Chiral sulfoxide-olefin ligands: Completely switchable stereoselectivity in rhodium-catalyzed asymmetric conjugate additions

Article abstract of DOI:10.1002/anie.201102586

Have it both ways: A novel class of chiral sulfoxide-olefin ligands was synthesized from a single chiral source. These ligands were evaluated in rhodium-catalyzed 1,4-additions of arylboronic acids to electron-deficient olefins, and remarkable olefin-directed reversal of stereoselectivity (up to >99 ee, R isomer; 98 ee, S isomer) was observed when the reversal ligand pair L1 (branched olefin) and L2 (linear olefin) were utilized (see scheme). Copyright

Full text of DOI:10.1002/anie.201102586

DOI: 10.1002/anie.201102586
Asymmetric Catalysis
Chiral Sulfoxide-Olefin Ligands: Completely Switchable Stereoselec-
tivity in Rhodium-Catalyzed Asymmetric Conjugate Additions**
Guihua Chen, Jiangyang Gui, Liangchun Li, and Jian Liao*
The design and synthesis of novel chiral ligands is an
important part of developing enantioselective transition-
metal-catalyzed reactions[1] which provide access to both
enantiomers.[2] Reaction parameters (such as pressure, sol-
vent, counterions, and additives),[3] the choice of metal,[4]
tunable ligands,[5] and so on,[6,7] play a critical role in the
optimization of a particular asymmetric transformation.
Among these criteria, the design of different ligands from a
single easily accessible chiral source is an attractive strategy.
As a ubiquitous structural element, olefins have attracted
intense attention as ligands in organometallic chemistry,[8]
owing to the independent contributions of Hayashi et al.
and Carreira and co-workers.[9] Several novel cyclic chiral
dienes were developed that exhibit unique and exciting
properties in transition-metal-catalyzed asymmetric reac-
tions.[10] Recently, Du and co-workers as well as Yu and co-
workers independently reported two types of acyclic chiral
diene ligands that provide good to excellent enantioselectivity
in asymmetric reactions.[11] Furthermore, olefins were also
successfully utilized in the design of hybrid bidentate ligands,
such as olefin-phosphine[12] and olefin-nitrogen ligands.[13]
Nevertheless, we are unaware of hybrid chiral sulfoxide-
olefin ligands.[14] Sulfoxides have a long history in asymmetric
catalysis,[15] and these compounds were recently highlighted
by Dorta and co-workers.[16] We have focused on the design of
chiral ligands based on the tert-butylsulfinyl moiety[17] since
these ligands provide encouraging results in transition-metal-
catalyzed asymmetric reactions.[18] Inspired by the previous
reports in this area, we elected to prepare a hydrid ligand
from the combination of an olefin with a tert-butylsulfinyl
moiety. Interestingly, the relative size of the substituents
very important for asymmetric induction, particularly for
asymmetric hybrid ligands, which could potentially control
the absolute configuration of the product. Herein, we
describe the development of a novel class of hybrid sulfox-
ide-olefin ligands and evaluate the efficiency and selectivity of
this type of ligand in the rhodium-catalyzed asymmetric 1,4-
addition of arylboronic acids to electron-deficient olefins; a
reaction which was originally reported by Miyaura, Hayashi,
and co-workers and is considered as one of the most
[19]
À
important methods for asymmetric C C bond formation.
The synthesis of the sulfoxide-olefin ligands L1–L5 is
outlined in Scheme 1. (R)-tert-Butyl tert-butanethiosulfinate
was added to the 1-bromo-2-vinylbenzenes 1–3 after a
standard halogen-metal exchange at low temperature, to
Scheme 1. Synthesis of chiral sulfoxide-olefin ligands L1–L5. Bn=ben-
zyl, THF=tetrahydrofuran.
=
attached to the C C bonds in a diene ligand is considered to
be the key factor for the origin of stereocontrol. We believe
that the position of the substituents on the olefin may also be
furnish the styrene-type ligand L1 and the branched olefin
ligands L2 and L3 in 38-77% yield. Similarly, the synthesis of
linear olefin ligands L4[20] and L5 was also accomplished from
(R)-2-(tert-butylsulfinyl)benzaldehyde (4) in a single step, in
71% and 79% yield, respectively, by using a Wittig and a
Horner–Wadsworth–Emmons reaction.
[*] G. Chen, J. Gui, Dr. L. Li, Prof. Dr. J. Liao
Natural Products Research Center, Chengdu Institute of Biology
Chinese Academy of Sciences, Chengdu 610041 (China)
and
To test these ligands, we initiated our studies with the
rhodium-catalyzed conjugate addition of phenylboronic acid
(5a) to cyclohexenone (6k). As illustrated in Table 1, ligand
screening revealed that all the sulfoxide-olefins tested were
effective ligands for this transformation in the context of the
reaction efficiency (74–93% yield). The most striking feature
of this study was the effect that the substituents on the olefin
had on enantioselectivity. For example, the monosubstituted
olefin L1, provided only modest enantioselectivity (Table 1,
entry 1), whereas the disubstituted ligands L2–L5 provided
good to excellent selectivities. Interestingly, the opposite
Chengdu Institute of Organic Chemistry
Chinese Academy of Sciences, Chengdu, 610041 (China)
and
Graduate School of Chinese Academy of Sciences
Beijing 100049 (China)
E-mail: jliao@cib.ac.cn
[**] We thank the NSFC(No. 21072186 and 20872139), CAS, Chengdu
Institute of Biology of CAS (Y0B1051100), the Major State Basic
Research Development Program (973 program, 2010CB833300),
and Jiangxi Key Laboratory of Functional Organic Molecules.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201102586.
Angew. Chem. Int. Ed. 2011, 50, 7681 –7685
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
7681

Communications
Table 1: Screening of reaction conditions.[a]
With the optimized reaction conditions established, a
wide range of arylboronic acids, cyclic/linear enones, and
cyclic esters were examined to investigate the scope of the
switch in stereochemistry (Table 2). Herein, L2 (Me) and L4
(Me), and L3 (Ph) and L5 (Ph) are defined as reversal ligand
pairs (RLPs), according to the substituents on the ligands
Entry
L
Solvent
Base
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
L1
L2
L3
L4
L5
L4
L4
L4
L4
L4
L4
L4
dioxane
dioxane
dioxane
dioxane
dioxane
THF
toluene
CH2Cl2
MeOH
EtOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
Et3N
KF
91
93
74
91
78
95
88
95
98
96
98
93
20 (R)
94 (R)
94 (R)
88 (S)
96 (S)
84 (S)
46 (S)
48 (S)
95 (S)
91 (S)
88 (S)
98 (S)
Table 2: Substrate scope of the rhodium-catalyzed 1,4-addition of
arylboronic acid to electron-deficient olefins.[a]
9
10
11[d]
12
MeOH
MeOH
[a] Reaction conditions: 0.3 mmol of 5a, 0.6 mmol of 6k, 1.2 mg of
[{Rh(C2H4)2Cl}2] (0.003 mmol, 2.0 mol% of Rh), 0.0072 mmol of L,
0.6 mL of solvent, 50 mol% of base, 408C, 3 h. [b] Yield of the isolated
product. [c] Determined by HPLC analysis on a chiral stationary phase.
The absolute configuration was determined by comparison with
literature data. [d] Et3N was used neat.
Entry
1
5
R
L
Yield [%][b]
ee [%][c]
absolute configuration of 7ak was obtained using the
branched L2 and L3 olefin ligands (R, up to 94% ee) and
linear L4 and L5 olefin ligands (S, up to 96% ee; Table 1,
entries 2–5). In additional studies, L4 was utilized to screen
the reaction conditions, and these studies demonstrated that
the nature of the solvent and base dramatically affect the
selectivity; excellent enantioselectivity (98% ee) was ach-
ieved using methanol and potassium fluoride (Table 1,
entry 12).[21]
We next examined other common arylboronic reagents in
this system, and these studies demonstrated that phenybor-
oxine and potassium trifluoroborate provided excellent yields
and good enantioselectivities. However, when sodium tetra-
phenylborate was used, only a trace amount of the product
was obtained (Scheme 2).
5a
H (6k)
L2
L4
L3
L5
L2
L4
L2
L4
L2
L4
L2
L4
L2
L4
L2
L4
L3
L5
L2
L4
L2
L4
L2
L4
L2
L4
L2
L4
L2
L4
L2
L4
L2
L4
L3
L5
L2
L4
98
93
98
97
98
90
98
96
98
97
80
82
93
85
98
98
82
82
97
98
81
97
98
97
98
98
97
94
98
97
83
97
98
91
97
99
57
30
>99 (R)
98 (S)
95 (R)
97 (S)
>99 (R)
97 (S)
99 (R)
96 (S)
94 (R)
97 (S)
>99 (R)
98 (S)
99 (R)
97 (S)
98 (R)
66 (S)
90 (R)
81 (S)
99 (R)
97 (S)
>99 (R)
97 (S)
>99 (R)
96 (S)
>99 (R)
85 (S)
>99 (R)
95 (S)
90 (R)
96 (S)
94 (R)
92 (S)
99 (R)
64 (S)
97 (R)
87 (S)
93 (R)
42 (S)
2
3
5a
5a
5a
5a
5a
5a
p-CH3 (6l)
4
m-CH3 (6m)
o-CH3 (6n)
5
6
p-CH3O (6o)
m-CH3O (6p)
o-CH3O (6q)
7
8
9
10
11
12
13
14
15
16
17
18
19
5a
5a
5a
5a
5a
5a
5a
5a
p-tBu (6r)
3,5-CH3 (6s)
p-F (6t)
p-CF3 (6u)
p-Cl (6v)
m-Cl (6w)
1-naph (6x)
2-naph (6y)
=
(E)-PhCH CH (6z)
5a
Scheme 2. Evaluation of other arylboronic reagents.
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Angew. Chem. Int. Ed. 2011, 50, 7681 –7685

Table 2: (Continued)
Entry
20
5
R
L
Yield [%][b]
ee [%][c]
5b
H (6k)
L2
L4
L3
L5
L2
L2
L4
L2
L2
98
98
90
97
97
71
85
96
95
96 (R)
26 (S)
77 (R)
93 (S)
98 (R)
87 (R)
78 (S)
44 (S)
65 (+)
21
22
23
5c
5d
H (6k)
H (6k)
24
25
5e
5 f
H (6k)
p-CH3 (6l)
Figure 1. ORTEP illustration of [(L3RhCl)2] with thermal ellipsoids
drawn at the 50% probability level.
[a] Reaction conditions: 0.3 mmol of 5, 0.6 mmol of 6, 1.2 mg [{Rh-
(C2H4)2Cl}2] (0.003 mmol, 2.0 mol% of Rh), 0.0072 mmol of L, 0.6 mL of
MeOH, 50 mol% of KF, 408C, 3 h. [b] Yield of the isolated product.
[c] Determined by HPLC analysis on a chiral stationary phase. The
absolute configuration was determined by comparison with literature
data. naph=naphthyl.
(R = Me or Ph; Scheme 1), and each pair could induce the
formation of both absolute configurations in the products. To
our delight, complete reversal of enantioselectivity was
observed for most of the substrates, with up to > 99% ee
(R) and 98% ee (S) when the L2 and L4 RLP was used
(Table 2, entries 1 and 6). In some specific cases the L2 and L4
RLP did not work well (Table 2, entry 20; L2 96% ee,
R isomer; L4 26% ee, S isomer), but complementary results
could be achieved with the L3 and L5 RLP (Table 2, entry 21;
L3 77% ee, R isomer; L5 93% ee, S isomer). For the
cycloheptenone 5c, L2 furnished excellent enantioselectivity,
but the related ligands L4 and L5 failed to provide inversion,
and only a trace amount of the product was formed (Table 2,
entry 22). Furthermore, modest yields and enantioselectiv-
ities were obtained when the cyclic ester 5d was used as the
substrate (Table 2, entry 23). Similar to 5c, acyclic enone 5e
and chalcone 5 f could smoothly react in the presence of L2 to
give the corresponding adducts with excellent yields and
modest enantioselectivities (Table 2, entries 24 and 25).[22]
To gain insight into this interesting phenomenon, some
structural information on the catalyst was obtained. Treat-
ment of L3 with [{Rh(C2H4)2Cl}2] in dichloromethane at 258C
for 30 minutes gave the corresponding sulfoxide-olefin/rho-
dium complex, [(L3RhCl)2]. Suitable crystals of this complex
for X-ray crystal-structure analysis were obtained by recrys-
tallization from dichloromethane/n-hexane (Figure 1).[23] In
this structure, the sulfur atom and the carbon-carbon double
bond of L3 coordinate to the rhodium atom, and notably the
rhodium atom coordinates with the a-Si face of the a-
phenylvinyl group. The phenyl and tert-butyl groups provide
an excellent stereoenvironment that presumably results in the
high enantioselectivity in the 1,4-addition. On the basis of the
switch in configuration, which is attributed to the olefin
substitution, the stereochemical pathway with Rh/L3 and Rh/
L5 can be rationalized as outlined in Figure 2. Thus, the initial
coordination of the rhodium species results in a trans rela-
tionship between the phenyl group and the olefin moiety, and
the substrate 2-cyclohexen-1-one binds to the rhodium center
at the position cis to the olefin ligand, because of steric
repulsion between the alkyl or phenyl group of the ligand with
Figure 2. Proposed stereochemical pathway showing the facial coordina-
tion of the rhodium atom with the enone substrate: a) Using L3, b) using
L5.
the carbonyl moiety, thus leading to the 1,4-adduct with the
desired configuration.
In conclusion, we have successfully developed a new
family of chiral sulfoxide-olefin ligands from a single chiral
source through a concise synthetic route, and evaluated these
ligands in the rhodium-catalyzed 1,4-addition of arylboronic
acids to electron-deficient olefins. These ligands demon-
strated that the olefin geometry can completely reverse the
absolute configuration of the product, thus simplifying the
process of accessing either enantiomer.
Experimental Section
In an argon atmosphere, at room temperature, [{Rh(C2H4)2Cl}2]
(1.2 mg, 0.003 mmol) and the sulfoxide-olefin ligand (1.6 mg,
0.0072 mmol) were added to a 10 mL Schlenk tube followed by
CH2Cl2 (0.50 mL). The reaction mixture was stirred at room temper-
ature for 30 min, then the CH2Cl2 was removed and the arylboronic
acid (0.60 mmol) was added. After purging the mixture with argon,
enone (0.30 mmol), methanol (0.60 mL) and KF (0.15 mL, 1.0m in
H2O, 0.15 mmol) were added sequentially. The reaction mixture was
stirred at 408C for 3 h, then the solvent was removed in vacuo and the
Angew. Chem. Int. Ed. 2011, 50, 7681 –7685
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www.angewandte.org
7683

Communications
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Received: April 14, 2011
Published online: June 17, 2011
Keywords: chirality · conjugate addition · rhodium · S ligands ·
.
stereoselectivity reversal
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1
[20] The Z isomer (< 5%) of L4 was observed by H NMR analysis
of the crude product.
[21] For the detailed screening of the reaction conditions, see the
Supporting Information.
[22] The absolute configuration of adduct 7ek was S, which is
=
probably influenced by the geometry of the C C bond of the
substrate. We attempted to prove this and (Z)-5 f was used,
however, only 50% conversion was achieved (64% ee for (+)-
7 fl) and 50% of (E)-5 f was obtained. For selected examples of
the reversal of stereoselectivity determined by the configuration
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[23] CCDC 824876 ([(L3RhCl)2]) contains the supplementary crys-
tallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Angew. Chem. Int. Ed. 2011, 50, 7681 –7685
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7685