5’
=
(CH=), 131.9 (C), 132.4 (C), 133.4 (C), 133.7 (d, C, JC,P
=
3
14.0 Hz, J5,4 =3.6 Hz), 4.06 (m, 1H, H-2), 4.37 (m, 1H, H-
1.5 Hz), 137.6 (C), 148.2, 149.4 (d, C, JC,P =4.5 Hz); anal.
calcd. (%) for C34H29O6PS: C 68.45, H 4.90, S 5.37; found: C
68.48, H 4.82, S 5.35.
3
3), 4.44 (m, 1H, H-4), 5.38 (d, 1H, H-1, J1,2 =3.6 Hz), 6.80–
7.50 (m, 7H, CH=); 13C NMR (400 MHz, C6D6): d=16.1
(CH3Ph), 16.4 (CH3Ph), 19.9 (CH3Ph), 20.0 (CH3Ph), 26.2
(CH3), 26.6 (CH3), 31.2 (CH3, t-Bu), 31.5 (CH3, t-Bu), 34.5
L9a: Yield: 382 mg (58%). 31P NMR (400 MHz, C6D6):
d=143.4 (s); 1H NMR (400 MHz, C6D6): d=1.14 (s, 3H,
CH3), 1.25 (s, 9H, CH3, t-Bu), 1.27 (s, 9H, CH3, t-Bu), 1.48
(s, 3H, CH3), 1.59 (s, 9H, CH3, t-Bu), 1.61 (s, 9H, CH3, t-
(C, t-Bu), 34.7 (C, t-Bu), 35.0 (C-5), 75.5 (d, C-3, JC,P
4.7 Hz), 77.6 (d, C-4, JC,P =3.8 Hz), 78.7 (d, C-2, JC,P
=
=
2
3.1 Hz), 103.6 (C-1), 112.7 (CMe2), 125.3 (CH=), 125.6
(CH=), 128.1 (CH=), 128.6 (CH=), 128.9 (CH=), 129.2
(CH=), 129.4 (C), 131.6 (C), 132.5 (C), 134.6 (C), 135.1 (C),
137.4 (C), 137.5 (C), 137.6 (C) 138.0 (C), 145.5 (C); anal.
calcd. (%) for C38H49O6PS: C 68.65, H 7.43, S 4.82; found: C
68.61, H 7.36, S 4.77.
Bu), 1.92 (s, 3H, CH3S), 2.46 (dd, 1H, H-5’, J5’,5 =14.4 Hz,
3J5’,4 =5.6 Hz), 2.71 (dd, 1H, H-5, 2J5,5’ =14.4 Hz, J5,4
=
3
3.2 Hz), 3.99 (m, 1H, H-2), 4.38 (m, 1H, H-4), 4.42 (m, 1H,
H-3), 5.42 (d, 1H, H-1, 3J1,2 =3.6 Hz), 7.20–7.70 (m, 4H,
CH=); 13C NMR (400 MHz, C6D6): d=17.7 (CH3-S), 27.3
(CH3), 27.5 (CH3), 32.1 (CH3, t-Bu), 35.2 (C, t-Bu), 35.9 (C,
t-Bu), 36.2 (C-5), 76.9 (C-3), 79.1 (C-2), 80.4 (C-4), 104.7 (C-
1), 113.5 (CMe2), 124.9 (CH=), 125.2 (CH=), 127.6 (CH=),
127.8 (CH=), 129.8 (C), 134.4 (C), 134.8 (C), 141.5 (C),
147.2 (C), 147.3 (C), 147.5 (C); anal. calcd. (%) for
C37H55O6PS: C 67.45, H 8.41, S 4.87; found: C 67.51, H 8.45,
S 4.81.
L8f: Yield: 458 mg (69%). 31P NMR (400 MHz, C6D6):
d)136.5 (s); 1H NMR (400 MHz, C6D6): d=1.11 (s, 3H,
CH3), 1.46 (s, 3H, CH3), 1.57 (s, 9H, CH3, t-Bu), 1.61 (s, 9H,
CH3, t-Bu), 1.69 (s, 3H, CH3Ph), 1.80 (s, 3H, CH3Ph), 2.06
(s, 3H, CH3Ph), 2.09 (s, 3H, CH3Ph), 2.74 (dd, 1H, H-5’,
2
2J5’,5 =14.0 Hz, 3J5’,4 =6.0 Hz), 3.15 (dd, 1H, H-5, J5,5’
=
3
14.0 Hz, J5,4 =2.8 Hz), 4.18 (m, 1H, H-3), 4.36 (m, 1H, H-
L10a: Yield: 588 mg (84%). 31P NMR (400 MHz, C6D6):
d=143.1 (s); 1H NMR (400 MHz, C6D6): d=1.13 (s, 3H,
CH3), 1.21 (s, 9H, CH3, t-Bu), 1.25 (s, 9H, CH3, t-Bu), 1.28
3
3), 4.43 (m, 1H, H-4), 5.35 (d, 1H, H-1, J1,2 =3.6 Hz), 6.80–
7.50 (m, 7H, CH=); 13C NMR (400 MHz, C6D6): d=16.1
(CH3Ph), 16.4 (CH3Ph), 20.0 (CH3Ph), 20.1 (CH3Ph), 26.4
(CH3), 26.5 (CH3), 31.2 (CH3, t-Bu), 31.5 (CH3, t-Bu), 34.5
(s, 9H, CH3, t-Bu), 1.47 (s, 3H, CH3), 1.61 (s, 9H, CH3, t-
2
Bu), 1.62 (s, 9H, CH3, t-Bu), 2.66 (dd, 1H, H-5’, J5’,5
=
(C, t-Bu), 34.7 (C, t-Bu), 35.0 (C-5), 76.2 (d, C-3, JC,P
1.6 Hz), 77.9 (d, C-4, JC,P =1.8 Hz), 78.2 (d, C-2, JC,P
=
=
14.0 Hz, 3J5’,4 =7.2 Hz), 2.95 (dd, 1H, H-5, 2J5,5’ =14.0 Hz,
3J5,4 =2.8 Hz), 3.95 (m, 1H, H-2), 4.35 (m, 1H, H-3), 4.49
2.3 Hz), 104.1 (C-1), 112.5 (CMe2), 125.5 (CH=), 127.8
(CH=), 128.1 (CH=), 128.3 (CH=), 128.5 (CH=), 128.9
(CH=), 129.2 (CH=), 130.9 (C), 131.0 (C), 131.8 (C), 132.1
(C), 132.2 (C), 132.5 (C), 134.4 (C), 135.2 (C) 137.3 (C),
137.6 (C), 138.0 (C), 138.1 (C), 144.6 (C), 145.3 (C); anal.
calcd. (%) for C38H49O6PS: C 68.65, H 7.43, S 4.82; found: C
68.63, H 7.41, S 4.81.
3
(m, 1H, H-4), 5.46 (d, 1H, H-1, J1,2 =4.0 Hz), 7.00–7.70 (m,
4H, CH=). 13C NMR (400 MHz, C6D6): d=27.3 (CH3), 27.5
(CH3), 31.7 (CH3, t-Bu), 32.0 (CH3, t-Bu), 32.1 (CH3, t-Bu),
32.2 (CH3, t-Bu), 32.3 (CH3, t-Bu), 35.2 (C, t-Bu), 36.3 (C, t-
Bu), 42.4 (C-5), 77.5 (C-3), 79.2 (C-2), 79.6 (C-4), 104.7 (C-
1), 113.5 (CMe2), 124.9 (CH=), 125.1 (CH=), 127.5 (CH=),
127.9 (CH=), 134.1 (C), 134.2 (C), 134.3 (C), 134.4 (C),
141.4 (C), 141.6 (C) 141.7 (C), 147.1 (C), 147.2 (C), 147.5
(C); anal. calcd. (%) for C40H61O6PS: C 68.54, H 8.77, S
4.57; found: C 68.52, H 8.75, S 4.53.
L8g: Yield: 322 mg (54%). 31P NMR (400 MHz, C6D6):
d=141.8 (s); 1H NMR (400 MHz, C6D6): d=1.10 (s, 3H,
2
CH3), 1.42 (s, 3H, CH3), 2.89 (dd, 1H, H-5’, J5’,5 =14.0 Hz,
3
3J5’,4 =4.4 Hz), 3.20 (dd, 1H, H-5, 2J5,5’ =14.0 Hz, J5,4
=
L11a: Yield: 452 mg (60%). 31P NMR (400 MHz, C6D6):
d=142.7 (bs); 1H NMR (400 MHz, C6D6): d=1.11(s, 3H,
CH3), 1.24 (s, 9H, CH3, t-Bu), 1.26 (s, 9H, CH3, t-Bu), 1.41
(s, 3H, CH3), 1.52 (s, 9H, CH3, t-Bu), 1.56 (s, 9H, CH3, t-
3.2 Hz), 4.04 (m, 1H, H-2), 4.38 (m, 2H, H-3 and H-4), 5.24
(d, 1H, H-1, 3J1,2 =3.2 Hz), 6.80–7.60 (m, 17H, CH=);
13C NMR (400 MHz, C6D6): d=26.4 (CH3), 26.5 (CH3), 34.5
(C-5), 76.3 (C-3), 77.8 (C-4), 78.5 (C-2), 104.0 (C-1), 112.8
(CMe2), 121.6 (CH=), 121.9 (CH=), 123.1 (C), 124.9 (d,
2
Bu), 2.58 (s, 6H, CH3-Ar), 2.62 (dd, 1H, H-5’, J5’,5 =14 Hz,
2
3
3J5’,4 =8.8 Hz), 3.06 (dd, 1H, H-5, J5,5’ =14 Hz, J5,4 =2.4 Hz),
3.93 (m, 1H, H-2), 4.16 (m, 1H, H-4), 4.28 (m, 1H, H-3),
5.40 (d, 1H, H-1, 3J1,2 =3.2 Hz), 6.80–7.60 (m, 7H, CH=);
13C NMR (400 MHz, C6D6): d=21.9 (CH3Ar), 26.4 (CH3),
31.0 (CH3, t-Bu), 31.2 (CH3, t-Bu), 34.3 (C, t-Bu), 35.2 (C, t-
Bu), 35.3 (C-5), 76.6 (C-4), 77.5 (C-3), 78.2 (C-2), 103.6 (C-
1), 112.5 (CMe2), 123.9 (d, CH=, JC,P =15.3 Hz), 126.6 (CH=
), 126.9 (CH=), 128.1 (CH=), 128.2 (CH=), 128.9 (CH=),
133.5 (C), 137.5 (C), 140.4 (C), 140.7 (C), 143.3 (C), 146.6
CH=, JC,P =7.8 Hz), 125.6 (CH=), 126.3 (d, CH=, JC,P
=
3.1 Hz), 127.0 (d, CH=, JC,P =8.9 Hz), 127.8 (CH=), 128.2
(CH=), 128.6 (CH=), 129.0 (CH=), 129.7 (CH=), 130.5
(CH=), 131.2 (C), 131.7 (C), 132.9 (C), 133.0 (C), 137.0 (C),
147.4 (d, C, JC,P =2.3 Hz), 148.0 (d, C, JC,P =4.6 Hz); anal.
calcd (%) for C34H29O6PS: C 68.45, H 4.90, S 5.37; found: C
68.52, H 4.89, S 5.34.
L8h: Yield: 364 mg (61%). 31P NMR (400 MHz, C6D6):
d=140.9 (s); 1H NMR (400 MHz, C6D6): d=1.11 (s, 3H,
Adv. Synth. Catal. 2013, 355, 143 – 160
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155

Mercedes Coll et al.
FULL PAPERS
(C), 146.7 (C); anal. calcd. (%) for C44H61O6PS: C 70.56, H
8.21, S 4.28; found: C 70.53, H 8.23, S 4.30.
(CH3), 31.7 (CH3, t-Bu), 31.8 (CH3, t-Bu), 35.1 (C, t-Bu),
35.2 (C, t-Bu), 53.8 (C-3), 63.7 (C-5), 78.7 (d, C-4, JC,P
=
L11e: Yield: 374 mg (54%). 31P NMR (400 MHz, C6D6):
d=135.9 (s); 1H NMR (400 MHz, C6D6): d=1.08 (s, 3H,
CH3), 1.38 (s, 3H, CH3), 1.54 (s, 9H, CH3, t-Bu), 1.58 (s, 9H,
CH3, t-Bu), 1.67 (s, 3H, CH3Ph), 1.69 (s, 3H, CH3Ph), 2.03
3.9 Hz), 86.3 (C-2), 105.7 (C-1), 112.2 (CMe2), 126.9 (CH=),
128.8 (CH=), 128.9 (CH=), 129.6 (CH=), 130.3 (CH=), 131.7
(C), 132.4 (C), 132.5 (C), 132.9 (C), 135.2 (C), 135.3 (C),
135.6 (C), 137.7 (C), 138.8 (C), 146.2 (C), 146.5 (C); anal.
calcd. (%) for C38H49O6PS: C 68.65, H 7.43, S 4.82; found: C
68.62, H 7.42, S 4.79.
(s, 3H, CH3Ph), 2.05 (s, 3H, CH3Ph), 2.79 (dd, 1H, H-5’,
2
2J5’,5 =13.6 Hz, 3J5’,4 =7.2 Hz), 3.11 (dd, 1H, H-5, J5,5’
=
3
13.6 Hz, J5,4 =2.8 Hz), 4.05 (m, 1H, H-2), 4.22 (m, 1H, H-
3), 4.27 (m, 1H, H-4), 5.39 (d, 1H, H-1, J1,2 =3.6 Hz), 6.90–
L12 f: Yield: 398 mg, 60%. 31P NMR (400 MHz, C6D6) d:
3
1
129.3 (s). H NMR (400 MHz, C6D6) d: 0.95 (s, 3H, CH3),
7.30 (m, 5H, CH=); 13C NMR (400 MHz, C6D6): d=16.5
(CH3Ph), 16.7 (CH3Ph), 20.2 (CH3Ph), 20.4 (CH3Ph), 26.6
(CH3), 26.8 (CH3), 31.5 (CH3, t-Bu), 31.8 (CH3, t-Bu), 34.8
(C, t-Bu), 35.1 (C, t-Bu), 37.2 (C-5), 76.3 (C-4), 77.8 (C-3),
79.2 (C-2), 103.8 (C-1), 113.0 (CMe2), 127.8 (CH=), 128.4
(CH=), 128.5 (CH=), 128.6 (CH=), 129.5 (C), 132.9 (C),
134.7 (C), 134.9 (C), 135.5 (C), 137.9 (C), 143.5 (C); anal.
calcd. (%) for C40H53O6PS: C 69.34, H 7.71, S 4.63; found: C
69.31, H 7.70, S 4.65.
1.38 (s, 3H, CH3), 1.60 (s, 9H, CH3, tBu), 1.61 (s, 9H, CH3,
tBu), 1.69 (s, 3H, CH3), 1.76 (s, 3H, CH3), 2.05 (s, 3H, CH3),
3
2.11 (s, 3H, CH3), 3.63 (d, 1H, H-3, J3,4 =4.4 Hz), 3.94 (m,
2
1H, H-5’), 4.46 (d, 1H, H-2, J2,1 =3.6 Hz), 4.52 (m, 1H, H-
3
5), 4.82 (m, 1H, H-4), 5.76 (d, 1H, H-1, J1,2 =3.6 Hz), 6.80–
7.30 (m, 7H, CH=). 13C NMR (400 MHz, C6D6) d: 16.1
(CH3-Ar), 16.4 (CH3-Ar), 20.0 (CH3-Ar), 20.1 (CH3-Ar),
25.9 (CH3), 26.5 (CH3), 31.0 (CH3, tBu), 31.2 (CH3, tBu),
34.5 (C, tBu), 34.6 (C, tBu), 53.0 (C-3), 63.5 (C-5), 78.2 (d,
C-4, JC,P =3.0 Hz), 85.4 (C-2), 105.0 (C-1), 111.5 (CMe2),
126.3 (CH=), 127.8 (CH=), 128.1 (CH=), 128.3 (CH=), 129.0
(CH=), 129.5 (CH=), 130.9 (C), 131.7 (C), 131.9 (C), 132.3
(C), 134.4 (C), 134.5 (C), 135.0 (C), 137.0 (C), 137.5 (C),
145.8 (C), 146.0 (C); anal. calcd. (%) for C38H49O6PS: C
68.65, H 7.43, S 4.82; found: C 68.60, H 7.41, S 4.78.
L11f: Yield: 436 mg (63%). 31P NMR (400 MHz, C6D6):
d=136.7 (s); 1H NMR (400 MHz, C6D6): d=1.20 (s, 3H,
CH3), 1.52 (s, 3H, CH3), 1.58 (s, 9H, CH3, t-Bu, 1.67 (s, 9H,
CH3, t-Bu), 1.77 (s, 3H, CH3Ph), 1.87 (s, 3H, CH3Ph), 2.14
(s, 3H, CH3Ph), 2.20 (s, 3H, CH3Ph), 2.56 (dd, 1H, H-5’,
2
2J5’,5 =13.6 Hz, 3J5’,4 =7.6 Hz), 2.99 (dd, 1H, H-5, J5,5’
=
3
13.6 Hz, J5,4 =2.0 Hz), 3.98 (m, 1H, H-3), 4.32 (m, 1H, H-
4), 4.48 (m, 1H, H-2), 5.47 (d, 1H, H-1, J1,2 =4.0 Hz), 6.90–
L13a: Yield: 500 mg (76%). 31P NMR (400 MHz, C6D6):
d=136.7 (s); 1H NMR (400 MHz, C6D6): d=1.07 (s, 3H,
CH3), 1.25 (s, 9H, CH3, t-Bu), 1.28 (s, 9H, CH3, t-Bu), 1.38
(s, 3H, CH3), 1.58 (s, 9H, CH3, t-Bu), 1.59 (s, 9H, CH3, t-
3
7.30 (m, 5H, CH=); 13C NMR (400 MHz, C6D6): d=16.3
(CH3Ph), 16.5 (CH3Ph), 20.1 (CH3Ph), 22.0 (CH3Ph), 26.5
(CH3), 26.6 (CH3), 31.4 (CH3, t-Bu), 31.6 (CH3, t-Bu), 34.6
(C, t-Bu), 34.8 (C, t-Bu), 36.8 (C-5), 76.8 (C-4), 78.0 (C-3),
78.3 (C-2), 104.1 (C-1), 112.6 (CMe2), 128.0 (CH=), 128.1
(CH=), 128.3 (CH=), 129.0 (CH=), 131.0 (C), 131.8 (C),
132.6 (C), 133.7 (C), 134.4 (C), 135.4 (C), 137.9 (C), 138.0
(C), 143.4 (C); anal. calcd. (%) for C40H53O6PS: C 69.34, H
7.71, S 4.63; found: C 69.37, H 7.74, S 4.61.
3
Bu), 2.10 (s, 3H, CH3), 2.94 (d, 1H, H-3, J3,4 =4.4 Hz), 4.29
3
(m, 2H, H-5ꢃ and H-5), 4.38 (d, 1H, H-2, J1,2 =3.6 Hz), 4.69
3
(m, 1H, H-4), 5.72 (d, 1H, H-1, J1,2 =3.6 Hz), 7.20–7.60 (m,
4H, CH=); 13C NMR (400 MHz, C6D6): d=15.3 (CH3-S),
27.0 (CH3), 27.5 (CH3), 31.8 (CH3, t-Bu), 32.1 (CH3, t-Bu),
35.2 (C, t-Bu), 36.2 (C, t-Bu), 54.0 (C-3), 64.7 (C-5), 79.4 (C-
4), 86.4 (C-2), 105.9 (C-1), 112.2 (CMe2), 125.0 (CH=), 125.1
(CH=), 127.5 (CH=), 127.7 (CH=), 134.0 (C), 134.3 (C),
141.1 (C), 147.3 (C), 147.5 (C), 147.7 (C); anal. calcd. (%)
for C37H55O6PS: C 67.45, H 8.41, S 4.87; found: C 67.40, H
8.38, S 4.86.
L12a: Yield: 536 mg (72%). 31P NMR (400 MHz, C6D6):
d=136.4 (s); 1H NMR (400 MHz, C6D6): d=0.95 (s, 3H,
CH3), 1.26 (s, 9H, CH3, t-Bu), 1.28 (s, 9H, CH3, t-Bu), 1.38
(s, 3H, CH3), 1.59 (s, 9H, CH3, t-Bu), 1.60 (s, 9H, CH3, t-
3
Bu), 3.68 (d, 1H, H-3, J3,4 =3.6 Hz), 4.38 (m, 2H, H-5ꢃ and
L14a: Yield: 415 mg (57%). 31P NMR (400 MHz, C6D6):
H-5), 4.47 (d, 1H, H-2, 3J1,2 =3.6 Hz), 4.82 (m, 1H, H-4),
5.78 (d, 1H, H-1, 3J1,2 =3.6 Hz), 6.80–7.60 (m, 9H, CH=);
13C NMR (400 MHz, C6D6): d=26.7 (CH3), 27.2 (CH3), 31.5
(CH3, t-Bu), 31.6 (CH3, t-Bu), 31.9 (CH3, t-Bu), 32.0 (CH3, t-
Bu), 35.0 (C, t-Bu), 36.0 (C, t-Bu), 53.8 (C-3), 64.4 (C-5),
78.9 (C-4), 86.2 (C-2), 105.8 (C-1), 112.3 (CMe2), 124.1 (d,
CH=, JC,P =13.0 Hz), 125.3 (CH=), 126.3 (CH=), 126.7 (d,
CH=, JC,P =20 Hz), 128.1 (CH=), 128.9 (CH=), 129.0 (CH=),
129.6 (CH=), 133.1 (C), 133.3 (C), 134.3 (C), 137.5 (C),
140.1 (C), 140.3 (C), 146.5 (C), 146.6 (C); anal. calcd. (%)
for C42H57O6PS: C 69.97, H 7.97, S 4.45; found: C 69.99, H
8.01, S 4.47.
d=142.5 (bs); H NMR (400 MHz, C6D6): d=1.09 (s, 3H,
1
CH3), 1.23 (s, 9H, CH3, t-Bu), 1.27 (s, 9H, CH3, t-Bu), 1.39
(s, 3H, CH3), 1.50 (s, 9H, CH3, t-Bu), 1.52 (s, 9H, CH3, t-
3
3
Bu), 3.39 (dd, 1H, H-3, J3,2 =4 Hz, J3,4 =10 Hz), 3.87 (m,
1H, H-5’), 4.03 (m, 1H, H-4), 4.19 (m, 1H, H-2), 4.31 (m,
3
1H, H-5), 5.71 (d, 1H, H-1, J1,2 =3.6 Hz), 6.80–7.60 (m, 9H,
CH=); 13C NMR (400 MHz, C6D6): d=26.2 (CH3), 26.6
(CH3), 30.7 (CH3, t-Bu), 30.9 (CH3, t-Bu), 31.2 (CH3, t-Bu),
31.1 (CH3, t-Bu), 34.3 (C, t-Bu), 35.3 (C, t-Bu), 49.6 (C-3),
61.9 (d, C-5, JC,P =8 Hz), 80.7 (C-4), 81.1 (C-2), 104.4 (C-1),
111.7 (CMe2), 123.9 (d, CH=, JC,P =7.6 Hz), 125.3 (CH=),
126.4 (CH=), 126.6 (d, CH=, JC,P =13 Hz), 128.1 (CH=),
128.8 (CH=), 128.9 (CH=), 130.8 (CH=), 133.2 (C), 133.5
(C), 135.1 (C), 140.3 (C), 146.2 (C), 146.5 (C); anal. calcd.
(%) for C42H57O6PS: C 69.97, H 7.97, S 4.45; found: C 70.01,
H 8.02, S 4.43.
L12e: Yield: 385 mg (58%). 31P NMR (400 MHz, C6D6):
d=128.7 (s); 1H NMR (400 MHz, C6D6): d=0.95 (s, 3H,
CH3), 1.36 (s, 3H, CH3), 1.57 (s, 9H, CH3, t-Bu), 1.58 (s, 9H,
CH3, t-Bu), 1.69 (s, 3H, CH3), 1.78 (s, 3H, CH3), 2.06 (s, 6H,
3
CH3), 3.70 (d, 1H, H-3, J3,4 =4.4 Hz), 3.92 (m, 1H, H-5’),
L15a: Yield: 395 mg (60%). 31P NMR (400 MHz, C6D6):
d=139.6 (s); 1H NMR (400 MHz, C6D6): d=1.12 (s, 3H,
CH3), 1.26 (s, 9H, CH3, t-Bu), 1.27 (s, 9H, CH3, t-Bu), 1.38
(s, 3H, CH3), 1.60 (s, 9H, CH3, t-Bu), 1.62 (s, 9H, CH3, t-
Bu), 1.76 (s, 3H, CH3-S), 2.63 (dd, 1H, H-3, 3J3,2 =4 Hz,
2
4.49 (d, 1H, H-2, J2,1 =3.6 Hz), 4.53 (m, 1H, H-5), 4.77 (m,
3
1H, H-4), 5.75 (d, 1H, H-1, J1,2 =3.6 Hz), 6.80–7.30 (m, 7H,
CH=); 13C NMR (400 MHz, C6D6): d=16.7 (CH3Ar), 17.0
(CH3Ar), 20.6 (CH3Ar), 20.7 (CH3Ar), 26.6 (CH3), 27.1
156
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ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 143 – 160

A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
3
3J3,4 =12 Hz), 3.97 (m, 1H, H-4), 4.06 (m, 1H, H-5’), 4.19
(m, 1H, H-4), 5.51 (d, 1H, H-1, J1,2 =4.0 Hz), 6.80–7.40 (m,
9H, CH=); 13C NMR (400 MHz, C6D6): d=21.0 (CH3Ph),
21.2 (CH3Ph), 21.6 (CH3Ph), 22.5 (CH3Ph), 22.7 (CH3Ph),
22.8 (CH3Ph), 26.7 (CH3), 27.0 (CH3), 35.9 (C-5), 78.0 (d, C-
4, JC,P =5.5 Hz), 78.9 (C-2), 81.0 (d, C-3, JC,P =20.2 Hz),
104.5 (C-1), 112.9 (CMe2), 125.8 (CH=), 126.1 (CH=), 128.4
(CH=), 128.7 (CH=), 128.2 (CH=), 130.2 (CH=), 136.2 (C),
139.4 (C), 141.9 (C), 142.5 (C); anal. calcd. (%) for
C32H39O4PS: C 69.79, H 7.14, S 5.82; found: C 69.82, H 7.18,
S 5.79.
3
(m, 1H, H-2), 4.32 (m, 1H, H-5), 5.65 (d, 1H, H-1, J1,2
=
3.6 Hz), 7.30–7.60 (m, 4H, CH=); 13C NMR (400 MHz,
C6D6): d=14.9 (CH3S), 26.6 (CH3), 26.9 (CH3), 31.5 (CH3, t-
Bu), 31.3 (CH3, t-Bu), 31.4 (CH3, t-Bu), 31.6 (CH3, t-Bu),
34.7 (C, t-Bu), 35.7 (C, t-Bu), 48.6 (C-3), 62.9 (d, C-5, JC,P
=
6.2 Hz), 80.7 (C-4), 82.0 (C-2), 104.7 (C-1), 111.9 (CMe2),
124.4 (CH=), 124.5 (CH=), 127.0 (CH=), 127.2 (CH=), 133.5
(C), 133.6 (C), 133.9 (C), 137.8 (C), 140.6 (C), 140.7 (C),
146.7 (C), 146.9 (C); anal. calcd. (%) for C37H55O6PS: C
67.45, H 8.41, S 4.87; found: C 67.38, H 8.37, S 4.89.
L11i: Yield: 286 mg (56%). 31P NMR (400 MHz, C6D6):
d=117.5 (s); 1H NMR (400 MHz, C6D6): d=1.04 (s, 3H,
CH3), 1.40 (s, 3H, CH3), 2.49 (s, 6H, CH3Ph), 2.57 (dd, 1H,
H-5’, J5’,5 =13.2 Hz, J5’,4 =7.2 Hz), 2.99 (dd, 1H, H-5, J5,5’
13.2 Hz, J5,4 =2.8 Hz), 3.87 (m, 1H, H-3), 4.08 (m, 1H, H-
2
3
2
Typical Procedure for the Preparation of Thioether-
Phosphinite Ligands L1–L15i–k
=
3
3
2), 4.29 (m, 1H, H-4), 5.40 (d, 1H, H-1, J1,2 =4.0 Hz), 7.00–
A solution of chlorodiarylphosphine (1.1 mmol) in THF
(4 mL) was slowly added at 08C to a solution of the corre-
sponding thioether-alcohol (1 mmol) and DMAP (5.7 mg,
0.05 mmol) in pyridine (1 mL). The reaction mixture was
stirred for 90 min at room temperature. Diethyl ether was
then added and the pyridine salts were removed by filtra-
tion. The residue was purified by flash chromatography
(eluent: toluene/NEt3 =100/1) to produce the corresponding
ligand as a colourless oil.
7.70 (m, 13H, CH=); 13C NMR (400 MHz, C6D6): d=26.3
(CH3), 26.4 (CH3), 36.5 (C-5), 77.3 (d, C-4, JC,P =6.2 Hz),
78.4 (d, C-2, JC,P =3.8 Hz), 81.4 (d, C-3, JC,P =19.4 Hz), 103.8
(C-1), 112.4 (CMe2), 128.0 (CH=), 128.1 (CH=), 128.2 (CH=
), 128.3 (CH=), 128.4 (CH=), 128.9 (CH=), 129.5 (CH=),
129.9 (CH=), 130.1 (CH=), 130.6 (CH=), 130.8 (CH=), 133.5
(C), 141.9 (C), 142.1 (C), 142.2 (C), 142.3 (C); anal. calcd.
(%) for C28H31O4PS: C 68.00, H 6.32, S 6.48; found: C 68.02,
H 6.35, S 6.49.
L8i: Yield: 317 mg (68%). 31P NMR (400 MHz, C6D6): d=
L11j: Yield: 203 mg (39%). 31P NMR (400 MHz, C6D6):
d=106.4 (s); 1H NMR (400 MHz, C6D6): d=1.04 (s, 3H,
CH3), 1.35 (s, 3H, CH3), 2.27 (s, 3H, CH3), 2.31 (s, 3H,
1
117.6 (s); H NMR (400 MHz, C6D6): d=1.08 (s, 3H, CH3),
2
3
1.45 (s, 3H, CH3), 2.92 (dd, 1H, H-5’, J5’3,5 =14.0 Hz, J5’,4
=
2
5.2 Hz), 3.28 (dd, 1H, H-5, J5,5’ =14.0 Hz, J5,4 =3.6 Hz), 4.10
2
CH3), 2.46 (s, 6H, CH3), 2.59 (dd, 1H, H-5’, J5’,5 =13.6 Hz,
(m, 1H, H-3), 4.15 (m, 1H, H-2), 4.54 (m, 1H, H-4), 5.43 (d,
3
3
3J5’,4 =7.2 Hz), 2.93 (dd, 1H, H-5, 2J5’,5 =13.6 Hz, J5,4
=
1H, H-1, J1,2 =3.6 Hz), 6.80–7.70 (m, 15H, CH=); 13C NMR
2.8 Hz), 3.83 (m, 1H, H-3), 4.15 (m, 1H, H-2), 4.22 (m, 1H,
(400 MHz, C6D6): d= 26.3 (CH3), 26.5 (CH3), 36.3 (C-5),
77.5 (d, C-4, JC,P =6.1 Hz), 78.3 (d, C-2, JC,P =3.1 Hz), 80.8
(d, C-3, JC,P =18.2 Hz), 103.9 (C-1), 112.5 (CMe2), 125.6
(CH=), 128.0 (CH=), 128.1 (CH=), 128.3 (CH=), 128.4
(CH=), 128.7 (CH=), 128.9 (CH=), 129.2 (CH=), 129.6
H-4), 5.42 (d, 1H, H-1, 3J1,2 =4.0 Hz), 6.80–7.70 (m, 11H,
CH=); 13C NMR (400 MHz, C6D6) d: 20.2 (d, CH3-Ar, JC,P
=
3.2 Hz), 20.4 (d, CH3-Ar, JC,P =4.0 Hz), 21.9 (CH3-Ar), 26.3
(CH3), 26.5 (CH3), 36.7 (C-5), 77.4 (d, C-3, JC,P =6.2 Hz),
78.6 (d, C-4, JC,P =4.8 Hz), 81.5 (d, C-2, JC,P =32.6 Hz), 103.7
(C-1), 112.3 (CMe2), 125.8 (CH=), 125.9 (CH=), 126.0 (CH=
), 127.8 (CH=), 129.0 (CH=), 129.7 (d, CH=, JC,P =6.2 Hz),
130.0 (d, CH=, JC,P =4.2 Hz), 130.6 (d, CH=, JC,P =8.0 Hz),
135.5 (C), 138.7 (C), 138.8 (C), 140.4 (C), 140.7 (C), 140.9
(C); anal. calcd. (%) for C30H35O4PS: C 68.94, H 6.75, S
6.14; found: C 68.93, H 6.74, S 6.12.
(CH=), 130.0 (CH=), 130.2ACTHNURGTNE(UNG CH=), 130.9 (CH=), 131.1 (CH=
), 137.2 (C), 141.9 (C), 142.0 (C), 142.1 (C), 142.2 (C); anal.
calcd. (%) for C26H27O4PS: C 66.94, H 5.83, S 6.87; found: C
66.91, H 5.82, S 6.89.
L8j: Yield: 192 mg (38%). 31P NMR (400 MHz, C6D6):
d=105.6 (s); 1H NMR (400 MHz, C6D6): d=0.99 (s, 3H,
CH3), 1.33 (s, 3H, CH3), 2.26 (s, 3H, CH3), 2.34 (s, 3H,
L11k: Yield: 52 mg (9%). 31P NMR (400 MHz, C6D6): d=
124.3 (s); H NMR (400 MHz, C6D6): d=1.19 (s, 3H, CH3),
1.46 (s, 3H, CH3), 2.19 (s, 3H, CH3), 2.21 (s, 3H, CH3), 2.23
(s, 3H, CH3), 2.43 (s, 3H, CH3), 2.51 (s, 3H, CH3), 2.54 (s,
2
3
CH3), 2.83 (dd, 1H, H-5’, J5’,5 =13.6 Hz, J5’,4 =5.2 Hz), 3.19
1
2
3
(dd, 1H, H-5, J5’,5 =13.6 Hz, J5,4 =2.0 Hz), 4.11 (m, 1H, H-
2), 4.17 (m, 1H, H-3), 4.39 (m, 1H, H-4), 5.34 (d, 1H, H-1,
3J1,2 =3.6 Hz), 6.80–7.70 (m, 13H, CH=); 13C NMR
(400 MHz, C6D6): d=20.1 (d, CH3-Ar, JC,P =4.2 Hz), 20.4 (d,
CH3-Ar, JC,P =5.2 Hz), 26.2 (CH3), 26.6 (CH3), 35.1 (C-5),
77.4 (d, C-4, JC,P =6.1 Hz), 78.4 (d, C-3, JC,P =3.8 Hz), 80.7
(C-2), 103.9 (C-1), 112.4 (CMe2), 125.7 (CH=), 126.0 (CH=),
128.1 (CH=), 128.9 (CH=), 129.1 (CH=), 129.3 (CH=), 129.9
(d, CH=, JC,P =4.0 Hz), 130.1 (d, CH=, JC,P =4.2 Hz), 130.6
(d, CH=, JC,P =7.2 Hz), 131.2 (d, CH=, JC,P =6.4 Hz), 135.0
(C), 139.2 (C), 139.4 (C), 141.6 (C); anal. calcd. (%) for
C28H31O4PS: C 68.00, H 6.32, S 6.48; found: C 67.95, H 6.29,
S 6.41.
2
3
9H, CH3), 2.89 (dd, 1H, H-5’, J5’,5 =13.2 Hz, J5’,4 =6.4 Hz),
3.31 (dd, 1H, H-5, 2J5’,5 =13.2 Hz, 3J5,4 =2.0 Hz), 4.11 (m,
1H, H-3), 4.33 (m, 1H, H-2), 4.48 (m, 1H, H-4), 5.47 (d,
1H, H-1, J1,2 =4.0 Hz), 6.80–7.40 (m, 7H, CH=); 13C NMR
3
(400 MHz, C6D6): d=21.0 (CH3Ph), 21.2 (CH3Ph), 21.4
(CH3Ph), 21.6 (CH3Ph), 22.3 (CH3Ph), 22.5 (CH3Ph), 22.7
(CH3Ph), 22.8 (CH3Ph), 26.4 (CH3), 26.8 (CH3), 36.4 (C-5),
77.4 (d, C-4, JC,P =4.4 Hz), 79.1 (C-2), 80.6 (d, C-3, JC,P
16.8 Hz), 104.6(C-1), 112.7 (CMe2), 125.7 (CH=), 126.0
=
AHCTUNGTRENNUNG
(CH=), 128.4 (CH=), 128.2 (CH=), 130.2 (CH=), 136.2 (C),
139.4 (C), 140.6 (C), 141.9 (C), 142.5 (C); anal. calcd. (%)
for C34H34O4PS: C 70.56, H 7.49, S 5.54; found: C 70.57, H
7.51, S 5.49.
L8k: Yield: 66 mg (11%). 31P NMR (400 MHz, C6D6): d=
1
124.2 (s); H NMR (400 MHz, C6D6): d=1.17 (s, 3H, CH3),
1.52 (s, 3H, CH3), 2.17 (s, 3H, CH3), 2.18 (s, 3H, CH3), 2.23
L12i: Yield: 340 mg (73%). 31P NMR (400 MHz, C6D6):
d=117.3 (s); 1H NMR (400 MHz, C6D6): d=0.93 (s, 3H,
CH3), 1.30 (s, 3H, CH3), 2.07 (s, 3H, CH3-S), 3.64 (d, 1H,
2
(s, 3H, CH3), 2.54 (s, 9H, CH3), 2.94 (dd, 1H, H-5’, J5’,5
=
14.0 Hz, 3J5’,4 =6.0 Hz), 3.35 (dd, 1H, H-5, 2J5’,5 =14.0 Hz,
3J5,4 =2.4 Hz), 4.09 (m, 1H, H-3), 4.31 (m, 1H, H-2), 4.55
Adv. Synth. Catal. 2013, 355, 143 – 160
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
157

Mercedes Coll et al.
FULL PAPERS
3
H-3, J3,4 =4.0 Hz), 4.25 (m, 1H, H-5’), 4.37 (m, 1H, H-5),
J
C,P =13.0 Hz), 84.2 (d, C-2, JC,P =6.1 Hz), 104.9 (C-1), 110.6
3
4.49 (d, 1H, H-2, J1,2 =4.0 Hz), 4.84 (m, 1H, H-4), 5.81 (d,
(CMe2), 125.3 (CH=), 128.1 (CH=), 128.3 (CH=), 128.4
(CH=), 128.7 (CH=), 128.8 (CH=), 128.9 (CH=), 130.0
(CH=), 133.0 (CH=), 133.2 (CH=), 133.7 (CH=), 133.9
(CH=), 136.2 (d, C, JC,P =11.5 Hz), 136.6 (C), 136.7 (d, C,
1H, H-1, J1,2 =4.0 Hz), 6.90–7.60 (m, 15H, CH=); 13C NMR
3
(400 MHz, C6D6): d=25.9 (CH3), 26.5 (CH3), 53.5 (C-3),
69.2 (d, C-5, JC,P =20.1 Hz), 78.6 (d, C-4, JC,P =8.5 Hz), 85.6
(C-2), 105.2 (C-1), 111.5 (CMe2), 126.3 (CH=), 128.1 (CH=),
128.2 (CH=), 128.3 (CH=), 128.9 (CH=), 129.0 (CH=), 129.1
(CH=), 129.2 (CH=), 129.7 (CH=), 130.4 (CH=), 130.5
(CH=), 130.6 (CH=), 130.7 (CH=), 134.6 (C), 137.4 (C),
142.0 (C), 142.1 (C), 142.2 (C), 142.3 (C); anal. calcd. (%)
for C26H27O4PS: C 66.94, H 5.83, S 6.87; found: C 66.88, H
5.79, S 6.86.
J
C,P =11.4 Hz); anal. calcd. (%) for C26H27O3PS: C 69.31, H
6.04, S 7.12; found: C 69.35, H 6.07, S 7.09.
L7l: Yield: 258 mg (54%). 31P NMR (400 MHz, C6D6): d=
1
À27.5 (s); H NMR (400 MHz, C6D6): d=0.95 (s, 3H, CH3),
1.41 (s, 3H, CH3), 2.58 (s, 6H, CH3Ph), 3.07 (d, 1H, H-3,
3J3,4 =4.8 Hz), 3.11 (m, 1H, H-5’), 3.23 (dd, 1H, H-5, J5,5’
=
2
3
13.6 Hz, J5,4 =8.8 Hz), 4.59 (m, 1H, H-2), 4.74 (m, 1H, H-
4), 5.27 (d, 1H, H-1, 3J1,2 =3.6 Hz), 6.90–7.50 (m, 11H,
CH=); 13C NMR (400 MHz, C6D6): d=21.9 (CH3Ph), 22.4
(CH3Ph), 25.8 (CH3), 26.7 (CH3), 37.3 (d, C-5, JC,P
18.5 Hz), 46.1 (d, C-3, JC,P =22.8 Hz), 78.4 (d, C-4, JC,P
26.4 Hz), 84.4 (d, C-2, JC,P =13.1 Hz), 105.0 (C-1), 110.4
(CMe2), 125.2 (CH=), 127.4 (CH=), 127.7 (CH=), 128.3
(CH=), 128.6 (CH=), 128.8 (CH=), 128.9 (CH=), 132.9
(CH=), 133.1 (CH=), 133.6 (CH=), 133.8 (CH=), 134 (CH=),
L12j: Yield: 232 mg (47%). 31P NMR (400 MHz, C6D6):
d=106.4 (s). 1H NMR (400 MHz, C6D6): d=0.92 (s, 3H,
CH3), 1.30 (s, 3H, CH3), 2.34 (s, 3H, CH3), 2.39 (s, 3H,
CH3), 3.62 (d, 1H, H-3, J3,4 =4.0 Hz), 4.26 (m, 1H, H-5’),
4.35 (m, 1H, H-5), 4.64 (d, 1H, H-2, J2,1 =3.2 Hz), 4.84 (m,
=
=
3
2
1H, H-4), 5.80 (d, 1H, H-1, 3J1,2 =3.2 Hz), 6.80–7.70 (m,
13H, CH=); 13C NMR (400 MHz, C6D6): d=20.8 (d, CH3-
Ar, JC,P =8.4 Hz), 21.1 (d, CH3-Ar, JC,P =8.4 Hz), 26.6 (CH3),
27.1 (CH3), 54.0 (C-3), 70.2 (d, C-5, JC,P =22.1 Hz), 79.2 (d,
C-4, JC,P =8.2 Hz), 86.1 (C-2), 105.8 (C-1), 112.2 (CMe2),
126.5 (CH=), 126.9 (CH=), 129.6 (CH=), 129.9 (CH=), 130.1
(CH=), 130.3 (CH=), 130.5 (d, CH=, JC,P =4.0 Hz), 130.8 (d,
CH=, JC,P =3.6 Hz), 131.1 (d, CH=, JC,P =6.2 Hz), 131.2 (d,
CH=, JC,P =6.4 Hz), 135.1 (C), 139.2 (C), 139.4 (C), 141.6
(C), 141.7 (C); anal. calcd. (%) for C28H31O4PS: C 68.00, H
6.32, S 6.48; found: C 67.97, H 6.31, S 6.45.
136.8 (d, C, JC,P =11.5 Hz), 137.4 (C), 143.4 (d, C, JC,P
11.8 Hz); anal. calcd. (%) for C28H31O3PS: C 70.27, H 6.53,
S 6.70; found: C 70.31, H 6.56, S 6.68.
=
Typical Procedure for the Preparation of
[IrACTHNURTGNEUGN(cod)(L)]BArF (L=L1–L15a–l)
The corresponding ligand (0.037 mmol) was dissolved in
CH2Cl2 (2 mL) and [Ir(m-Cl)(cod)]2 (12.5 mg, 0.0185 mmol)
L14i: Yield: 294 mg (63%). 31P NMR (400 MHz, C6D6):
d=117.7 (s); 1H NMR (400 MHz, C6D6): d=1.12 (s, 3H,
CH3), 1.42 (s, 3H, CH3), 3.49 (m, 1H, H-3), 3.97 (m, 1H, H-
5’), 4.05 (m, 1H, H-5), 4.11 (m, 1H, H-2), 4.22 (m, 1H, H-
A
ACHTUNGTRENNUNG
was added. The reaction mixture was refluxed at 508C for
1 hour. After 5 min at room temperature, NaBArF (38.6 mg,
0.041 mmol) and water (2 mL) were added and the reaction
mixture was stirred vigorously for 30 min at room tempera-
ture. The phases were separated and the aqueous phase was
extracted twice with CH2Cl2. The combined organic phases
were dried with MgSO4, filtered through a plug of celite and
the solvent was evaporated to give the product as red-
orange solids.
3
4), 5.39 (d, 1H, H-1, J1,2 =4.0 Hz), 6.90–7.60 (m, 15H, CH=
); 13C NMR (400 MHz, C6D6): d=26.9 (CH3), 27.3 (CH3),
50.8 (C-3), 68.4 (d, C-5, JC,P =19.0 Hz), 82.0 (C-2), 82.7 (d,
C-4, JC,P =6.1 Hz), 105.0 (C-1), 112.4 (CMe2), 127.4 (CH=),
128.9 (CH=), 129.6 (CH=), 129.7 (CH=), 129.9 (CH=), 130.7
(CH=), 130.9 (CH=), 131.6 (CH=), 131.8 (CH=), 132.0
(CH=), 136.2 (C), 143.2 (C), 143.4 (C); anal. calcd. (%) for
C26H27O4PS: C 66.94, H 5.83, S 6.87; found: C 66.92, H 5.80,
S 6.846.
Typical Procedure for the Hydrogenation of Olefins
The alkene (1 mmol) and Ir complex (2 mol%) were dis-
solved in CH2Cl2 (2 mL) in a high-pressure autoclave. The
autoclave was purged four times with hydrogen. Then, it
was pressurized at the desired pressure. After the desired re-
action time, the autoclave was depressurised and the solvent
evaporated off. The residue was dissolved in Et2O (1.5 mL)
and filtered through a short plug of celite.
Typical Procedure for the Preparation of Thioether-
Phosphine ligands L1–L15l
A tetrahydrofuran solution of potassium diphenylphosphine
(1.1 mmol, 2.2 mL of a 0.5m solution) was slowly added at
À788C to a solution of the corresponding thioether-triflate
(1 mmol) in THF (2 mL). The reaction mixture was stirred
during 30 min at room temperature. THF was evaporated
and the reaction was diluted with toluene (3 mL). The in-
soluble salts were removed by filtration. The filtrated was
purified by flash chromatography (eluent: toluene) in silica
to produce the corresponding ligand as a white solid.
1
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,[5e] S2,[29a] S3/S4,[5e] S5,[29a] S6/S7,[5e] S8/S9,[15a] S10,[5e]
S11/S12,[5m] S13/S14,[5e] S15,[29b] S16/S17,[17a] S18/S19,[5e] S20/
S21,[18a] S22/S23,[29c] S24,[5h] S25,[5e] S26,[29c] S27–S31,[5e] S32[29d]
and S33[5e] were determined using the conditions previously
described.
L1l: Yield: 216 mg (48%). 31P NMR (400 MHz, C6D6): d=
1
À27.2 (s); H NMR (400 MHz, C6D6): d=0.91 (s, 3H, CH3),
3
1.35 (s, 3H, CH3), 3.21 (d, 1H, H-3, J3,4 =4.8 Hz), 3.33 (m,
Typical Procedure for Catalyst Recycling
2
3
1H, H-5’), 3.52 (dd, 1H, H-5, J5,5’ =13.2 Hz, J5,4 =7.2 Hz),
4.61 (m, 1H, H-2), 4.91 (m, 1H, H-4), 5.25 (d, 1H, H-1,
3J1,2 =4.0 Hz), 7.00–7.60 (m, 15H, CH=); 13C NMR
(400 MHz, C6D6): d=25.9 (CH3), 26.5 (CH3), 35.8 (d, C-5,
After each catalytic run, the autoclave was depressurised.
The colourless propylene carbonate solution was then ex-
tracted with dry/deoxygenated hexane under an argon at-
mosphere in order to remove the substrate and the hydro-
J
C,P =21.3 Hz), 45.7 (d, C-3, JC,P =21.4 Hz), 78.3 (d, C-4,
158
asc.wiley-vch.de
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 143 – 160

A Modular Furanoside Thioether-Phosphite/Phosphinite/Phosphine Ligand Library
genated product. After the extractions, the corresponding
amount of substrate was then added for starting a new run.
Soc. 2009, 131, 13236; k) A. Wang, R. P. A. Fraga, E.
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W. Chen, X.-L. Hou, Adv. Synth. Catal. 2010, 352, 103;
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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.
[6] M. Coll, O. Pꢀmies, M. Diꢁguez, Chem. Commun.
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[7] Soon after Pfaltzꢃs group reported the use of proline-
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