Monohydride-Dichloro Rhodium(III) Complexes with Chiral Diphosphine Ligands as Catalysts for Asymmetric Hydrogenation of Olefinic Substrates

Article abstract of DOI:10.1002/chem.202000542

We report full details of the synthesis and characterization of monohydride-dichloro rhodium(III) complexes bearing chiral diphosphine ligands, such as (S)-BINAP, (S)-DM-SEGPHOS, and (S)-DTBM-SEGPHOS, producing cationic triply chloride bridged dinuclear rhodium(III) complexes (1 a: (S)-BINAP; 1 b: (S)-DM-SEGPHOS) and a neutral mononuclear monohydride-dichloro rhodium(III) complex (1 c: (S)-DTBM-SEGPHOS) in high yield and high purity. Their solid state structure and solution behavior were determined by crystallographic studies as well as full spectral data, including DOSY NMR spectroscopy. Among these three complexes, 1 c has a rigid pocket surrounded by two chloride atoms bound to the rhodium atom together with one tBu group of (S)-DTBM-SEGPHOS for fitting to simple olefins without any coordinating functional groups. Complex 1 c exhibited superior catalytic activity and enantioselectivity for asymmetric hydrogenation of exo-olefins and olefinic substrates. The catalytic activity of 1 c was compared with that of well-demonstrated dihydride species derived in situ from rhodium(I) precursors such as [Rh(cod)Cl]₂ and [Rh(cod)₂]⁺[BF₄]^? upon mixing with (S)-DTBM-SEGPHOS under dihydrogen.

Full text of DOI:10.1002/chem.202000542

A Journal of
Accepted Article
Title: Monohydride-dichloro Rhodium(III) Complexes with Chiral
Diphosphine Ligands as Catalysts for Asymmetric Hydrogenation
of Olefinic Substrates
Authors: Kosuke Higashida, Fabian Brüning, Nagataka Tsujimoto,
Kenya Higashihara, Haruki Nagae, Antonio Togni, and
Kazushi Mashima
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.202000542
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Chemistry - A European Journal
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RESEARCH ARTICLE
Monohydride-dichloro Rhodium(III) Complexes with Chiral
Diphosphine Ligands as Catalysts for Asymmetric Hydrogenation
of Olefinic Substrates
[
a]
[b]
[a]
[a]
[a]
Kosuke Higashida, Fabian Brüning, Nagataka Tsujimoto, Kenya Higashihara, Haruki Nagae,
[
b]
[a]
Antonio Togni,* and Kazushi Mashima*
Abstract: We report full details of the synthesis and characterization
of monohydride-dichloro rhodium(III) complexes bearing chiral
diphosphine ligands, such as (S)-BINAP, (S)-DM-SEGPHOS, and
BIPOP ligand,[7] however, these chiral rhodium(I) catalyst
systems do not work well for the asymmetric hydrogenation of
non-chelating olefin substrates.[8]
(
S)-DTBM-SEGPHOS, producing cationic triply-chloride bridged
dinuclear rhodium(III) complexes (1a: (S)-BINAP; 1b: (S)-DM-
SEGPHOS) and neutral mononuclear monohydride-dichloro
In contrast to the rhodium system, chiral cationic iridium
complexes serve as catalysts for the asymmetric hydrogenation
of unfunctionalized olefins:[9]-[14] in 1998, Pfaltz et al.
a
rhodium(III) complex (1c: (S)-DTBM-SEGPHOS) in high yield and
high purity. Their solid state structure and solution behavior were
determined by crystallographic studies as well as full spectral data,
including DOSY NMR spectroscopy. Among these three complexes,
demonstrated that cationic iridium complexes bearing
phosphanodihydrooxazole ligand (P^N ligand, Figure 1a) were
a
efficient catalysts for the asymmetric hydrogenation of (E)--
methylstilbene derivatives.[
9a]
Later, not only the Pfaltz group,
[9]
1
c has a rigid pocket surrounded by two chloride atoms bound to the
but also several other groups, independently reported asymmetric
hydrogenation of unfunctionalized olefins, such as cyclic olefins
and exo-olefins, using various chiral P^N ligands.[10],[11] Iridium
cationic complexes with bidentate carbene oxazoline ligands[12],[13]
and a thioether-phosphite ligands[14] also showed high catalytic
activity and enantioselectivity. Recently, cobalt-based catalyst
systems were reported:[15],[16] Chirik et al. found that cobalt
t
rhodium atom together with one Bu group of (S)-DTBM-SEGPHOS
for fitting to simple olefins without any coordinating functional groups.
Complex 1c exhibited superior catalytic activity and enantioselectivity
for asymmetric hydrogenation of exo-olefins and olefinic substrates.
The catalytic activity of 1c was compared with that of well-
demonstrated dihydride species derived in situ from rhodium(I)
+
–
precursors such as [Rh(cod)Cl]
2
and [Rh(cod)
2
] BF
4
upon mixing with
1
complexes bearing a tridentate C -symmetric bis(imino)pyridine
(S)-DTBM-SEGPHOS under dihydrogen.
ligand (Figure 1b) acted as superior catalyst for the asymmetric
hydrogenation of exo-olefins[
15a]
as well as cyclic olefins.
[15c]
Introduction
Asymmetric hydrogenation by chiral transition metal complexes is
one of the most important and practically applicable reactions for
atom-economical and environmentally benign synthesis of chiral
[
1],[2]
organic compounds.
Intensive research has focused on the
rational design and synthesis of chiral chelating ligands with
different chiral skeletons for adjusting targeted asymmetric
hydrogenations in combination with standard metal precursors
whereas little attention has been paid to metal catalyst precursors.
Figure 1. Examples of (a) iridium and (b) cobalt catalysts for asymmetric
hydrogenation of unfunctionalized olefins.
In fact, asymmetric hydrogenation of functionalized olefins such
as -unsaturated acids,[3] enamides,[4] enol ester,[5] and so on[6]
In 2016, we have reported that rhodium(III) complexes with
commercially available chiral diphosphine ligands (Figure 2), 1a
(S)-BINAP), 1b ((S)-DM-SEGPHOS), and 1c ((S)-DTBM-
SEGPHOS), served as highly enantioselective catalysts for
asymmetric hydrogenation of both unfunctionalized olefins such
as -methylstilbene and functionalized olefins e.g. allylic alcohols.
In addition, we determined the bifacial dinuclear structure of
has been catalyzed by chiral rhodium complexes derived in situ
(
by mixing rhodium(I) precursors such as [Rh(diene)Cl]
2
and
] X with suitable chiral chelating diphosphine ligands.
Other than the recently reported rhodium(I) complex with a MeO-
+
-
[
Rh(diene)
2
[
[
a]
b]
Dr. K. Higashida, Mr. N. Tsujimoto, Mr. K. Higashihara, Dr. H.
Nagae, Prof. Dr. K. Mashima
Department of Chemistry
Graduate School of Engineering Science, Osaka University
Toyonaka, Osaka 560-8531, Japan
E-mail: mashima@chem.es.osaka-u.ac.jp
Mr. F. Brüning, Prof. Dr. A. Togni
Department of Chemistry and Applied Biosciences
Swiss Federal Institute of Technology
Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland
E-mail: antonio.togni@inorg.chem.ethz.ch
cationic triply-chloride bridged complex 1a by X-ray single crystal
analysis.[17a] Herein, we report full details of the preparation and
characterization of cationic dinuclear rhodium(III) complex 1b as
well as a neutral mononuclear monohydride-dichloro rhodium(III)
complex 1c which has been assigned as cationic dinuclear
complex in previous report.[17a] The solid and solution structures
of 1c were revealed by crystallographic studies and DOSY NMR
spectroscopy, respectively. We demonstrated that complex 1c
exhibited a superior catalytic activity and enantioselectivity for the
asymmetric hydrogenation of simple olefins and some related
olefinic substrates in comparison with those of standard rhodium
Supporting information for this article is given via a link at the end of
the document
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Chemistry - A European Journal
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RESEARCH ARTICLE
Cl) Rh(cod)].[
19a]
They clarified that the second replacement of
catalyst systems, i.e., a dihydridemonochloro rhodium(III) catalyst
and a cationic dihydride rhodium(III) catalyst generated in situ by
2
COD of [(diphosphine)Rh(-Cl)
replacement of COD of [Rh(cod)Cl]
2
Rh(cod)] was slower than the first
respectively treating rhodium(I) precursors, [Rh(cod)Cl]
2
and
2
, presumably due to the
+
-
[
Rh(diene) ] X , with (S)-DTBM-SEGPHOS under dihydrogen gas.
2
extended trans-effect in a double square planer geometry
connected by two chloride atoms. Furthermore, they reported that
a
reaction of [Rh(cod)Cl]
2
with sterically hindered DTBM-
Rh(cod)] as a
SEGPHOS afforded [(DTBM-segphos)Rh(-Cl)
2
single product, and the second replacement of COD did not
proceed.[19b] Accordingly, the successful preparation of 1a—c in
a highly pure form was attributed to avoiding the extended trans-
8
effect of dinuclear rhodium(I) d species by generating octahedral
Figure 2. Rhodium(III) monohydride complexes 1a—c as the catalyst for
asymmetric hydrogenation of simple olefins.
6
rhodium(III) d species, whose COD was labile.
Schematic structures of these three complexes are shown in
Scheme 1, and selected bond parameters are summarized in
Table 1. Complexes 1a and 1b have a cationic triply-chloride
bridged bifacial dinuclear rhodium(III) skeleton with different
stereochemistry relatively to the hydride position on each rhodium
atom, i.e., syn for 1a and anti for 1b, although the outer facial
geometry of two phosphorous atoms and one hydrogen atom in
each rhodium atom of 1b is highly twisted compared with that for
1a owing to the steric bulkiness of (S)-DM-SEGPHOS. The trans
effect of the hydrogen atom significantly elongates the bond
distance of Rh—Cl1* (2.5736(10) Å) and its operation-correlated
Rh*—Cl1 for 1b, and the bond distances of Rh1—Cl3 (2.5742(18)
Å) and Rh2—Cl3 (2.5699(18) Å) for 1a. Such a bifacial dinuclear
geometry has one hydride ligand on the rhodium atom at the cis-
Results and Discussion
Preparation
Rhodium(III) Complexes 1a, 1b, and 1c
We previously reported the syntheses of 1a—c by adding ethereal
HCl to an in situ mixture of [Rh(cod)Cl] (COD 1,5-
and
Characterization
of
Monohydride
2
=
cyclooctadiene) with two equivalents of the corresponding chiral
diphosphine ligands, and confirmed the dinuclear structure of 1a
crystallographically.[17a] A similar dinuclear complex 1b and a
mononuclear complex 1c were prepared by the same procedure
of 1a (Scheme 1a), and the structures of complexes 1b and 1c
were determined by single crystal X-ray analyses (Scheme 1b
and 1c, vide infra). Noteworthy was that the addition of ethereal
HCl was essentially required to isolate these rhodium(III)
complexes in high yield with high purity.[18] The reaction of
1
position in relation to two phosphine atoms, consistent with the H
NMR and 31P{ H} NMR spectra of 1a and 1b. In the H NMR
spectra, hydride signals were observed as doublet of triplets at -
15.9 ppm (1JRh-H = 22.5 Hz and 2JP-H = 15.8 Hz) for 1a and at -16.1
ppm (1JRh-H = 21.8 Hz and 2JP-H = 16.1 Hz), respectively, for 1b.
In the 31P{ H} NMR spectra, one dd signal and one ddd signal
were observed at 48.6 (1JRh-P = 137 Hz, 2JP-P = 27 Hz) and 36.1
ppm (1JRh-P = 134 Hz, 2JP-P = 26 Hz, 2JP-H = 3 Hz), respectively, for
1a, and two ddd signals were detected at 48.3 (1JRh-P = 135 Hz,
2JP-P = 26 Hz, and 2JP-H = 8 Hz) and 41.1 ppm (1JRh-P = 136 Hz,
2JP-P = 26 Hz, and 2JP-H = 12 Hz) for 1b.[20] Accordingly, these two
complexes existed in solution as each pure single isomer.
1
1
[
Rh(cod)Cl]
at room temperature for 7 minutes afforded a mixture of [{(S)-DM-
segphos}Rh(-Cl) Rh(cod)] and [Rh(-Cl) {(S)-DM-segphos}] in
2 2 2
with two equivalents of (S)-DM-SEGPHOS in CD Cl
1
2
2
2
the ratio of 3:1, and more than 1 hour was required to complete
the ligand exchange reaction. Our observation was consistent
with the reports by Heller et al. that the ligand-exchange reaction
of [Rh(cod)Cl]
BINAP, SEGPHOS, DM-SEGPHOS, and DIFLUORPHOS,
proceeded in a stepwise manner to give [Rh(diphosphine)Cl]
through a mixed ligated dinuclear complex [(diphosphine)Rh(-
2
and two equivalents of diphosphines, such as
2
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RESEARCH ARTICLE
Scheme 1. (a) Preparation of rhodium(III) monohydride complexes 1a—c. Molecular structures and Top views of cationic dinuclear complexes 1b (b) and 1c (c).
A solvent molecule and all hydrogen atoms on (S)-DM-SEGPHOS and (S)-DTBM-SEGPHOS are omitted for clarity. Position of hydride atom is located based on
calculation.
The increased steric congestion of (S)-DTBM-SEGPHOS
compared with (S)-BINAP and (S)-DM-SEGPHOS makes 1c
mononuclear, where the rhodium atom adopts a highly distorted
square-pyramidal geometry with one phosphorus atom, two
chloride atoms, and one hydrogen atom as four corners of the
square and the other phosphine atom at the apical position. The
bond distances of Rh—Cl1 (2.3872(12) and Rh—Cl2 (2.3858(13)
Å) in 1c are clearly shorter than these found for 1a (2.42—2.57 Å)
signal was observed as double doublets of doublets at -16.5 ppm
( JRh-H = 20.0 Hz, 2JP-H = 12.1 Hz, and 2JP-H = 6.8 Hz), and, in its
1
3
1
1
P{ H} NMR spectrum, two phosphorous nuclei were observed
as dd signal at 62.5 ( JRh-P = 138 Hz and 2JP-P = 26 Hz) and ddd
signal at 32.6 ppm ( JRh-P = 130 Hz, 2JP-P = 26 Hz, and 2JP-H = 5
Hz),[20],[21] suggesting that the geometry around the rhodium
center of 1c was rigidly fixed with keeping a mononuclear five
coordinated structure that is responsible for the high
enantioselectivity of the simple olefin hydrogenation (vide infra).
1
1
1
and 1b (2.44—2.57 Å). In the H NMR spectrum of 1c, a hydride
Table 1. Selected Distances and Angles for 1a,[17a] 1b and 1c.
1a
1b
1c
Distances (Å)
Rh—Cl1
Rh1—Cl1
Rh1—Cl2
Rh1—Cl3
Rh1—P1
Rh1—P2
2.4509(19)
2.4489(18)
2.5742(18)
2.273(2)
Rh2—Cl1
Rh2—Cl2
Rh2—Cl3
Rh2—P3
Rh2—P4
2.4242(18)
2.4468(19)
2.5699(18)
2.2597(19)
2.277(2)
2.4408(9)
2.4436(9)
2.5736(10)
2.2576(9)
2.2658(9)
Rh—Cl1
Rh—Cl2
Rh—P1
Rh—P2
2.3872(12)
2.3858(13)
2.2467(11)
2.1846(11)
Rh—Cl2
Rh—Cl1*
Rh—P1
Rh—P2
2.268(2)
Angles (deg)
P1—Rh1—P2
P1—Rh1—Cl1
P2—Rh1—Cl2
Cl1—Rh1—Cl2
P1—Rh1—Cl2
P2—Rh1—Cl1
92.27(8)
91.75(7)
95.19(7)
80.50(6)
167.68(7)
175.48(7)
P3—Rh1—P4
P3—Rh2—Cl1
P4—Rh2—Cl2
Cl1—Rh2—Cl2
P3—Rh2—Cl2
P4—Rh2—Cl1
91.00(7)
95.43(7)
92.69(7)
81.08(6)
176.26(7)
166.60(7)
P1—Rh—P2
P1—Rh—Cl1
P2—Rh—Cl2
Cl1—Rh—Cl2
P1—Rh—Cl2
P2—Rh—Cl1
94.02(3)
90.62(3)
92.62(3)
82.87(3)
169.49(3)
175.31(3)
P1—Rh—P2
P1—Rh—Cl1
P2—Rh—Cl2
Cl1—Rh—Cl2
P1—Rh—Cl2
P2—Rh—Cl1
H—Rh—Cl1
95.07(4)
95.55(4)
90.62(4)
92.17(5)
163.23(5)
132.43(5)
146(2)
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To examine whether complexes 1a—c exist as mono- or
dinuclear species in solution, the diffusion coefficients of all
complexes and diphosphine ligands were determined by DOSY
NMR spectroscopy. The experimental diffusion coefficients were
additionally normalized using the solvent signal as an internal
reference (Table 2). The normalized coefficients for complexes
map[24] of 1c and those of a cationic rhodium complex, [Rh((S)-
DTBM-segphos)]+:[25] topographic steric map shows steric
bulkiness around the rhodium atom with a warm color. As shown
in Figure 3b, it is visible that the tert-butyl substitution of (S)-
DTBM-SEGPHOS in 1c is the largest sterically hindered group
that blocks one potential approach of the olefinic substrate to the
rhodium-hydride moiety, and two chloride ligands strictly control
the selection of one of the enantio-faces of -methylstilbene,
resulting in high enantioselectivity. In sharp contrast, Figures 3c
and 3d show a space-filling model and a topographic steric map
a and 1b (D1a = 6.09×10- m /s and D1b = 5.98×10 m /s,
10
2
-10
2
1
respectively) are significantly smaller than those of their
corresponding ligands (DBINAP = 8.84×10- m /s and DDM-SEGPHOS
10
2
=
8.42×1010 m /s). In contrast, the normalized coefficients of 1c
2
6.83×10-
10
m /s) and its ligand DTBM-
2
of [Rh{(S)-DTBM-segphos}] , where two tert-butyl substitutions of
+
(
D
DTBM-SEGPHOS
=
SEGPHOS (DDTBM-SEGPHOS = 6.81×10- m /s) are almost identical.
Since diffusion coefficients decrease as the size of a molecule
increases, our results show that 1a and 1b are significantly larger
than their corresponding ligands, whereas 1c shows almost the
same diffusion behavior as DTBM-SEGPHOS and thus has a
similar hydrodynamic volume. Consequently, we conclude that
10
2
(S)-DTBM-SEGPHOS in [Rh{(S)-DTBM-segphos}] become two
+
parallel fences creating two large open sites, leading to low
enantioselectivity.
1
a and 1b do not exist as mononuclear species in solution, in
[
22]
contrast to complex 1c.
This observation is consistent with their
respective mono- and dinuclear structures determined by X-ray
single crystal analysis (vide supra). complementary,
A
quantitative approach by comparison of the estimated molecular
sizes by the Stokes-Einstein relation indicates that the sizes for
1a and 1b are consistent with a dinuclear structure (see SI for
details). These observations demonstrate that the rhodium(III)
complexes 1a—c are maintained as single species in both
solution and solid state without any substrate or hydrogen.
Table 2. Diffusion Coefficients of Chiral Diphosphine Ligands and
Complexes 1a—c.
2
compounds
D
normalised [m /s]
(
(
(
S)-BINAP
8.84×10-10
S)-DM-SEGPHOS
S)-DTBM-SEGPHOS
8.42×10-10
Figure 3. (a) Space-filling model of 1c, (b) Topographic steric map of 1c, and
(c) Space-filling model of cationic complex without hydride, [Rh((S)-DTBM-
segphos)] , (d) Topographic steric map of [Rh((S)-DTBM-segphos)] . The
structure of [Rh((S)-DTBM-segphos)]+ was optimized by using the
B3LYP/def2SVP density-functional theory.
6.81×10-10
+
+
1
1
1
a
b
c
6.09×10-10
5.98×10-10
6.83×10-10
The fitting suitability of -methylstilbene to the catalyst pocket
around a Rh—H bond prompted us to predict that 1c becomes an
efficient catalyst for asymmetric hydrogenation of a non-chelating
Diffusion coefficients of of diphosphine ligands and rhodium complexes were
1
determined by H NMR diffusion experiments of 20 mM solutions in CD
2
Cl
2
at 298 K using a diffusion delay  = 0.50 ms. Normalised values were
calculated according to the formula log Dnorm = log Dref, fix – log Dref, measured
+
olefins, not only (E)--methylstilbene ((E)-2), which is our
[
23]
log Dmeasured
2
using the solvent signal of CDHCl as internal reference.
previous model substrate,[
17a]
but also (E)-1-benzylidene-2,3-
and (Z)-3-benzylidene-2,3-
dihydrobenzofuran (6), which have a similar shape as (E)--
methylstilbene (2). The same optimized conditions were
dihydro-1H-indene
(4)
Asymmetric Hydrogenation of Simple Olefinic Substrates
Mononuclear complex 1c was found to be the best catalyst
among the three complexes for asymmetric hydrogenation of -
employed for the asymmetric hydrogenation experiments as
previously reported. Substrate 4 gave (R)-1-benzyl-2,3-dihydro-
1H-indene ((R)-5) in 96% ee with the same enantio-face
methylstilbene (2a),[17a] whereas a mixture of 1c and NaBPh
, a
and two equivalents of (S)-DTBM-
SEGPHOS as well as a cationic mixture of [Rh(cod) and
]+BF –
4
neutral mixture of [Rh(cod)Cl]
2
selectivity as -methylstilbene (entry 2).
In the case of
2
4
asymmetric hydrogenation of 6 by complex 1c, (R)-3-benzyl-2,3-
dihydrobenzofuran ((-)-7) was obtained in quantitative yield and
excellent enantioselectivity (entry 3). On the other hand, the use
one equivalent of (S)-DTBM-SEGPHOS resulted in lower
enantioselectivities (Table 3, entry 1, vide infra and Table S1).
Figures 3a—d show a space-filling model and topographic steric
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Chemistry - A European Journal
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RESEARCH ARTICLE
of a mixture of (E)-2 and (Z)-2 (22:78) as substrate afforded the
opposite enantiomer (S)-3 in 45% ee.
yield, respectively, with moderate to high enantioselectivities
(entries 8 and 9).
Table 4. Asymmetric Hydrogenation of Cyclic Olefins Catalyzed by Complex 1c.
Table 3. Asymmetric Hydrogenation of Simple Olefins Catalyzed by 1c.
entry starting material
product
time [h] yield [%] ee [%]
entry
1
product
solvent
toluene
temp. [ºC] time [h] yield [%] ee [%]
1[a]
20
18
20
96
95
96
94
100
20
97
95(-)
2
3
>99
>99
(
R)-11a
R = H
2[a]
3[a]
4[a]
5[a]
6[a]
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
80
80
80
80
80
18
18
18
18
18
94
86
96
99(+)
96(+)
99(+)
-
(
+)-11b
Yield was determined by 1H NMR analysis. Ee was determined by HPLC
analysis. [a] Included in our previous report.[17a]
R = para-MeO
(
+)-11c
R = meta-MeO
11d
No
reaction
Next, we conducted the hydrogenation of 1,1-dimethyl-2-
R = ortho-MeO
phenyl-1H-indene (8), indoles
10a—e and 12, 2-
(
+)-11e
96
99(+)
phenylbenzo[b]thiophene 1,1-dioxide (14), and 1,1-dimethyl-2-
phenyl-1H-benzo[b]silole (16), and the results are shown in Table
R = para-CF3
4
. When 1,1-dimethyl-2-phenyl-1H-indene (8) was hydrogenated
by 1c, we obtained 1,1-dimethyl-2-phenyl-2,3-dihydro-1H-indene
(-)-9) in 97% yield with 95% ee (entry 1). Asymmetric
No
reaction
7[a]
1,4-dioxane
80
18
-
(
hydrogenation of 1-(2-phenyl-1H-indol-1-yl)ethan-1-one (10a),
which fits to the rigid pocket of 1c, also proceeded smoothly to
give 1-(2-phenylindolin-1-yl)ethan-1-one (11a) as an (R)-form in
high yield with high enantioselectivity (entry 2). Asymmetric
hydrogenation of N-acetylindole derivatives 10b—e having a
functional group on the Ph group was conducted, and 10b, 10c,
and 10e, which have a methoxy or trifluoromethyl group at the
para- or meta- position, respectively, were hydrogenated under
the optimized conditions to give the corresponding products 11b,
8
9
toluene
toluene
100
100
40
20
99
93
77(-)
93(-)
11c, and 11e in excellent yields and with excellent
enantioselectivities (entries 3, 4, and 6). On the other hand,
indole 11d, having a methoxy group at the ortho-position of the
Ph group did not give the corresponding hydrogenated product
Isolated yield. Ee was determined by HPLC analysis. [a] 2 mol% of 1c was
used.
(
entry 5). When 1-(3-phenyl-1H-indol-1-yl)ethan-1-one (12) was
used as the substrate for the asymmetric hydrogenation by 1c, no
reaction was observed (entry 7). The asymmetric hydrogenation
of heterocyclic compounds such as 2-phenylbenzo[b]thiophene
1,1-dioxide (14) and 1,1-dimethyl-2-phenyl-1H-benzo[b]silole (16)
afforded the corresponding products 15 and 17 in 96% and 93%
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Chemistry - A European Journal
10.1002/chem.202000542
RESEARCH ARTICLE
We further investigated the scope of rhodium(III) complex
recognizes the Re- or Si-face of the substrates without any
1c as the catalyst for asymmetric hydrogenation. The asymmetric
coordination of the functional groups of substrates. Facile
hydrogenation of olefins bearing an ester group at the vicinal
position is unsuitable for rhodium(I) catalysts because of the low
coordinating ability of the conjugated ester group.[26][27] Thus, a
specially designed diphosphine ligand was required in order to
achieve high enantioselectivity.[28] In contrast, our rhodium(III)
complex exhibited high catalytic activity and enantioselectivity
toward asymmetric hydrogenation of ethyl (E)-3-phenylbut-2-
enoate (18) to give the corresponding product (R)-19 in 98% yield
and 90% ee (eq. 1). This selectivity is higher than that obtained
insertion of the coordinated olefin into the Rh—H bond of A gives
a Rh—alkyl complex B reversibly.[32] The resulting Rh—alkyl
complex reacts with dihydrogen through a -bond metathesis
pathway to afford the chiral alkanes along with the regeneration
of 1c. Noteworthy of this mechanism is that oxidative addition to
low valent rhodium(I), giving dihydride species, is excluded.
using both the neutral precursor [Rh(cod)Cl]
of (S)-DTBM-SEGPHOS, or the cationic precursor of
Rh(cod) ]BF and one equivalent of (S)-DTBM-SEGPHOS
Table S2).
2
and two equivalents
[
2
4
(
Reaction Mechanism
Figure 4. Proposed reaction mechanism.
We conducted some controlled experiments to clarify the reaction
mechanism using 1c. When complex 1c was exposed to 1 bar of
hydrogen gas in toluene-d
at 80 °C, 1c remained intact as Conclusion
8
evident from H and 31P{ H} NMR measurements at 80 °C (eq. 2).
The hydride of 1c (2 mol%) without hydrogen gas reversibly
inserted into (Z)-stilbene to give a mixture of (E)- and (Z)-stilbene
in a 35:65 ratio (eq. 3) and isomerized 1-hexene to a mixture of
1
1
We demonstrated that the addition of HCl to the isolated dinuclear
rhodium(I) complex, [Rh(-Cl)(diphosphine)]
2
, and an in situ
mixture of [Rh(cod)Cl] , two equivalents of chiral diphosphine
2
ligands, and an excess amount of ethereal HCl proceeded
smoothly to produce the corresponding cationic triply-chloride
bridged dinuclear rhodium(III) complexes 1a and 1b as well as a
mononuclear rhodium(III) complex 1c in high yield and high purity.
Complex 1c exhibited the best catalyst performance for
asymmetric hydrogenation of various simple olefins, because the
catalyst pocket of the monohydride-dichloro rhodium(III) center is
quite rigid and narrow, even in solution as evident from NMR
(
E)- and (Z)-2-hexene in 85% conversion (eq. 4). In the
isomerization of 21, a first-order rate dependence on the catalyst
concentration was observed over 3-fold range (Figure S18).
These results suggested that a C=C double bond was easily
inserted into Rh—H bond of mononuclear complex 1c. Hence,
the reaction mechanism of asymmetric hydrogenation by 1c
differed from unsaturated mechanism,[29] dihydride mechanism,[30]
and cooperative dinuclear mechanism[31] of asymmetric
hydrogenation catalyzed by conventional rhodium(I) complexes.
measurements, including DOSY.
Therefore, we used a
topographic steric map based on the crystal structure of 1c to
expand the substrate scope and predict the selection of one of
two enantio-faces.
Experimental Section
All reactions and manipulations involving air- and moisture-sensitive
organometallic compounds were operated using the standard Schlenk
techniques under argon gas. Monohydride rhodium(III) complexes were
prepared by the improved method of previous report.[17a] 1,4-Dioxane was
dried and deoxygenated by distillation over sodium benzophenone ketyl
under argon atmosphere. Alternatively, CH
and deoxygenated by using Grubbs column (Glass Counter Solvent
Dispending System, Nikko Hansen & Co, Ltd.).[33] Benzene-d
was
and thoroughly degassed by trap-to-trap distillation
2 2
Cl and toluene were dried
6
According to these results, we suggested a possible reaction
mechanism of asymmetric hydrogenation of olefins by the
mononuclear monohydride-dichloro rhodium(III) complex 1c
distilled over CaH
2
before use. Compounds 4,[
11e]
6,[11e] 8,[34] 14,
[35]
16
[36]
were prepared
1
13
1
according to the literature. H NMR (400 MHz), C{ H} NMR (100 MHz),
P{ H} NMR (162 MHz), and F{ H} NMR (376 MHz) spectra were
measured on Bruker Avance III-400 spectrometers. All H NMR chemical
31
1
19
1
(
Figure 4). Olefins coordinate to 1c to afford complex A, in which
1
the highly rigid pocket of the rhodium(III) species efficiently
shifts were reported in ppm () relative to tetramethylsilane at  0.00 or
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Chemistry - A European Journal
10.1002/chem.202000542
RESEARCH ARTICLE
solvent residual signal (CHCl
3
at  7.26 ppm, CH
2
Cl
2
at  5.32 ppm, C
6
D
6
X-ray Analysis
at 7.15 ppm). All 13C{ H} NMR chemical shifts were reported in ppm ()
1
The crystals of 1b and 1c were mounted on the CryoLoop (Hampton
Research Corp.) with a layer of light mineral oil and placed in a nitrogen
stream at 113(2) K. A measurement was made on a Rigaku XtaLAB P200
diffractometer using multi-layer mirror monochromated Mo-Ka (0.71075 Å)
radiation with CrystalClear program.[40] Crystal data and structure
refinement parameters are in Table S4. The structure of complex 1b was
solved by SHELXT-2014[41a] and refined on F by full matrix least-squares
method, using SHELXL-2015[41] in the Olex2 program.[42] The structure
was solved by SIR 92[43] and refined on F2 by full-matrix least-squares
method, using SHELXL-2016[41] in the Crystal Structure Analysis
Package.[44] Non-hydrogen atoms were anisotropically refined. H-atoms
were included in the refinement on calculated positions riding on their
31
1
relative to carbon resonances of CDCl at  77.16. All P{ H} NMR
3
chemical shifts were reported in ppm () relative to phosphine resonances
in external standard of phosphoric acid at  0.00. All 19F{ H} NMR chemical
shifts were reported in ppm () relative to fluorine resonances in external
standard of ,,-trifluorotoluene at  -63.90. Diffusion experiments were
measured on Bruker AVANCE III HD 500 MHz spectrometer. HPLC
spectra were recorded on a JASCO UV-4075. Optical rotation values were
recorded on Anton Paar MCP100 polarimeter at 589 nm (sodium lamp)
and are given in 10-1 deg cm2 g . High resolution mass spectra were
obtained on JEOL JMS-700 and Thermo Fisher Scientific Orbitrap XL. All
melting points were recorded on BUCHI Melting Point M-565. Flash
column chromatography was performed using silica gel 60 (0.040-0.0663
nm, 230-400 mesh ASTM) with hexane (>95 %, KANTO CHEMICAL CO.,
INC.) and EtOAc (>99 %, NACALAI TESQUE, INC.). Hydrogenation
reaction was conducted using Biotage Endeavor® or TAIATSU stainless
autoclave.
1
2
-1
2
2 2
carrier atoms.
The function minimized was [Σw(Fo - Fc ) ]
2
2
2
2
2
(w = 1 / [σ (Fo ) + (aP) + bP]), where P = (Max(Fo ,0) + 2Fc ) / 3 with
2
2
σ (Fo ) from counting statistics. The function R1 and wR2 were
(Σ||Fo| – |Fc||) / Σ|Fo| and [Σw(Fo –Fc ) / Σ(wFo )]1/2, respectively. The
2
2
2
4
ORTEP-3 program was used to draw the molecule.[45]
General
Procedure
for
Rhodium
Catalyzed
Asymmetric
Preparation of rhodium(III) complexes 1
Hydrogenation
These complexes were prepared by modified method of the reported
An olefinic substrate (0.20 mmol) was added to a glass tube in an
autoclave, and the autoclave was charged with argon gas. A rhodium
catalyst (8.0 mol, 4.0 mol%) was dissolved in dry solvent (3 mL) under
argon atmosphere, and the solution was transferred to the glass tube in
the autoclave. When the mixture of rhodium(I) pre-catalyst and chiral
diphosphine ligand were used as a catalyst system, the solution was
stirred for 30 minutes before injection to the autoclave. Then, the
procedure.[17a] [Rh(cod)Cl]
2
(222 mg, 0.450 mmol) was dissolved in
toluene (10 mL) under argon atmosphere. A solution of chiral diphosphine
ligand (0.91 mmol, 2.01 equiv) in toluene (20 mL) was added to the
solution of [Rh(cod)Cl]
2
, and the resulting mixture was stirred overnight at
room temperature. 2.0 M HCl/Et
2
O (4.5 mL, 9.0 mmol, 20 equiv,
purchased from SIGMA-ALDRICH with Sure/Seal bottle) was added to the
mixture. After stirring for 2 hours at room temperature, all volatiles were
removed under reduced pressure. The crude residue was purified by
reprecipitation with DCM/hexane (1/20) twice to afford the corresponding
complex.
autoclave was charged with H
bar. The reaction mixture was stirred for periodic time. After the reaction,
gas was released, and phenanthrene was added to the reaction mixture
2
gas, and the pressure was increased to 30
H
2
as an internal standard. All volatiles were removed under reduced
pressure. The yield was determined by 1H NMR analysis, and the
enantiomeric excess was determined by HPLC analysis.
[
{Rh(H)((S)-binap)}
2
(-Cl)
Cl , 400 MHz, 30 °C):  8.08 (t, J = 9.1 Hz, 2H), 8.00
d, J = 8.3 Hz, 2H), 7.85-7.70 (m, 8H), 7.61-7.46 (m, 8H), 7.44-7.21 (m, 20
3
]Cl (1a): Brown solid. IR (KBr): (Rh-H): 2136
-1
1
cm ; H NMR (CD
(
2
2
Diffusion Experiments
H), 7.08 (t, J = 7.9 Hz, 2H), 7.03 (t, J = 7.9 Hz, 2H), 6.98 (brs, 4H), 6.91 (t,
All diffusion experiments were acquired on a Bruker AVANCE III HD 500
MHz spectrometer using a double stimulated echo pulse sequence
according to Mueller et al,[37],[38] with alternative phase cycling as described
by G. Morris.[39] All experiments were 1H NMR measurements and
J = 7.8 Hz, 2H), 6.82 (t, J = 7.1 Hz, 2H), 6.70-6.54 (m, 10H), 6.31 (d, J =
8.8 Hz, 2H), -15.9 (dt, J = 22.5,15.8 Hz, 1H). 31P{ H} NMR (CD
1
2
Cl
2
, 162
MHz, 30 °C): 48.6 (dd, J = 137, 27 Hz), 36.1 (ddd, J = 134, 26 Hz, 3 Hz).
2 2
performed at 298 K with samples of 20 mM concentration in CD Cl . A
maximum gradient strength of g = 50 G/cm was used and each experiment
was acquired with 32 gradient steps with varying gradient strength from
[
{Rh(H)((S)-DM-segphos)}
2
(-Cl)
3
]Cl (1b): White solid. IR (KBr): (Rh-H)
-1 1
2
7
4
2
123 cm ; H NMR (CD Cl , 400 MHz, 30 °C):  7.34 (d, J = 12.1 Hz, 6H),
2 2
.21 (s, 4 H), 7.10-6.96 (m, 12H), 6.56 (d, J = 8.3 Hz, 4H), 6.37-6.28 (m,
H), 5.85 (d, J = 12.8 Hz, 6H), 5.50 (s, 2H), 5.33 (m, 2H), 2.37 (s, 24H),
.28 (s, 12H), 1.94 (s, 12H), -16.1 ppm (dt, J = 21.8, 16.1 Hz, 1H); 31P{ H}
2
% to 98%. To gain insight systematic errors caused by convection of the
CD Cl , all diffusion experiments were performed twice using two different
diffusion delays ∆ = 1.00 s and ∆ = 0.50 s. The diffusion coefficients for
the remaining solvent signal in CD Cl were then determined for each
2
2
1
NMR (CD
J = 136, 26, 12 Hz).
2
Cl , 162 MHz, 30 °C): 48.3 (ddd, J = 135, 26, 8 Hz), 41.1 (ddd,
2
2
2
experiment separately and the mean values from all experiments of
2
9.49(64) ∙ 10-10 m2s-1 (for ∆ = 1.00 ms) and 29.84(70) ∙ 10-10 m2s-1 (for ∆ =
2
Rh((S)-DTBM-segphos)HCl (1c): Orange solid. IR (KBr): (Rh-H) 2007
0.50 ms) reveal a small, but systematic error of in comparison to the
-1 1
cm ; H NMR (CD
2
Cl
2
, 400 MHz, 30 °C):  7.82 (d, J = 13.4 Hz, 3H), 7.74
[
39]
value of 31.7 ∙ 10-10 m s . Consequently, the obtained
2 -1
literature
(d, J = 11.6 Hz, 3H), 6.56 (d, J = 7.9 Hz, 1H), 6.48-6.38 (m, 3 H), 5.82 (s,
diffusion coefficients for the solute for each value of ∆ (0.50 or 1.00 s) are
directly comparable, whereas absolute coefficient values should be used
with care. Data analysis and determination of the diffusion coefficients by
1H), 5.73 (s, 1H), 5.67 (d, J = 5.5 Hz, 2H), 5.36 (d, J = 4.6 Hz, 2H), 3.77
(
s, 3H), 3.75 (s, 3H), 3.70 (s, 3H), 3.67 (s, 3H), 1.43 (s, 36H), 1.38 (s, 36H),
31
1
2
2
2
ꢀ
3
–16.5 (ddd, J = 20.0, 12.1, 6.8 Hz, 1H); P{ H} NMR (CD
2 2
Cl , 162 MHz,
−
푫훾
푔
훿
(∆−
)
curve fitting according to 퐼 = 퐼 푒
was done using the Topspin
0
30 °C): 62.5 (dd, J = 138, 26 Hz), 32.6 (ddd, J = 130, 26, 5 Hz).
Bruker T1/T2 software using integral areas. For each compound, three
separate integral regions were defined and three diffusion coefficients from
each experiment and the corresponding mean values plus standard
deviation are given below, for both ∆. The normalized diffusion coefficients
(
(
R)-1-benzyl-2,3-dihydro-1H-indene ((R)-5): Colourless oil. 1H NMR
CDCl , 400 MHz, 30 ºC):  7.33-7.25 (m, 2H), 7.25-7.18 (m, 4H), 7.18-
3
formula:[23]
7.07 (m, 3H), 3.44 (quint, J = 7.3 Hz, 1H), 3.13 (dd, J = 13.6, 5.8 Hz, 1H),
were
obtained
using
the
empirically
derived
2
1
1
.93-2.73 (m, 2H), 2.69 (dd, J = 13.5, 9.2 Hz, 1H), 2.20-2.07 (m, 1H), 1.83-
.70 (m, 1H); 13C NMR (CDCl
, 100 MHz, 30 °C):  147.0, 144.3, 141.0,
29.2, 128.4, 126.6, 126.1 , 126.0 , 124.7, 123.9, 46.6, 41.6, 32.1, 31.3;
log Dnorm = log Dref, fix – log Dref, measured + log Dmeasured
Volume ratios complex/ligand in Table S3 was calculated according to
Stokes-Einstein assuming spherical geometries by the dividing the ratios
of (1/Dnorm)3 of the corresponding ligands and complexes.
(5)
3
4
8
i
HPLC (Daicel OJ-H, temperature: 30 °C, hexane : PrOH = 95 : 5, detector :
15 nm, flow rate 0.5 mL/min, t (-) = 9.5 min, t
(+) = 10.6 min). []20
2
1
2
D
=
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Chemistry - A European Journal
10.1002/chem.202000542
RESEARCH ARTICLE
10.6 Hz, 1H), 2.93 (d, J = 16.0 Hz, 1H), 2.07 (brs, 3H); 13C{ H} NMR (CDCl
1
+
7.2 (c = 0.57, CHCl
3
) (for an ee of 96%). The absolute configuration was
3
,
[
11e]
determined by the optical rotation in comparison with literature.
100 MHz, 30 °C):  169.3, 147.1, 143.2, 128.6, 128.1, 126.4, 125.6, 125.1,
1
24.5, 122.7, 117.2, 63.2, 38.9, 24.2; C-F coupling constants could not be
13
1
19
1
1
determined by C{ H} NMR analysis due to broad signals. F{ H} NMR
3
-benzyl-2,3-dihydrobenzofuran ((-)-7): Yellow oil. H NMR (CDCl
3
, 400
(
CDCl
3
, 376 MHz, 30 °C):  -63.8; HPLC (Daicel AD-H, temperature: 30 °C,
MHz, 30 °C):  7.35 (t, J = 7.3 Hz, 2H), 7.28 (m, 1H), 7.22 (d, J = 7.3 Hz,
i
hexane : PrOH = 90 : 10, detector : 215 nm, flow rate 1.0 mL/min, t
9
>99%). HRMS (FAB ) m/z calcd. for
1
(-) =
) (for an ee of
306.1106 found
2
4
3
H), 7.16 (t, J = 7.8 Hz, 1H), 7.01 (d, J = 7.3 Hz, 1H), 6.91-6.77 (m, 2H),
.3 min, t
2
(+) = 10.5 min); []20D = +155.8 (c = 0.94, CHCl
3
.56 (t, J = 9.0 Hz, 1H), 4.29 (dd, J = 9.0, 5.9 Hz, 1H), 3.82-3.70 (m, 1H),
+
.08 (dd, J = 13.9, 6.4 Hz, 1H), 2.86 (dd, J = 13.9, 8.9 Hz, 1H); 1 C{ H}
3
1
C
17
H
15ONF
3
306.1105.
NMR (CDCl
3
, 100 MHz, 30 °C):  160.1, 139.3, 130.4, 129.1, 128.7, 128.5,
1
26.6, 124.7, 120.4, 109.8, 76.5, 43.6, 41.2; HPLC (Daicel OJ-3,
i
temperature: 30 °C, hexane : PrOH = 95 : 5, detector : 215 nm, flow rate
.0 mL/min, t (+) = 9.4 min, t = -34.8 (c = 0.65, CHCl
(-) = 9.8 min); []20
for an ee of 94%). The absolute configuration was determined by the
HPLC measurement in comparison with literature.[11e]
2-phenyl-2,3-dihydrobenzo[b]thiophene 1,1-dioxide ((R)-15): Pale
1
1
(
1
2
D
3
)
brown solid. H NMR (CDCl
3
, 400 MHz, 30 °C):  7.80 (d, J =7.7 Hz, 1H),
7.62 (td, J = 7.6, J = 1.2 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.49-7.40 (m,
6H), 4.68 (t, J = 8.4 Hz, 1H), 3.65 (d, J = 8.4 Hz, 2H); 13C{ H} NMR (CDCl
1
3
,
100 MHz, 30 °C):  138.6, 136.5, 133.6, 130.3, 129.6, 129.5, 129.2, 129,1,
1
27.2, 122.5, 67.6, 33.0; HPLC (Daicel AS-H, temperature: 30 °C,
1
5
2
1
7
,1-dimethyl-2-phenyl-2,3-dihydro-1H-indene ((-)-9): White solid. mp
4.9-61.2 °C (2 °C/min); IR (KBr,  /cm ): 3066 w, 3031 w, 2958 s, 2938 m,
883 m, 2849 m, 1602 w, 1582 w, 1494 m, 1477 s, 1453 s, 1381 w, 1361 m,
i
-
1
hexane : PrOH = 70 : 30, detector : 215 nm, flow rate 1.0 mL/min, t
1
(-) =
(+) = 18.4 min); []20
= -77.9 (c = 0.57, CHCl ) (for an ee of
D 3
16.5 min, t
2
7
7%). The absolute configuration was determined by the optical rotation
290 w, 1262 w, 1227 w, 1185 w, 1109 w, 1082 m, 1026 w, 775 m, 763 s,
in comparison with literature.[
49]
1
32 m, 707 s; H NMR (CDCl
3
, 400 MHz, 30 °C):  7.42-7.19 (m, 9H, Ar,
Ph), 3.46-3.33 (m, 2H, PhCH, ArCH), 3.27-3.14 (m, 1H, ArCH), 1.42 (s,
1
3
1
4
i
H, CH
3
), 0.87 (s, 3H, CH
3
); 13C{ H} NMR (CDCl
3
, 100 MHz, 30 °C): 
1,1-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[b]silole
((-)-17):
52.2, 141.5, 141.0, 129.0, 128.1, 126.8, 126.7, 126.5, 124.6, 122.5, 57.6,
7.3, 36.0, 27.3, 24.9; HPLC (Daicel OJ-H, temperature: 30 °C, hexane :
PrOH = 95 : 5, detector : 215 nm, flow rate 0.5 mL/min, t
Colorless oil. 1H NMR (CDCl
3
, 400 MHz, 30 °C): 7.52 (d, J = 7.0 Hz, 1
H7.39-7.29 (m, 2H), 7.26-7.19 (m, 3H) 7.13-7.04 (m, 3H), 3.51 (dd, J =
16.5, 8.3 Hz, 1H), 3.37 (dd, J = 16.5, 7.5 Hz, 1H),2.83 (t, J = 7.9 Hz, 1H),
1
(+) = 9.6, t
2
(-) =
1
6.3; []20
D
= -155.4 (c = 0.24, CHCl
3
) (for an ee of 95%); HRMS (ESI)
13
1
3
0.39 (s, 3H), -0.03 (s, 3H); C{ H} NMR (CDCl , 100 MHz, 30 °C):  151.8,
+
(
m/z): [M+H] calcd for C17
H
18, 223.1481; found, 223.1477.
144.6, 138.7, 132.5, 129.8, 128.5, 126.6, 126.3, 125.6, 124.5, 39.4, 35.6,
i
-
1.9, -3.9; HPLC (Daicel OJ-3, temperature: 30 °C, hexane : PrOH = 95 :
-(2-phenylindolin-1-yl)ethan-1-one ((R)-11a): Yellow oil. 1H NMR
CDCl , 400 MHz, 30 °C):  8.33 (d, J = 7.2 Hz, 1H), 7.37-7.05 (m, 7 H),
5, detector : 215 nm, flow rate 1.0 mL/min, t
1 2
(+) = 6.9 min, t (+) = 35.5 min);
1
(
[
]20 ) (for an ee of 93%).[50]
D
=-151.6 (c = 0.82 , CHCl
3
3
7
1
.05-7.00 (m, 1H), 5.34 (d, J = 9.2 Hz, 1H), 3.75 (dd, J = 15.4, 10.4 Hz,
H), 2.94 (dd, J = 16.1, 1.9 Hz, 1H) 2.01 (s, 3H); 13C{ H} NMR (CDCl
1
Ethyl 3-phenylbutanoate ((R)-19): Colorless oil. 1H NMR (CDCl
, 400
3
3
, 100
MHz, 30 °C):  169.5, 143.4, 143.2, 129.2, 127.8, 127.7, 125.0, 124.9,
MHz, 30 °C):  7.32-7.26 (m, 2H), 7.23-7.16 (m, 3H), 4.07 (q, J = 7.2 Hz,
1
24.1, 117.0, 63.5, 38.9, 24.2; HPLC (Daicel AD-H, temperature: 30 °C,
2H), 3.27 (sext, J = 7.8 Hz, 1H), 2.57 (qd, J = 15.6, 8.1 Hz, 1H), 1.30 (d, J
i
= 7.0 Hz, 3H), 1.17 (t, J = 7.2 Hz, 3H); 13C{ H} NMR (CDCl
1
hexane : PrOH = 90 : 10, detector : 215 nm, flow rate 1.0 mL/min, t
1
(-) =
) (for an ee of
9%). The absolute configuration was determined by the optical rotation
3
, 100 MHz,
1
1.6 min, t
2
(+) = 15.9 min). [20
D
= +147.6 (c = 0.95, CHCl
3
30 °C):  172.5, 145.9, 128.6, 126.9, 126.5, 60.4, 43.1, 36.7, 21.9, 14.3;
HPLC (Daicel OD-H, temperature: 30 °C, hexane : iPrOH = 98 : 2,
9
in comparison with literature after deprotection of an acetyl group.[46]
detector : 215 nm, flow rate 0.5 mL/min, t
20
= -23.7 (c = 1.08, CHCl ) (for an ee of 89%). The absolute
1 2
(-) = 9.2 min, t (+) = 11.3 min).
[
D
3
configuration was determined by the optical rotation in comparison with
literature.[28]
1
-(2-(4-methoxyphenyl)indolin-1-yl)ethan-1-one ((+)-11b): Colorless oil.
1
H NMR (CDCl
3
, 400 MHz, 30 °C):  8.34 (brs, 1H), 7.31-7.25 (m, 1H),
7
3
1
1
.16-7.00 (m, 4H), 6.85 (d, J = 8.4 Hz, 2H), 5.34 (d, J = 8.7 Hz, 1H), 3.80-
.69 (m, 4H), 2.96 (d, J = 16.1 Hz, 1H), 2.06 (s, 3H); 13C{ H} NMR (CDCl
1
3
,
00 MHz, 30 °C):  169.6, 159.1, 143.3, 135.3, 129.3, 127.7, 126.2, 124.9,
Acknowledgements
24.0, 117.0, 114.5, 63.1, 55.3, 39.1, 24.1; HPLC (Daicel AD-H,
i
temperature: 30 °C, hexane : PrOH = 90 : 10, detector : 215 nm, flow rate
(+) = 25.0 min); []20
This work was supported by JSPS KAKENHI This work was
supported by JSPS KAKENHI JP15H05808 and JP15K21707 in
a Grant-in-Aid for Scientific Research on Innovative Areas,
Precisely Designed Catalysts with Customized Scaffolding (No.
1.0 mL/min, t
1
(-) = 18.9 min, t
2
D
= +98.0 (c = 0.96,
CHCl
3
) (for an ee of 96%).[47]
1
-(2-(3-methoxyphenyl)indolin-1-yl)ethan-1-one ((+)-11c): White solid.
1
H NMR (CDCl
H), 7.16-7.10 (m, 1H), 7.06 (t, J = 7.2 Hz, 1H), 6.81-6.67 (m, 3H), 5.36 (d,
J = 9.3 Hz, 1H), 3.83-3.69 (m, 4H), 2.99 (d, J = 16.0 Hz, 1H), 2.07 (s, 3H);
3
, 400 MHz, 30 °C):  8.36 (d, J = 7.0 Hz, 1H), 7.30-7.18 (m,
2702), JP16H06934 in a Grant-in-Aid for Research Activity Start-
2
up of The Ministry of Education, Culture, Sports, Science, and
Technology, Japan. This work was partly achieved through the
use of PC cluster for large-scale visualization at the Cybermedia
13
1
C{ H} NMR (CDCl , 100 MHz, 30 °C):  169.5, 160.2, 144.8, 143.4, 130.3,
3
129.2, 127.7, 124.8, 124.0, 117.2, 116.9, 112.6, 111.0, 63.4, 55.2, 38.8,
i
Center, Osaka University.
K.H. was supported by JSPS
24.1. HPLC (Daicel AD-H, temperature: 30 °C, hexane : PrOH = 90 : 10,
detector : 215 nm, flow rate 1.0 mL/min, t
1
(+) = 11.2 min, t
2
(-) = 17.0 min);
Research Fellowship for young scientists. We thank Dr. Tsuneaki
Yamagata, Ms. Natsuki Yoshioka for their experimental
contribution in the early stage of the project.
[
]20 ) (for an ee of 99%).[48]
= +164.1 (c = 0.82, CHCl
D 3
1
-(2-(4-(trifluoromethyl)phenyl)indolin-1-yl)ethan-1-one
((+)-11e):
-
1
Colorless oil. IR (KBr,  /cm ): 3449 br, 3070 w, 3048 w, 2955 w, 2858 w,
664 s, 1620 m, 1599 m, 1481 s, 1463 m, 1394 s, 1326 s, 1275 m, 1167
m, 1124 s, 1111 s, 1067 s, 1017 m, 755 m; 1H NMR (CDCl
, 400 MHz,
5 °C):  8.26 (brs, 1H), 7.56 (d, J = 7.8 Hz, 2H), 7.34-7.23 (m, 3H), 7.17-
.08 (m, 1H), 7.05 (t, J = 7.4 Hz, 1H), 5.49 (brs, 1H), 3.78 (dd, J = 15.0,
Keywords: Asymmetric hydrogenation • Rhodium •
monohydride • mononuclear complex • simple olefin
1
3
5
7
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Chemistry - A European Journal
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RESEARCH ARTICLE
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RESEARCH ARTICLE
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Chemistry - A European Journal
10.1002/chem.202000542
RESEARCH ARTICLE
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H
2
SO in EtOH (2.0 mL)/H O (1.0 mL) under reflux conditions for 12
4
2
hours to afford (+)-R-2-phenyl indoline (>99% ee, 16.0 mg, 0.082 mmol)
1
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3
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J = 7.2 Hz, 1H), 7.12-7.03 (m, 2H), 6.74 (t, J = 7.4 Hz, 1H), 6.68 (d, J =
7
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1
1
3
, 100
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1
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i
hexane : PrOH = 80 : 20, detector : 215 nm, flow rate 1.0 mL/min, t
1
(-) =
9.6 min, t
2
(+) = 15.0 min); []20
D
= +89.4 (c = 0.33 in CHCl
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[
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Asymmetric
simple olefins was achieved by
using monohydride-dichloro
rhodium(III) complexes 1a—c which
were characterized by NMR
spectroscopy, including DOSY
NMR, and X-ray single crystal
hydrogenation
of
Kosuke Higashida, Fabian Brüning,
Nagataka Tsujimoto, Kenya
Higashihara, Haruki Nagae, Antonio
Togni,* and Kazushi Mashima*
Page No. – Page No.
Monohydride-dichloro Rhodium(III)
Complexes with Chiral
Diphosphine Ligands as Catalysts
for Asymmetric Hydrogenation of
Olefinic Substrates
analysis.
Among these three
complexes, 1c has a rigid pocket
surrounded by two chloride atoms
bound to the rhodium atom for fitting
to simple olefins without any
coordinating functional groups.
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Title
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