Planar-chiral phosphine-olefin ligands exploiting a (Cyclopentadienyl)manganese(I) scaffold to achieve high robustness and high enantioselectivity

Article abstract of DOI:10.1021/jacs.6b11243

A series of 2-methyl-1,3-propenylene-bridged (η⁵-diarylphosphinocyclopentadienyl)(phosphine)manganese(I) di-carbonyl complexes 2 have been developed as a new class of phosphine-olefin ligands based on a planar-chiral transition-metal scaffold,

Full text of DOI:10.1021/jacs.6b11243

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Article
Planar-Chiral Phosphine-Olefin Ligands Exploiting
a (Cyclopentadienyl) manganese (I) Scaffold to
Achieve High Robustness and High Enantioselectivity
Ken Kamikawa, Ya-Yi Tseng, Jia-Hong Jian, Tamotsu Takahashi, and Masamichi Ogasawara
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 03 Jan 2017
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Planar-Chiral Phosphine-Olefin Ligands Exploiting a (Cyclopentadi-
enyl)manganese(I) Scaffold to Achieve High Robustness and High
Enantioselectivity
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Ken Kamikawa,*,† Ya-Yi Tseng,† Jia-Hong Jian,‡ Tamotsu Takahashi,‡ and Masamichi Ogasawa-
ra*,‡,§
† Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
‡ Institute for Catalysis, Hokkaido University, Kita-ku, Sapporo 001-0021, Japan
§ Department of Natural Science, Graduate School of Science and Technology, Tokushima University, Tokushima
770-8506, Japan
ABSTRACT:
A
series
of
2-methyl-1,3-propenylene-bridged
(η5-
diarylphosphinocyclopentadienyl)(phosphine)manganese(I) dicarbonyl complexes 2 have been developed as a new class
of phosphine-olefin ligands based on a planar-chiral transition-metal scaffold, which show the better robustness as well as
the higher enantioselectivity over phosphine-olefin ligands 1 that are with a planar-chiral (η6-arene)chromium(0) frame-
work. The practical enantiospecific and scalable synthesis of 2 has been established. Phosphine-olefin ligands 2 enable to
construct the effective chiral environment around a transition-metal center upon coordination, and thus their rhodium(I)
complexes exhibit excellent catalytic performances in the various asymmetric addition reactions of arylboron nucleo-
philes. Complex 2b, which is with bis(3,5-dimethylphenyl)phosphino group on the cyclopentadienyl ring, is found to be a
superior chiral ligand in the rhodium-catalyzed asymmetric 1,4-addition reactions of arylboronic acids to various cy-
clic/acyclic enones giving the corresponding arylation products in over 99% ee. On the other hand, 2c and 2d, which are
with bis[3,5-bis(trifluoromethyl)phenyl]phosphino and bis(3,5-di-tert-buthyl-4-methoxyphenyl)phosphino groups respec-
tively, are highly efficient chiral ligands in the rhodium-catalyzed asymmetric 1,2-addition reactions of the arylboron nu-
cleophiles to imines or aldehydes showing up to 99.9% ee. The X-ray crystallographic studies of (R)-2b and [RhCl((S*)-
2b)]2 reveal the absolute configuration of 2b and its phosphine-olefin bidentate coordination to a rhodium(I) cation.
Structural comparison with [RhCl((R*)-1b)]2 postulates the origins of the higher enantioselectivity of newly developed
phosphine-olefin ligands 2.
tion-metal catalysis. Recently, chiral phosphine-olefin
ligands have been emerged as a new promising class of
INTRODUCTION
ligands, whose structural motifs can be regarded as a hy-
brid of classical chiral phosphines and chiral dienes (Fig-
ure 1).3 In 2012, we developed highly enantioselective ki-
netic resolution of various racemic planar-chiral (π-
arene)chromium species by the molybdenum-catalyzed
asymmetric ring-closing metathesis (ARCM). During the
course of the studies, we unexpectedly recognized highly
effective chiral phosphine-olefin ligand (R)-1a which was
based on the planar-chiral (arene)chromium scaffold.
Ligand (R)-1a showed very high enantioselectivity and
reactivity in the rhodium-catalyzed asymmetric 1,4-
addition reaction (the Hayashi-Miyaura conjugate addi-
tion reaction) of cyclohexenone with phenylboronic acid
(99.5% ee, 98%).4a This result prompted us to investigate
the further details of this unique phosphine-olefin ligand.
After the extensive screening, we found out that planar-
Enantioselective reactions catalyzed by chiral transi-
tion-metal complexes are very powerful methods to sup-
ply various chiral building blocks in modern organic syn-
thesis. The most common method for chiral modification
of transition-metal catalysts is introduction of appropriate
chiral ligands onto a metal center, and thus, design and
synthesis of new chiral ligands, which could provide high
activity and high enantioselectivity for the metal catalysts,
has been a central subject in the development of asym-
metric reactions.1 Chiral phosphines are arguably the chi-
ral ligands most extensively studied for transition-metal-
catalyzed asymmetric reactions. Meanwhile, conceptually
novel chiral dienes have been elaborated over the last
decade and have demonstrated to be superior to tradi-
tional chiral phosphines in various rhodium- and iridium-
catalyzed asymmetric reactions.2 While chiral diene lig-
ands enable to construct the effective chiral environment
around the metal center, their coordination to a transi-
tion metal is generally weaker than that of phosphorus-
based ligands, which diminish their applicability in transi-
chiral ligand (R)-1b, which possesses
a
bis(3,5-
dimethylphenyl)phosphino group on the η6-arene ring,
was superior to precedent (R)-1a in the rhodium-
catalyzed reactions (Scheme 1).4b While planar-chiral
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(arene)chromium-based ligands (R)-1 showed the very
Page 2 of 12
R2P
1
2
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Planar-chiral phosphine-olefin ligands
based on an (arene)chromium framework
high performance in the Hayashi-Miyaura reaction of the
series of cyclic enones and related substrates, it was real-
ized that (R)-1 had some drawbacks: (i) instability of the
ligands toward air-oxidation especially in a solution state,
and (ii) insufficient enantioselectivities and reactivities in
the reactions with acyclic enones. We thought that the
former point was particularly critical for the practical ap-
plication of the phosphine-olefin ligands, since the exces-
sive fragility made handling of the compound difficult.
Me
Cr
CO
2 CO
P
1) Higly tunable scaffolds
Ph
2) High enantioselectivities for cyclic enones
3) High reactivities for cyclic enones
(R)-1a, b
a: R = Ph; b: R = 3,5-Xylyl
cyclic enones
O
O
[RhCl(C2H4)2]2 (2.5 mol %)
(R)-1b (5.2 mol %)
9
X
X
+
ArB(OH)2
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*
KOH (0.5 equiv)
dioxane/H2O = 10/1
50 °C, 9 h
Ar
n
n
up to 99.9% ee
92-99% yield
n = 0; X = C; Ar = Ph
n = 1; X = O, C; Ar = Ph, p-MeC6H4, p-CF3C6H4
acyclic enones
[RhCl(C2H4)2]2 (2.5 mol %)
(R)-1b (5.2 mol %)
O
O
Ar
*
+
ArB(OH)2
KOH (0.5 equiv)
dioxane/H2O = 10/1
50 °C, 9 h
n
n
up to 88% ee
34-43% yield
n = 0, 4; Ar = Ph
With the background mentioned above, we started the
present studies with intention to improve the stability of
the chiral ligands. The fragility of (arene)chromium-based
phosphine-olefin ligands 1 is ascribed to the presence of
the (arene)chromium substructure, since they suffer from
the photo-induced oxidative degradation (Scheme 2).5 We
envisioned
that
the
replacement
of
the
(arene)chromium(0) moiety in 1 with an isoelectronic and
more robust (cyclopentadienyl)manganese(I) moiety
might be an answer to this problem. The enantiospecific
and scalable synthesis of these (cyclopentadi-
enyl)manganese(I)-based phosphine-olefin ligands 2 has
been developed. Indeed, manganese complexes 2 show
much better robustness than 1 as we expected. Further-
more, the introduction of the CpMn(I) framework in 2
gives us an extra (and more important) benefit: planar-
chiral phosphine-olefin ligands 2 are far superior to
(arene)Cr-based "first-generation" phosphine-olefin lig-
ands 1 in terms of the enantioselectivities and catalytic
activities in a wide range of rhodium-catalyzed asymmet-
ric reactions. The Rh(I) catalysts coordinated with (R or
S)-2 are applicable to the asymmetric 1,4-arylation of not
only cyclic but acyclic enones and the asymmetric 1,2-
arylation of imines/aldehydes to give the corresponding
addition products in >99% ee in many cases.
Figure 1. Structures of representative chiral phosphine-olefin
ligands.
Scheme 1. Rhodium-Catalyzed Asymmetric 1,4-
Addition
Reactions
Using
Planar-Chiral
(Arene)chromium-Based Phosphine-Olefin Ligand
(R)-1.4
Scheme 2. Photo-Induced Oxidative Degradation of
(π-Arene)chromium Complexes (R)-1.5
In this article, we would like to report the results of our
studies on the innovative "second-generation" planar-
chiral phosphine-olefin ligands, which are with an (η5-
cyclopentadienyl)manganese(I) framework.
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RESULTS AND DISCUSSION
1
2
Design and Stereospecific Preparation of Planar-
Chiral (Cyclopentadienyl)manganese(I)-Based Phos-
phine-Olefin Ligands 2. To retain the efficient chiral
environment in (R)-1, the key structural motifs such as
the bridging structure between the π-arene and the
chromium-bound phosphine and a methyl group on the
olefin unit should be adopted in a newly designed lig-
and.4b On the other hand, the photo/oxygen-sensitive (π-
arene)chromium(0) moiety needed to be replaced with a
robust component of an isoelectronic structure. From
these perspectives, we designed "second-generation" pla-
nar-chiral phosphine-olefin ligands (R)-2, which are with
a (η5-cyclopentadienyl)manganese(I) scaffold as a new
planar-chiral platform (Figure 2). While the partially ionic
metal/π-ligand interaction in 2 (i.e., the coordination of
an anionic cyclopentadienide to a manganese(I) cation in
2 and the coordination of an electronically neutral arene
to a chromium(0) atom in 1) may lead to the better stabil-
ity of 2, the different phosphine-olefin bite angles be-
tween 1 and 2, which are originated from a five-membered
Cp ligand in 2 and a six-membered π-arene ligand in 1,
may lead to the different reactivities and selectivities in
the applied transition-metal-catalyzed asymmetric reac-
tions.
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The enantiospecific and multi-gram scale synthesis of
the designed planar-chiral CpMn(I)-based phosphine-
olefin ligands was achieved as outlined in Scheme 3. The
key synthetic intermediate in the synthesis is enantio-
merically pure 1-bromo-2-formylcymantrene (S)-5, which
was prepared from Jaouen's chiral acetal 3.8a The ortho-
The 1st Generation P-olefin Ligands
The 2nd Generation P-olefin Ligands
R2P
R2P
(arene)Cr(0)
CpMn(I)
Me
Cr
Me
Mn
CO
CO
P
P
Ph2
CO
CO
Ph2
t
(R)-1
(S)-2
lithiation of 3 using BuLi in ether at –78 °C took place
with excellent diastereoselectivity as reported,8a and sub-
sequent bromination with 1,2-dibromotetrachloroethane
gave bromo-acetal 4 in 86% yield. After the hydrolysis of
Figure 2. Design of second-generation phosphine-olefin lig-
ands (S)-2 based on the (cyclopentadienyl)manganese(I)
framework.
4
with aqueous hydrochloric acid, 1-bromo-2-
formylcymantrene 5 was obtained in 83% yield and 99.8%
ee. The absolute configuration of the product was deter-
mined to be (S) by the analogy with the previous report.8c
Recrystallization of the product from hexane/ethyl ace-
tate afforded enantiomerically pure (S)-5. The Wittig
methylenation of the formyl substituent and the photo-
induced ligand exchange reaction with diphenylmethal-
It should be noted that the (R)/(S)-nomenclature rules
commonly used for notating the absolute configuration of
planar-chiral (η5-cyclopentadienyl)metal complexes6,7 are
different from those used for the (R)/(S)-notation of (η6-
arene)metal complexes.5c,7b Consequently, the two planar-
chiral compounds shown in Figure 2 have opposite
(R)/(S)-descriptors to each other, although the relative
orientations between the PR2 group and the bridging ole-
fin moiety are same in both (R)-1 and (S)-2.
lylphosphine
gave
(cyclopentadi-
enyl)(phosphine)manganese(I) complex (S)-7 in good
yield. The subsequent ruthenium-catalyzed ring-closing
metathesis of (S)-7 provided bridging bromide (S)-8 in
95% yield. In the final step, a series of phosphine-olefin
ligands (S)-2a-d with a respective diarylphosphino group
on the cyclopentadienyl unit were obtained in good yields
by the conventional lithiation/phosphanylation sequence.
In the same way, the corresponding antipodes, (R)-2a-d,
could be synthesized by using (R)-1,2,4-butanetriol as a
chiral auxiliary in manganese complex 3. The absolute
configuration of (+)-2b was the confirmed as (R) by the
single-crystal X-ray crystallography (see Figure 6 (a)).
Scheme 3. Stereospecific Preparation of Planar-
Chiral (Cyclopentadienyl)manganese(I)-Based Phos-
phine-Olefin Ligands.
Alternatively, (S)- and (R)-8 were obtained by the enan-
tiomeric resolution of preformed rac-8 by HPLC with a
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preparative chiral stationary phase column (Daicel Chi-
Page 4 of 12
1
ralcel OD).
2
3
4
Comparison of Air-Oxidation Tolerance between
CpMn(I)- and (Arene)Cr(0)-Based Ligands.
The stability of the ligands is crucial for their practical
applications in catalytic organic transformations. The
photo-induced oxidative decomposition of (arene)Cr-
based ligands 1 (see Scheme 2) results in high oxidation-
state chromium residue, which may oxidize a transition-
metal catalyst as well as a phosphine moiety of the ligand.
Since these undesired side reactions directly affect lower-
ing reactivities and enantioselectivities of the catalytic
processes, the stability of the transition-metal-based lig-
ands is pivotal for the further development of our planar-
chiral phosphine-olefin ligands. The tolerance (or sensi-
tivity) to air-oxidation of the CpMn(I)- and the
(arene)Cr(0)-based phosphine-olefin ligands was moni-
tored by the 31P-NMR measurements (Figures 3 and 4).
Phosphorus atoms P1 of the free phosphine moieties in
both rac-2b and rac-1b were protected as the correspond-
ing phosphine selenides, and the air-oxidation experi-
ments were carried out for rac-2b-Se and rac-1b-Se. The
31P-NMR spectra of rac-2b-Se showed the two signals at δ
27.9 and 93.5, which were assigned to P1 and P2 atoms,
respectively. As we expected, the manganese compound
was persistent in the air-oxidation, and the two spectra
taken in 10 min and in 14 h after the NMR sample prepa-
ration are essentially identical and showed no traces of
decomposition (Figure 3).
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Figure 4. 31P-NMR trace of rac-1b-Se solution in CDCl3 pre-
pared under air: (a) 10 min, (b) 2 h, and (c) 14 h after the
sample preparation.
On the other hand, the 31P-NMR spectra of (arene)Cr-
based rac-1b-Se changed drastically over time (Figure 4).
The freshly prepared sample of rac-1b-Se showed two
resonances at δ 35.8 and 82.2, which were assigned to P1
and P2 atoms, respectively, in the 31P-NMR spectrum (Fig-
ure 4, (a)). As time proceeded, the oxidative degradation
31
of rac-1b-Se was detected in the P-NMR spectra. In the
NMR sample kept under air for 2 h, four new peaks
emerged at δ –10.6, 30.9, 32.7, and 96.4 in addition to the
original two signals (Figure 4, (b)). The decomposition
was completed within 14 hours and the two signals from
rac-1b-Se were disappeared (Figure 4, (c)). The decompo-
sition process was also visibly observed: the clear orange
solution of rac-1b-Se (Figure 5, (a)) turned into a hetero-
geneous mixture of a yellow supernatant and green pre-
cipitate during 15 hours (Figure 5, (b)). On the contrary,
the clear yellow solution of manganese-based rac-2b-Se
did not change at all under the same conditions.
Figure 3. 31P-NMR trace of rac-2b-Se solution in CDCl3 pre-
pared under air: (a) 10 min, and (b) 14 h after the sample
preparation.
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5
(R)-2c
(R)-2d
60 (11am)
43 (11am)
94 (R)
32 (R)
1
2
3
4
5
6
7
8
6
a The reaction was carried out in dioxane/H2O (10/1) in the
presence of the rhodium catalyst (5 mol %) generated in situ
b
from [RhCl(C2H4)2]2 and the chiral ligand. Isolated yield by
silica gel chromatography. c Determined by chiral HPLC anal-
ysis. d Taken from ref-4b. The reaction mixture was stirred for
24 h.
9
The results in Table 1 indicated the superiority of
CpMn(I)-based ligands 2 over (arene)Cr(0)-based homo-
logues 1 in the Rh-catalyzed asymmetric 1,4-addition reac-
tions (see, entries 1 vs 3; entries 2 vs 4). With the more
promising ligand system in hands, the additional applica-
tion of 2b was examined and the results are summarized
in Table 2. The Rh/2b catalytic system was effective in the
1,4-addition to the longer acyclic enones as well. The ad-
dition of 10m to 3-hepten-2-one (9b) took place smoothly
to give the addition product 11bm in 92% yield and 99%
ee (entry 1). When 3-nonen-2-one (9c) was used as a sub-
strate, phenyl-addition product 11cm was obtained in a
remarkable level of enantioselectivity of 99.8% ee in 77%
yield (entry 2). The yields of the addition products gradu-
ally decreased as elongation of the alkyl chain in the acy-
clic enone, however, the high enantioselectivity was re-
tained in the phenylation of 3-decen-2-one (9d) with
99.7% ee (entry 3). The low yield (43%) in the reaction of
9d (entry 3) can be ascribed to competitive hydrolysis of
phenylboronic acid 10m.9a With the longer alkyl chain in
9d, the phenylrhodation to 9b (insertion of 9b to the Rh-
Ph intermediate)9b becomes slower, while 10m is hydro-
lyzed by a side reaction. Indeed, the reaction in entry 3
showed complete consumption of 10m within 48 h even
with a substantial amount of unreacted 9d.10
10
11
12
13
14
Figure 5. Photos of NMR sample tube containing a solution
of rac-1b-Se in CDCl3: (a) right after preparation, (b) kept for
15 h under air.
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Application of Planar-Chiral CpMn(I)-Based Lig-
ands to Rh-Catalyzed Asymmetric Reactions. A series
of CpMn(I)-based planar-chiral ligands 2a-d, the 2nd
generation phosphine-olefin ligands, were applied to the
various Rh-catalyzed asymmetric reactions. Firstly, the
potential of 2 was evaluated on the asymmetric 1,4-
addition reaction of phenylboronic acid (10m) to 3-
penten-2-one (9a).2,9 The asymmetric 1,4-addition reac-
tions to acyclic enones are known to be difficult to con-
trol due to their conformational flexibility, however, a
problematic reaction system was chosen as a benchmark
test of 2a-d. Indeed, as reported in 2014, the rhodium cat-
alyst generated in situ from [RhCl(C2H4)2]2 and (R)-1a or
(S)-1b promoted the asymmetric phenylation of 9a in low
yields with only 57% ee or 88% ee, respectively (Table 1,
entries 1 and 2).4b Meanwhile, the enantioselectivity was
improved to 92% ee by the use of (R)-2a, but the yield of
the product (11am) was still low in 32% (entry 3). To our
delight, both reactivity and enantioselectivity were mark-
edly updated by the use of (S)-2b which is with a bis(3,5-
dimethylphenyl)phosphino substituent on the cyclopen-
tadienyl ring to give 11am in 99% yield with 98% ee (entry
4). Electron deficient ligand (R)-2c also showed an excel-
lent enantioselectivity (94% ee), but the yield was moder-
ate (entry 5). The ligand (R)-2d, which is with an electron
Furthermore, CpMn-based ligand 2b showed the near-
perfect performance in the asymmetric 1,4-addition to a
series of cyclic enones (entries 4-10). In addition, various
arylboronic acids 10 were applied in the 1,4-addition to 9f
showing the enantioselectivities of over 99.2% ee with
nearly quantitative yields regardless of the nature of the
aryl substituents in 10 (entries 5-9).
Table 2. Rhodium-Catalyzed Asymmetric 1,4-Addition
of Arylboronic Acids (10) to Enones (9)a
rich
and
bulky
bis(3,5-di-tert-butyl-4-
methoxyphenyl)phosphino group, showed the very low
reactivity and enantioselectivity (entry 6).
Table 1. Rhodium-Catalyzed Asymmetric 1,4-Addition
of Phenylboronic Acid (10m) to 3-Penten-2-one (9a)a
entry
chiral ligand
(R)-1a
yield (%)b
31 (11am)
34 (11am)
32 (11am)
99 (11am)
% eec
57 (S)
88 (R)
92 (R)
98 (S)
1d
2d
3
(S)-1b
entry
1
sub-
strate
ArB(OH) 2b
yield (%)b
% eec
98.9
(R)-2a
2
4
(S)-2b
9b
10m
(S) 92 (11bm)
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(S)
ined in the 1,2-addition of phenylboroxine to the other
1
2
3
4
5
6
7
8
imine substrates (Table 4). The phenylation of p-
methoxybenzaldehyde N-tosylimine proceeded quantita-
tively with very high enantioselectivities using either of
(S)-2c or (S)-2d (entries 1 and 2). It is worth mentioning
that the ligand (S)-2c afforded the desired product in ex-
tremely high enantioselectivity of 99.9% ee. The similar
trend in high reactivities and selectivities was observed in
the reaction of o-methoxybenzaldehyde N-tosylimine
(entries 3 and 4). The activity of [Rh]/(S)-2c catalysis was
slightly diminished compared to that of [Rh]/(S)-2d for
the reaction of the N-tosylimine having an electron with-
drawing substituent, although the enantioselectivities
were still very high (entries 5 and 6). The lower activity of
(S)-2c shown in entry 5 is correlated with the reactivity
toward electron deficient p-chlorobenzaldehyde N-
tosylimine (Table 3, entry 5). To our delight, both ligands
were also applicable in the asymmetric reaction of the
imine substrates having a heteroarene substituent, and
the addition products were obtained in >99.7% ee (entries
7-10). All in all, both (S)-2c and 2d are equally reactive
and highly enantioselective in the rhodium-catalyzed
asymmetric 1,2-addition reactions giving the addition
products over 99.0% ee in all cases.
9c
10m
99.8
(S)
2d
3e
4
(S)
77 (11cm)
9d
9e
10m
10m
(S) 43 (11dm) 99.7 (S)
99.6
(R) 99 (11em)
(S)
9f
9f
9f
10n
10o
10p
99.8
(R)
5
(S)
(S)
99 (11fn)
99 (11fo)
9
99.9
(R)
6
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
99.9
(S)
7
8
9
(R)
(R)
(R)
99 (11fp)
99 (11fq)
99 (11fr)
9f
9f
10q
10r
99.2 (S)
99.6
(S)
9g
10m
99.9
(S)
10
(R) 99 (11gm)
a The reaction was carried out in dioxane/H2O (10/1) in the
presence of the rhodium catalyst (5 mol %) generated in situ
b
from [RhCl(C2H4)2]2 and 2b. Isolated yield by silica gel
chromatography. c Determined by chiral HPLC analysis. d The
e
reaction mixture was stirred for 24 h. The reaction mixture
was stirred for 48 h.
Table 4. Rhodium-Catalyzed Asymmetric 1,2-Addition
of Phenylboroxine to Arylaldehyde N-Tosyliminesa
Newly developed CpMn(I)-based ligands 2 were also
tested in the rhodium-catalyzed asymmetric 1,2-addition
of phenylboroxine to p-chlorobenzaldehyde N-tosylimine
(Table 3).11 For this reaction, (S)-2c and (S)-2d were found
to be the most promising ligands showing very high enan-
tioselectivities in 99.6% ee and 99.2% ee, respectively,
although the yield of the desired addition product with
(S)-2c was moderate (entries 5 and 6).
entry
Ar in to-
sylimine
(S)-2
yield
(%)b
% eec
Table 3. Rhodium-Catalyzed Asymmetric 1,2-Addition
of Phenylboroxine to p-Chlorobenzaldehyde N-
Tosyliminea
1
2
2c
2d
2c
2d
2c
2d
2c
2d
2c
2d
99
99
99
99
88
96
99
97
99
89
99.9 (S)
99.6 (S)
99.9 (S)
99.0 (S)
99.8 (S)
99.6 (S)
99.8 (S)
99.8 (S)
99.9 (S)
99.7 (S)
p-C6H4OMe
o-C6H4OMe
p-C6H4CF3
2-furyl
3
4
5
6
7
entry
chiral ligand
(R)-1a
yield (%)b
% eec
88 (S)
8
9
10
1d
2d
3
94
98
64
99
62
92
2-thienyl
(S)-1b
93 (R)
85 (S)
(S)-2a
a The reaction was carried out in dioxane/H2O (50/1) in the
presence of the rhodium catalyst (5 mol %) generated in situ
4
(S)-2b
94 (S)
99.6 (S)
99.2 (S)
b
from [RhCl(C2H4)2]2 and (R)-2. Isolated yield by silica gel
5
(S)-2c
chromatography. c Determined by chiral HPLC analysis.
6
(S)-2d
Optically active chiral diarylmethanols are important
synthetic intermediates as key building blocks for various
biologically active compounds. A straightforward method
of preparing these compounds is an asymmetric nucleo-
philic addition of an aryl nucleophile to an appropriate
arylaldehyde. The reactions between an arylzinc reagent
and an arylaldehyde have been studied in the presence of
a chiral Lewis-base with fair success.12 The transition-
a The reaction was carried out in dioxane/H2O (50/1) in the
presence of the rhodium catalyst (5 mol %) generated in situ
b
from [RhCl(C2H4)2]2 and the chiral ligand. Isolated yield by
silica gel chromatography. c Determined by chiral HPLC anal-
ysis. d Taken from ref-4b.
After the initial screening experiments shown in Table 3,
applicability of both (S)-2c and (S)-2d was further exam-
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Journal of the American Chemical Society
metal-catalyzed variants of these asymmetric reactions
have been developed as well. To our best knowledge, the
1
2
first example of the transition-metal-catalyzed reaction
was reported by Miyaura and co-workers in 1998 using a
rhodium catalyst and phenylboronic acid as a nucleo-
phile.13a Since then, rhodium catalysts coordinated with a
chiral ligand have played central roles in the asymmetric
reactions.13 As summarized in Scheme 4, however, the
rhodium-catalyzed reactions clearly need further im-
provement in terms of enantioselectivities. Whereas (S)-
2c and (S)-2d showed the excellent performance in the
rhodium-catalyzed 1,2-addition to the imines (Tables 3
and 4), next we turned our attention to their application
in the related 1,2-addition of phenylboronic acid to 1-
naphthaldehyde. Although the rhodium catalyst generat-
ed from [RhCl(C2H4)2]2 and (S)-2c showed poor results
(27% ee and 26% yield), Rh/(S)-2d catalyst afforded the
desired diarylmethanol in excellent enantioselectivity of
99.3% ee in 51% yield (Scheme 4, top). For this reaction,
the clear difference in enantioselectivities was observed
between (S)-2c and (S)-2d. The asymmetric reaction be-
tween phenylboronic acid and 1-naphthaldehyde was also
reported using nickel14 or ruthenium15 catalysts. And, the
ruthenium catalyst showed the highest enantioselectivity
so far with 98% ee (Scheme 4, bottom).15 It should be
mentioned that the Rh/(S)-2d catalyst outperformed the
ruthenium catalyst as well in the 1,2-addition reaction in
terms of the enantioselectivity. The results shown in
Scheme 4 displayed the great potential of phosphine-
olefin ligands 2 in transition-metal-catalyzed asymmetric
reactions.
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
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35
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37
38
39
40
41
42
43
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46
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50
51
52
53
54
55
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57
58
59
60
Consideration of Structural Difference between 2b
and 1b. Single crystals of (+)-2b suitable for X-ray crystal-
lography were grown from the chloroform solution as
orange prisms. The crystal structure of (+)-2b is shown in
Figure 6 (a) (see the Supporting Information for details),
which revealed the absolute configuration of dextrorota-
tory 2b ([α]D26 +135.1 (c 0.5, CHCl3)) to be (R). The config-
urations of the other CpMn-based phosphine-olefin lig-
ands 2 are determined by analogy.
Scheme 4. Rhodium-Catalyzed Asymmetric 1,2-
Addition of Phenylboronic Acid to 1-Naphthaldehyde.
The single-crystal X-ray analysis of the homologous
bis(3,5-dimethylphenyl)phosphino-derivative
of
the
(arene)Cr(0)-based phosphine-olefin ligand, rac-1b, was
also conducted for comparison, and its ball & stick draw-
ings is shown in Figure 6 (b). Although both 2b and 1b
display similar overall structures each other, the local
substructures around the central metals (Mn in 2b; Cr in
1b) show a clear contrast between the two.16 The metal
(Cr)-phosphorus bond in 1b (2.280(1) Å) is ca. 3% longer
than that in 2b (Mn(1)-P(2) = 2.209(1) Å), and the η6-
arene ligand in 1b is larger than the η5-cyclopentadienyl
ligand in 2b. Although arene(centroid)-Cr(1) distance
(1.674 Å) in 1b is considerably shorter than Cp(centroid)-
Mn(1) distance in 2b (1.773 Å), the chelate ring size in 2b
is smaller than that in 1b. Consequently, Cp(centroid)-
Mn(1)-P(2) angle in 1b (121.88°) is much smaller than
arene(centroid)-Cr(1)-P(2) angle in 1b (124.68°).
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(a)
(b)
1
2
3
4
5
6
7
arene(centroid)
Cp(centroid)
P(1)
8
9
P(1)
1.674 Å
1.773 Å
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Mn
Cr
124.68°
121.88°
P(2)
P(2)
2.209(1) Å
2.280(1) Å
Figure 6. Ball & stick drawings of (a) (R)-2b and (b) rac-1b with selected atom numbering. All hydrogen atoms are omitted for
clarity.
(a)
(b)
C(40)
C(41)
O(2)
86.1(2)°
O(3)
P(1)
Rh(1)
Mn(1)
P(2)
P(4)
Cl(2)
Rh(2)
Cl(1)
Mn
Rh
P(1)
C(1)
Cl(2)
Cl(1)
C(1)
P(3)
Mn(2)
O(1)
O(4)
C(2)
Figure 7. Ball & stick drawings of (a) [RhCl/(S*)-2b]2 ((S*,S*)-12) and (b) monomeric substructure of (S*,S*)-12 with selected atom
numbering. All hydrogen atoms and cocrystallized solvent molecules are omitted for clarity. Both xylyl groups on P(3) atom are
disordered over two positions (one of the two observed P(3)-xylyl2 groups is shown in (a). See Supporting Information for detail).
A part of structure (b) is shown as a wireframe drawing for clarity.
Next, the coordination mode of phosphine-olefin ligand
2b to a rhodium(I) center was examined by the X-ray
crystallography. A (ꢀ-Cl)2-bridged dinuclear rhodium(I)
complex with 2b, [Rh(I)/2b]2 (12), was prepared from
[RhCl(CH2=CH2)2]2 and rac-2b (1 equiv. to Rh) nearly
quantitatively. Whereas racemic 2b was used for the
preparation of 12, the rhodium complex comprises of both
(R,R)- and (S,S)-12 enantiomers in the 1:1 molar ratio. In-
terestingly, complex 12 showed the strong preference for
the formation of the homoenantiomeric dimer, and the
corresponding mesomeric dimer, (R,S)-12, was not detect-
ed either in the solid state (by the X-ray crystallography)
or in solution (by the NMR spectroscopy). Single-crystals
of 12 were obtained as dark brown prisms by recrystalliza-
tion from dichloromethane/hexane. Complex 12 cocrystal-
lizes with two dichloromethane molecules per dimeric
unit, and the ball and stick drawing of (S*,S*)-12 is shown
in Figure 7 (a) (see Supporting Information for details).
The determined solid-state structure of (S*,S*)-12 is pseu-
do-C2-symmetric and consists of two similar but crystal-
lographically independent [Rh(I)/(S*)-2b] units. The crys-
tal structure confirms the bidentate coordination of 2b to
the Rh(I) cation as a phosphine-olefin chelate. The bond
lengths of the coordinating olefin moieties (C(1)-C(2) and
C(40)-C(41)) in (S*,S*)-12 are 1.423(8) and 1.41(2) Å, respec-
tively, which are ca. 6% longer than that in free ligand
(R)-2b.
The X-ray single-crystal analysis of the Rh(I) complex
coordinated with 1b, [RhCl/(R*)-1b]2 ((R*,R*)-SI1), was also
examined for comparison (not shown in the main text,
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see Supporting Information), which reveals the crystal
structures of the two rhodium complexes are quite similar.
1
2
The clear difference between the two structures is detect-
ed in the phosphine-rhodium-olefin bite angles (Figure 7
(b)). While the average bite angle in (S*,S*)-12 is 86.1(2)°
[P(1)-Rh(1)-C(1) = 86.5(2)°, P(3)-Rh(2)-C(40) = 85.7(2)°],
that in (R*,R*)-SI1 is 84.5(1)°. The two donor moieties
(Xyl2P-substituent and the olefin) in 2b are arrayed on the
five-membered CpMn scaffold. On the other hand, the
structural core in 1b is the six-membered (arene)Cr on
which the two donors are arranged. Our previous studies
revealed that the orientations of the two phosphorus-
bound aryl groups as well as of the olefin-bound methyl
group are primarily constructing the chiral environment
around the rhodium center.4b The different bite angles
between 2b and 1b should lead to the different orienta-
tions of the Xyl2P- and the -CH=CMe- moieties in the Rh
complexes,17 which may be an origin of the better enanti-
oselectivity of 2b.
3
4
5
6
7
8
9
10
11
12
13
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43
44
45
46
47
48
49
50
51
52
53
54
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56
57
58
59
60
Consideration of Stereochemical Pathways in Rho-
dium-Catalyzed 1,4- and 1,2-Addition Reactions. On
the basis of the results in Table 1 and the structural anal-
yses mentioned above, the stereochemical pathway of the
1,4-addition reaction of phenylboronic acid (10m) to 3-
pentene-2-one (9a) catalyzed by Rh/(S)-2b can be ration-
alized as shown in Scheme 5-(a). The phenylrhodium spe-
cies has trans-relationship between the Rh-bound phenyl
group and the olefin ligand,3g and 9a coordinates to the
rhodium center with its si-face at the cis-position of the
olefin ligand to minimize the steric repulsion with coor-
dinating (S)-2b. Subsequent insertion of 9a to the Rh-Ph
bond followed by hydrolysis gives the 1,4-adduct with (S)-
configuration. On the other hand, coordination of 9a to
the rhodium center with the re-face was disfavored due to
the steric repulsion between the acetyl tether in 9a and
the methyl group on the ligating olefin moiety in (S)-2b.
CONCLUSIONS
A new family of chiral phosphine-olefin bidentate lig-
ands 2, whose chirality is based on a planar-chiral (η5-
cyclopentadienyl)manganese(I) dicarbonyl scaffold, has
been developed. Ligand 2 shows the better robustness as
well as the higher enantioselectivity over homologous (η6-
arene)chromium(0)-based planar-chiral phosphine-olefin
ligands 1. We have developed the general and enantiospe-
cific synthetic method of 2 that can be conducted in a
macroscale with ease. Whereas the chelate coordination
of 2 to a rhodium(I) cation constructs the effective chiral
environment at the rhodium(I) center, the rhodium com-
plexes of 2 display excellent catalytic performances in the
various asymmetric reactions with arylboron nucleophiles.
Likewise, the stereochemical pathway of the 1,2-addition
of phenylboroxine to arylaldehyde imine can be rational-
ized in the similar way (Scheme 5-(b)). Thus, the imine
approaches the rhodium with its si-face at the cis-position
of the olefin ligand to give (S)-enantiomer of the phenyla-
tion product.
Ligand
2b,
which
is
with
bis(3,5-
dimethylphenyl)phosphino group on the cyclopentadi-
enyl ring, shows very high enantioselectivity in the rhodi-
um-catalyzed asymmetric 1,4-addition reactions of aryl-
boronic acids to various cyclic and acyclic enones to give
the corresponding arylation products in up to 99.9% ee.
Scheme 5. Proposed Stereochemical Pathways for (a)
Rh/(S)-2b-Catalyzed Enantioselective 1,4-Addition of
Phenylboronic Acid to 3-Pentene-2-one and (b)
Rh/(S)-2d-Catalyzed Enantioselective 1,2-Addition of
Phenylboroxine to Arylaldehyde N-Tosylimine.
Ligands
2c
(with
bis[3,5-
bis(trifluoromethyl)phenyl]phosphino group) and 2d
(with bis(3,5-di-tert-buthyl-4-methoxyphenyl)phosphino
group) are suited for the rhodium-catalyzed asymmetric
1,2-addition reactions of the arylboron nucleophiles to
imines or aldehydes showing up to 99.9% ee selectivity.
ASSOCIATED CONTENT
Supporting Information. Experimental procedures, com-
pound characterization data, and crystallographic data of
(R)-2b, rac-1b, [RhCl/(S*)-2b]2 ((S*,S*)-12), [RhCl/(R*)-1b]2
((R*,R*)-SI1) in CIF formats. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
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Chemistry; Astruc, D., Ed.; Wiley-VCH: Weinheim, 2002; Chap-
kamikawa@c.s.osakafu-u.ac.jp
ogasawar@tokushima-u.ac.jp
1
2
3
4
5
6
7
8
ter 11, p. 368. (c) Gibson, S. E.; Ibrahim, H. Chem. Commun. 2002,
2465. (d) Kündig, E. P.; Pache, S. H. Sci. Synth. 2003, 2, 155. (e)
Salzer, A. Coord. Chem. Rev. 2003, 242, 59. (f) Schmalz, H.-G.;
Dehmel, F. In Transition Metals for Organic Synthesis. Building
Blocks and Fine Chemicals; Beller, M.; Bolm, C., Eds.; Wiley-
VCH: Weinheim, 2004, Vol. 1, Chapter 3.12, p. 601. (g) Transition
ACKNOWLEDGMENT
This work was supported by a Grant-in-Aid for Scientific
Research on Innovative Areas "Precisely Designed Catalysts
with Customized Scaffolding" to K.K. (Grant #JP16H01039)
from JSPS, Japan, and a Grant-in-Aid for Scientific Research
(B) to M.O. (Grant #15H03805) from MEXT, Japan. K.K. and
M.O. also thank the Naito Foundation. K.K. thanks Yamada
Science Foundation. We also thank Prof. Ikuko Miyahara
(Osaka City University) and Prof. Shin Takemoto (Osaka
Prefecture University) for supporting the measurements of
X-ray analysis.
Metal Arene
π-Complexes in Organic Synthesis and Catalysis,
Kündig, E. P., Ed.; Springer, Berlin, 2004, Topics in Organome-
tallic Chemistry Vol. 7. (h) Uemura, M. Org. React. 2006, 67, 217.
(i) Rosillo, M.; Dominguez, G.; Perez-Castells, J. Chem. Soc. Rev.
2007, 36, 1589.
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Schlögl, K.; Fried, M.; Falk, H. Monatsh. Chem. 1964, 95, 576. (c)
Schlögl, K.; Falk, H. Angew. Chem. Int. Ed. 1964, 3, 512.
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(10) The reaction between 4-phenylbut-3-en-2-one and 10m in
the presence of [RhCl(C2H4)2]2/2b (5 mol %/Rh) was very tardy.
And thus, the competitive hydrolysis of 10m was predominant
furnishing the addition product in <20% yield.
(11) For selected examples, see: (a) Kuriyama, M.; Soeta, T.;
Hao, X.; Chen, Q.; Tomioka, K. J. Am. Chem. Soc. 2004, 126, 8128.
(b) Tokunaga, N.; Otomaru, Y.; Okamoto, K.; Ueyama, K.; Shin-
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1295; (c) Huang, W.-S.; Pu, L. J. Org. Chem. 1999, 64, 4222. For
some asymmetric addition of diarylzinc generated from aryl-
boronic acid, see: (d) Bolm, C.; Rudolph, J. J. Am. Chem. Soc.
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(4) (a) Ogasawara, M.; Wu, W.-Y.; Arae, S.; Morita, T.;
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(5) (a) Pape, A. R.; Kaliappan, K. P.; Kündig, E. P. Chem. Rev.
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Tetrahedron, 2007, 63, 12961. (c) Focken, T.; Rudolph, J.; Bolm, C.
(14) (a) Arao, T.; Kondo, K.; Aoyama, T. Tetrahedron Lett.,
1
2
3
4
5
6
7
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Synthesis, 2005, 429. (d) Zhang, W.; Qin, Y.; Zhang, S.; Luo, M.
ARKIVOC, 2005, 14, 39. (e) Jagt, R. B. C.; Toullec, P. Y.; de Vries, J.
G.; Feringa, B. L.; Minnaard, A. J. Org. Biomol. Chem., 2006, 4,
773. (f) Duan, H.-F.; Xie, J.-H.; Shi, W.-J.; Zhang, Q.; Zhou, Q.-L.
Org. Lett., 2006, 8, 1479. (g) Arao, T.; Sato, K.; Kondo, K.; Aoya-
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Kondo, K.; Aoyama, T. Synlett, 2006, 648. (j) Arao, T.; Suzuki,
K.; Kondo, K.; Aoyama, T. Synthesis, 2006, 3809. (k) Nishimura,
T.; Kumamoto, H.; Nagaosa, M.; Hayashi, T. Chem. Commun.
2009, 5713. (l) Ma, Q; Ma, Y.; Liu, X.; Duan, W.; Qu, B.; Song, C.
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K.; Aoyama, T. Synthesis, 2008, 3585.
(15) Kurihara, K.; Yamamoto, Y.; Miyaura, N. Angew. Chem. Int.
Ed., 2009, 351, 4414.
(16) Tseng, Y.-Y.; Kamikawa, K.; Wu, Q.; Takahashi, T.;
Ogasawara, M. Adv. Synth. Catal. 2015, 357, 2255.
(17) For reviews on the influence of the bite-angle of bidentate
phosphine ligands, see: (a) van Haaren, R. J.; Oevering, H.;
Coussens, B. B.; van Strijdonck, G. P. F.; Reek, J. N. H.; Kamer, P.
C. J.; van Leeuwen, P. W. N. M. Eur. J. Inorg. Chem. 1999, 1237.
(b) Oestreich, M. Eur. J. Org. Chem. 2005, 783. (c) Johns, A. M.;
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2006, 128, 1828.
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O
Me
1
2
R2
P
Me
n
[Rh]
3
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PhB(OH)2
Me
Mn
CO
CO
P
Ph2
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Ph
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Me
R = Ph, Xylyl,
(CF3)2C6H3, DTBM
Me
98-99.8% ee
n
[Rh/(S*)-2b]
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