A New Type of Chiral Cyclic Sulfinamide–Olefin Ligands for Rhodium-Catalyzed Asymmetric Addition

Article abstract of DOI:10.1002/ejoc.201601206

A new type of chiral cyclic sulfinamide–olefin ligands, N-allylic 2,3-dihydro-1,2-benzoisothiazole 1-oxides, with 2,3-dihydro-1,2-benzoisothiazole 1-oxide as a unique chiral skeleton, is developed for the highly enantioselective rhodium-catalyzed asymmetr

Full text of DOI:10.1002/ejoc.201601206

A Journal of
Accepted Article
Title: A New Type of Chiral Cyclic sulfinamide-Olefin Ligands for Rhodium-Catalyzed
Asymmetric Addition
Authors: Quan Wen; Qingle Zeng; Li Zhang; Jing Xiong
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201601206
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European Journal of Organic Chemistry
10.1002/ejoc.201601206
COMMUNICATION
A New Type of Chiral Cyclic sulfinamide-Olefin Ligands for
Rhodium-Catalyzed Asymmetric Addition**
Quan Wen, Li Zhang, and Jing Xiong, Qingle Zeng*
Abstract: A new type of chiral cyclic sulfinamide-olefin ligands N-
allylic 2,3-dihydro-1,2-benzoisothiazole 1-oxides with 2,3-dihydro-
R''
R
X
Z
1,2-benzoisothiazole 1-oxide as unique chiral skeleton is developed
for highly enantioselective rhodium-catalyzed asymmetric 1,4-
additions of ,-unsaturated cyclic carbonyl compounds and 1,2-
addition of benzil. Both enantiomers with 99%ee of chiral cyclic
sulfinamide-olefin ligands could be easily prepared from inexpensive
and commercially available starting materials and directly used in
asymmetric catalysis, and thus both enantiomers of the addition
products could be obtained in high yields (up to 98%) and excellent
enantioselectivities (up to 98%ee).
Y
S
N
S
R'
O
X = NH, NR or CR1R2,
Y = CH2 or CR1R2
or X-Y = C6H4
Z = tert-Bu, 4-Tol
R = H, alkyl, aryl
O
R', R'' = H, alkyl, aryl
sulfinamide/sulfoxide-based olefin
cyclic sulfinamide-olefin
Figure 1. The general formula of chiral sulfinamide/sulfoxide-based olefin
ligands and our designed chiral cyclic sulfinamide-olefin ligands.
Chiral compounds exhibit more and more extensive applications
in pharmaceuticals, agricultural chemicals and materials.
Transition metal-catalyzed asymmetric syntheses with chiral
ligands are one of the most efficient approaches to prepare
chiral compounds.[1] Chiral ligands with appropriate chiral
skeletons are the key factor to achieve high enantioselectivity for
asymmetric reactions. Therefore, in addition to the extensively
investigated phosphorus-based chiral ligands,[2] to explore novel
chiral ligands with other kinds of coordination atoms and/or
functional groups is of great interest in organic and
organometallic chemistry.[3]
During our research in chiral sulfur chemistry,[14] we noticed
unsubstituted chiral cyclic sulfinamide, namely, 2,3-dihydro-1,2-
benzoisothiazole 1-oxide, was firstly reported by Fensterbank
group,[15] which is readily synthesized with 94%ee via
intramolecular radical cyclization. Although only 94%ee
enantiomeric purity of 2,3-dihydro-1,2-benzoisothiazole 1-oxide
is not high enough to be used as chiral ligand source, we
thought that
a
modified procedure or an additional
recrystallization may improve its enantiomer purity. Later
Rodríguez-Fernández’s group further developed the synthetic
method of 3-substiuted chiral cyclic sulfinamides with 98%de,[16]
which offers more chances to modify the chiral structural motif.
To the best of our knowledge, chiral cyclic sulfinamide 2,3-
dihydro-1,2-benzoisothiazole 1-oxide are not used as chiral
ligand skeleton in catalytic asymmetric transformation. Herein
we describe our discovery of chiral N-allylic 2,3-dihydro-1,2-
benzoisothiazole 1-oxides, especially N-cinnamyl 2,3-dihydro-
1,2-benzoisothiazole 1-oxide, as efficient chiral ligands used in
highly enantioselective rhodium-catalyzed asymmetric 1,4-
addition reaction of arylboronic acids to ,-unsaturated
carbonyl compounds (Scheme 1).
Among them, chiral ligands, such as chiral sulfoxides,[4] chiral
sulfoxide-phosphines,[5] chiral dienes,[6] P/N-olefins[7] are
becoming the focus of asymmetric catalysis.
Most recently, a series of chiral sulfinamide/sulfoxide-based
olefin ligands are developed in Knochel,[8] Xu,[9] Du,[10] Liao,[11]
Wan,[12] and Chen[13] groups. All of the reported ligands hold an
open chain sulfinyl group (Figure 1). Therefore it occurred to us
that whether the activity and enantioselectivity of catalytic
reaction would be maintained or improved if rigid chiral cyclic
sulfinamides was introduced into the ligands (Figure 1).
R'
N
S
R
C
O
O
L1 - L4
O
+
ArB(OH)2
Ar
( )
n
X
X
( )
n
[Rh(C2H4)2Cl]2
K3PO4, dioxane, 40 o
1a, X=CH2, n=2
1b, X=CH2, n=1
1c, X=O, n=2
2
3
Scheme 1. Rhodium-catalyzed asymmetric 1,4-addition with chiral N-allylic
2,3-dihydro-1,2-benzoisothiazole 1-oxides
[*]
Q. Wen, L. Zhang, J. Xiong, Prof. Dr. Q. Zeng
State Key Laboratory of Geohazard Prevention and
Geoenvironment Protection (Chengdu University of Technology),
College of Materials, Chemistry & Chemical Engineering
Chengdu University of Technology
1#, Dongsanlu, Erxianqiao, Chengdu 610059, Sichuan, P. R. China.
E-mail: qinglezeng@hotmail.com
http://www.cmcc.cdut.edu.cn/show-13-141-1.html
We thank the Ministry of Science and Technology of the People’s
Republic of China (No. 2013DFA21690), the National Natural
We started our research by preparing the unsubstituted chiral
cyclic sulfinamide (S)-2,3-dihydro-1,2-benzoisothiazole 1-oxide
(Fig. 2). Fortunately, modification on the base of Fensterbank’s
procedure[15] by using toluene in place of benzene, increasing
o
[**]
reaction temperature to 110 C, and prolonging injection time of
a toluene solution of AIBN and Bn3SnH, afforded the cyclic
sulfinamide (S)-2,3-dihydro-1,2-benzoisothiazole 1-oxide with
extremely high ee value up to 99%ee, which was directly used in
synthesis of chiral ligands. And then chiral 3-ethyl and 3-phenyl
2,3-dihydro-1,2-benzoisothiazole 1-oxides were prepared
Science Foundation of China (No. 21372034), the Science
Technology Department of Sichuan Province (No. 2016HH0074),
the Education Department of Sichuan Province (No. 16ZA0084).
&
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/ejoc..
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European Journal of Organic Chemistry
10.1002/ejoc.201601206
COMMUNICATION
according to Rodríguez-Fernández’s procedure,[16] which are
reported to have >98%dr diastereomer purity.
proves that the stereochemistry of catalytic reaction is governed
by S-chirality.
Once chiral cyclic sulfinamides were prepared, chiral cyclic
sulfinamide-olefin ligands were readily synthesized via simple
SN2 nucleophilic substitution of allylic halides and chiral cyclic
sulfinamide in the presence of the base sodium hydride. Luckily,
chirality of N-cinnamyl-2,3-dihydro-1,2-benzoisothiazole 1-oxide
(L1) was well kept and no any racemization occurred during the
basic reaction conditions, and thus chiral ligand L1 had 99%ee.
The absolute configurations were established by single-crystal
X-ray diffraction analysis of (S)-N-cinnamyl 2,3-dihydro-1,2-
benzoisothiazole 1-oxide (L1) (Figure 2), whose crystal structure
data has been deposited at the Cambridge Crystallographic
Data Centre with a CCDC deposition number of CCDC 1501739.
The single crystal X-ray diffraction analysis confirmed that the
chiral configuration was completely inverted at the sulfur atom
during the intramolecular homolytic substitution, which is
conformed to Fensterbank’s[15] and Rodríguez-Fernández’s
results.[16] From the crystal diagram, we can imagine that the two
aromatic rings will be like two chiral fences to produce an
excellent chiral surrounding when it coordinates with rhodium or
other appropriate center metal to form a complex. Unfortunately,
attempts to obtain single crystals of the rhodium complex of L1
failed.
Increase the amount of catalyst [Rh(C2H4)2Cl]2 and chiral
ligand L1 resulted in the rise of yields and enantioselectivities
(Entries 5 to 8), and at last 96%ee and 98% yield were obtained
in the presence of 2.5 (mol)% [Rh(C2H4)2Cl]2 and 5 (mol)% chiral
ligand L1 (Entry 8). Further increase of rhodium catalyst and L1
did not give better results.
Encouraged by the preliminary results, we hope to further
improve the enantioselectivity and yield of reaction through
optimizing the base and solvent. However, further screening of
base kinds and solvent types did not improve the results (see
the supporting information).
Table 1. Screening of chiral cyclic sulfinamide-olefin ligand in rhodium-
catalyzed 1,4-addition of 4-methoxyphenylboronic acid to cyclohexenone.
O
chiral Ligand
B(OH)2
O
[Rh(C2H4)2Cl]2
(R)
+
K3PO4, dioxane, 40 o
C
O
O
1a
2a
3a
Ph
(E)
(S)
(E)
(S)
(E)
N
N
Ph
N
Ph
N
Ph
S
S
S
S
(S)
O
(S)
(S)
O
(S)
O
O
L1
L2
L4
L3
Entry
1d
2
Rh (%)
Ligand
(S)-L1
(S)-L2
(1S,3S)-L3
(1S,3S)-L4
(S)-L1
(S)-L1
(S)-L1
Ligand (%)
Yield (%)b
ee (%)c
90
82
70
65
92
93
94
2
2
2
2
2
4
5
5
2
2
2
2
3
4
4
5
82
80
72
79
82
89
95
98
3e
4e
5
6
7
8
Figure 2. X-ray crystal structures of (S)-N-cinnamyl 2,3-dihydro-1,2-
benzoisothiazole 1-oxide (L1)
(S)-L1
96
[a] Reaction conditions: Cyclohexenone (0.5 mmol), arylboronic acid (1 mmol),
[Rh(C2H4)2Cl]2, chiral sulfinamide ligand, K3PO4 (0.25 mmol), dioxane (5 mL),
water (1 mL), argon, 40 oC, 4 h. [b] Isolated yield. [c] Determined by HPLC
analysis with a chiral stationary phase. All products are R form. [d] With
99%ee (S)-L1 as chiral ligand. [e] L3 and L4 with 98%de according to the
literature.[16]
With chiral cyclic sulfinamide-olefin ligands in hand, we chose
the Rh-catalyzed 1,4-addition of phenylboronic acid to
cyclohexenone as the model reaction to evaluate their catalytic
performance (Table 1). To our delight, the products were
obtained in good yield (82%) and pretty good enantioselectivity
(90%ee) in the presence of 1 mol% [Rh(C2H4)2Cl]2 and 2 mol%
chiral ligand (S)-L1 (Entry 1).
When allyl group took place of cinnamyl group on the chiral
sulfinamide ligand, the yield is similar to the former, but the ee
value of the product was decreased to 82%ee (Entry 2). It
seems that a phenyl moiety at the end of allyl group acts as a
chiral shield and favors the chiral induction.
With the optimized conditions in hand, reaction of ,-
unsaturated cyclic carbonyl compounds 1a-1c and various
arylboronic acids 2 were evaluated (Table 2).
Several points are noteworthy: Firstly, all of the reactions for
which L1 were used as ligands furnished high yields (80%~98%)
and excellent enantioselectivities (86%ee~98%ee) (Entries 1 to
21). All confirmed configuration of the products with (S)-L1 as
However, chiral sulfinamide ligands with 3-substituted
groups, both with ethyl (L3) and with phenyl (L4), did not benefit
chiral induction as well as the reaction rate for this reaction
(Entries 3 and 4). It seems that a 3-substituted group hinders the
coordination efficiency of rhodium and the sulfinamide-olefin
ligand.
ligand were
R form, while (R)-L1 afforded S form 3-
tolylhexanone. As means extremely strong chiral induction ability
with L1.
All of the four chiral sulfinamide ligands afforded R form
addition product 3-phenycyclohexanone (Entries 1 to 4), which
Table 2. Evaluation of reaction of ,-unsaturated cyclic carbonyl compounds
1a-1c and arylboronic acids 2.[a]
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European Journal of Organic Chemistry
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COMMUNICATION
(5mol%) (S)-L1
2.5%mol [Rh(C2H4)2Cl]2
rhodium-catalzyed 1,2-addition reaction of benzil and
phenylboronic acid, and (R)-form product with 90% yield and
90%ee was obtained (Scheme 3).
O
(R)Ar
n
O
+
ArBH(OH)2
( )
n
X
X
K3PO4, dioxane, 40 oC
( )
2
1a, X=CH2, n=2
1b, X=CH2, n=1
1c, X=O, n=2
3
Ph
5 mol% L1
2.5 mol% [Rh(C2H4)2Cl]2
B(OH)2
O
Ph
O
O
(R)
+
O
Entry
1
Ar
3
Yield
(%)[b]
98
90
97
97
96
97
98
95
97
94
95
96
86
80
97
92
94
83
96
96
97
ee
(%)[c]
96
97
98
97
95
98
98
94
93
91
95
95
94
93
89
91
86
88
92
96
94
Config.[d]
Ph
Ph
K3PO4, dioxane, 40 o
C
O
HO
90% yield, 90%ee
1
2
3
4
5
6
7
8
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1b
1b
1c
1c
4-MeOC6H5
C6H5
3a
3b
3c
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
3o
3p
3q
3r
R[8]
R[9d]
4
2a
5
4-MeC6H5
4-MeC6H5
3-MeC6H5
2-MeC6H5
4-t-BuC6H5
4-ClC6H5
3-ClC6H5
2-ClC6H5
4-FC6H5
4-BrC6H5
2-naphthyl
4-C2H3C6H5
C6H5
4-MeC6H5
2-MeC6H5
4-t-BuC6H5
4-MeOC6H5
4-MeC6H5
4-MeOC6H5
R[17]
S[e],[17]
R[10a]
NC[9c]
R[18]
Scheme 2. Rh-catalyzed 1,2-addition reaction of benzil and phenylboronic
acid with (S)-L1 as ligand.
R[19]
9
R[10a]
R[10a]
NC[9c]
NC[20]
R[21]
10
11
12
13
14
15
16
17
18
19
20
21
In summary, we have developed a new type of chiral cyclic
sulfinamide-olefin ligands from commercially available,
inexpensive starting materials. Wide structural diversity of chiral
ligands can be achieved by changing the synthetic routes. For
rhodium-catalyzed asymmetric addition reactions, both
enantiomers could be furnished in high yields with excellent
enantioselectivity by employment of (S)- and (R)-L1,
respectively. Chiral cyclic sulfinamide-olefin ligand with only
99%ee afforded 1,4-addition products with up to 98%ee. The
salient features of these new chiral ligands, including their rigid
cyclic structure, air stability, the practical preparation from
readily available starting materials, easy modification, and good
results in enantioselective transformations, render these ligands
very attractive. Further studies, such as investigation of the
performance of these ligands in other metal-catalyzed
asymmetric reactions, are currently underway in our laboratory.
NC[22]
R[18]
NC[9c]
NC[23]
NC[13]
R[24]
3s
3t
R[25]
NC[26]
[a] Reaction conditions: Cyclohexenone (0.5 mmol), arylboronic acid (1 mmol),
[Rh(C2H4)2Cl]2 (0.0125 mmol), 99%ee (S)-L1 (0.025 mmol), K3PO4 (0.25
mmol), dioxane (5 mL), water (1 mL), argon, 40 oC, 3 h, unless otherwise
noted. [b] Isolated yield. [c] Determined by HPLC analysis with a chiral
stationary phase. [d] The absolute configurations of 3a-3t were determined by
comparison of their chiral HPLC elution order with those reported (see the
supporting information). NC means no comparison of the configuration with
the literature data. [e] Ligand (R)-L1 (0.025 mmol) was used.
Experimental Section
Secondly, both enantiomers of a chiral compound are often
required in organic synthesis, fine chemicals, medicinal and
pharmaceutical industries. To our gratification, both enantiomers
of the product 3-(4-tolyl)cyclohexanones could be obtained in
high yields and with 98%ee (R form) and 97%ee (S form),
respectively, when the sulfinamide ligands (S)- and (R)-L1 were
applied (Entries 3 and 4).
Thirdly, para- and ortho-methyl- and para-tert-butyl-
phenylboronic acid afforded the highest enantioselectivities of
98%ee among the tested arylboronic acids (Entries 3, 6 and 7).
It should be emphasized that 98%ee of the products are
produced not by 100%ee but by only 99%ee chiral ligand (S)-L1.
Fourthly, halo, vinyl and alkoxyl groups are compatible in the
addition. These addition product is easily further derived into
various valuable compounds.
Fifthly, cyclic lactone 5,6-dihydropyran-2-one afforded nearly the
same high yields and enantioselectivities as cyclohexenone
(Entries 20-21). However, cyclopentenone is a homologen of
cyclohexenone, but for the same kinds of arylboronic acids,
cyclopentenone generally afforded lower ee values (Entries 15
to 19). The reason probably is that four hydrogen atoms of two
methylene groups out of the plane of cyclopentenone hamper
efficiency of rhodium’s vertical coordination with cyclopentenone.
Although Xu[27] and Kiar[28] have reported efficient rhodium-
catalyzed 1,2-additions of arylboronic acids to benzil, to our
delight, this new type of chiral ligand also performed well in
Typical procedure for the synthesis of chiral cyclic sulfinamide (S)-2,3-
dihydro-1,2-benzoisothiazole 1-oxide: To an oven-dried 25 mL test tube
with ground joint equipped with
iodobenzyl)-2-methylpropane-2-sulfinamide (1 mmol, 337 mg), AIBN
(0.38 mmol, 64 mg), and degassed toluene (2 mL). The test tube was
sealed and evacuated and refilled with argon for three cycles. And it was
a stir bar were added (R)-N-(2-
o
put into an oil bath preheated at 110 C. A solution of AIBN (1.09 mmol,
179 mg), Bn3SnH (0.9 mmol, 264 mg) and degassed toluene (5 mL) was
injected into the test tube via syringe with two hours. After injection the
test tube kept stirring at 110 oC for another four hours. After cooling to
room temperature, the reaction mixture was quenched with water (20
mL) and extracted with ethyl acetate (20 mL) for three times. The
combined organic layer was dried with anhydrous MgSO4 and filtered.
After removal of the solvent under reduced pressure, the residue was
purified by flash column chromatography (eluted using gradient mixtures
of petroleum ether and ethyl acetate (0-100% ethyl acetate)) on silica gel
to afford (S)-2,3-dihydro-1,2-benzoisothiazole 1-oxide as a white solid
(0.994 g, 65%, 99%ee). Mp: 125-126 oC for 99%ee (lit.[15b]: mp. 120 oC
21.5
[15b]
20
for 94%ee). [α]D
98.9° (c = 1, EtOH)).
= −123.39° (c = 0.124, CH2Cl2) (lit.
[α]D = −
Typical procedure for the synthesis of (S)-cinnamyl-2,3-dihydro-1,2-
benzoisothiazole 1-oxide (L1): To an oven-dried 25 mL test tube with
ground joint equipped with a stir bar were added (S)-2,3-dihydro-1,2-
benzoisothiazole 1-oxide (1 mmol, 153.0 mg), 60% NaH (2 mmol, 40 mg),
THF (2 mL). The test tube was sealed and evacuated and refiled with
argon for three cycles. The test tube was put into an ice water bath and
stirred for a half hour. A solution of cinnamyl bromide (1.01 mmol, 0.199
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European Journal of Organic Chemistry
10.1002/ejoc.201601206
COMMUNICATION
g) and THF (3 mL) was injected into the test tube via a syringe. And the
test tube was sealed and evacuated and refiled with argon for three
cycles. The test tube was put into an ice water bath and stirred for five
hours. The reaction mixture was quenched with water (15 mL) and
extracted with ethyl acetate (15 mL) for three times. The combined
organic layer was dried with anhydrous MgSO4 and filtered. After removal
of the solvent under reduced pressure, the residue was purified by flash
column chromatography (eluent: gradient mixtures of petroleum ether
and ethyl acetate (0-100% ethyl acetate)) on silica gel to afford (S)-
cinnamyl-2,3-dihydro-1,2-benzoisothiazole 1-oxide (L1) as a white solid
(245 mg, 91% yield, 99%ee). [α]D20.7 +52.27 (c 0.2, CH2Cl2), mp. 114-116
oC.
Chem. Soc. 2007, 129, 5336-5337; d) X. Hu, M. Zhang, Z. Cao, H. Du,
Org. Lett. 2009, 11, 4744-4747.
[7]
a) P. Maire, S. Deblon, F. Breher, J. Geier, C. Böhler, H. Rüegger, H.
Schönberg, H. Grützmacher, Chem. Eur. J. 2004, 10, 4198-4205; b) R.
Shintani, W.-L. Duan, T. Nagano, A. Okada, T. Hayashi, Angew. Chem.,
Int. Ed., 2005, 44, 4611-4614; c) P. Kasák, V. B. Arion, M. Widhalm,
Tetrahedron: Asymm. 2006, 17, 3084-3090; d) B. T. Hahn, F. Tewes, R.
Frölich, F. Glorius, Angew. Chem., Int. Ed. 2010, 49, 1143-1146.
T. Thaler, L.-N. Guo, A. K. Steib, M. Raducan, K. Karaghiosoff, P.
Mayer, P. Knochel, Org. Lett. 2011, 13, 3182-3185.
[8]
[9]
a) Y. Li, M.-H. Xu. Chem. Commun., 2014, 50, 3771-3782; b) W. Y. Qi,
T. S. Zhu, M. H. Xu, Org. Lett. 2011, 13, 3410-3413; c) S. S. Jin, H.
Wang, M. H. Xu, Chem. Commun. 2011, 47, 7230-7232; d) S. S. Jin, H.
Wang, T. S. Zhu, M. H. Xu, Org. Biomol. Chem. 2012, 10, 1764-1768;
e) T. S. Zhu, S. S. Jin, M. H. Xu, Angew. Chem., Int. Ed. 2012, 51,
780-783; f) H. Wang, T. Jiang, M. H. Xu, J. Am. Chem. Soc. 2013, 135,
971-974.
Typical procedure for the synthesis of optically active 3-(4-
methoxyphenyl)cyclohexan-1-one (3a): To an oven-dried 25 mL test tube
with ground joint equipped with
a
stir bar were added 4-
methoxyphenylboronic acid (1 mmol, 0.152 g), (S)-N-cinnamyl 2,3-
dihydro-1,2-benzoisothiazole 1-oxide (0.025 mmol, 0.0067 g),
[Rh(C2H4)2Cl]2 (0.0125 mmol, 0.0048 g), 1,4-dioxane (2 mL). The test
tube was sealed with a sleeve rubber stopper and evacuated and refilled
[10] a) X. Feng, Y. Wang, B. Wei, J. Yang, H. Du, Org. Lett. 2011, 13, 3300-
3303; b) X. Q. Feng, Y. Z. Nie, J. Yang, H. F. Du, Org. Lett. 2012, 14,
624-627; c) Y. Z. Wang, X. Q. Feng, H. F. Du, Org. Lett. 2011, 13,
4954-4957; d) Z. Q. Liu, X. Q. Feng, H. F. Du, Org. Lett. 2012, 14,
3154-3157.
o
with argon for three cycles. It was put into an oil bath preheated at 40 C
for 0.5 hour. And then a solution of cyclohexenone (0.5 mmol, 0.048 g),
K3PO4 (0.25 mmol, 0.053 g), 1,4-dioxane (3 mL) and water (1 mL) was
transferred to the test tube by a syringe. The test tube was further
evacuated and refilled with argon for three cycles. And it was put into the
oil bath preheated at 40 oC for 3 hour. The reaction mixture was added
water (15 mL) and extracted with ethyl acetate (15 mL) for three times.
The combined organic layer was dried over anhydrous MgSO4 and
filtrated. After removal of the solvent under reduced pressure, the residue
was purified by flash column chromatography on silica gel to afford 3a
(100 mg, 98% yield, 96%ee).
[11] a) G. Chen, J. Gui, L. Li, J. Liao, Angew. Chem., Int. Ed., 2011, 50,
7681-7685; b) L. Du, P. Cao, J. W. Xing, Y. Z. Lou, L. Y. Jiang, L. C. Li,
J. Liao, Angew. Chem., Int. Ed. 2013, 52, 4207-4211.
[12] F. Xue, X. Li, B. Wan, J. Org. Chem., 2011, 76, 7256-7262.
[13] Q. Chen, C. Chen, F. Guo, W. Xia, Chem. Commun., 2013, 49, 6433-
6435.
[14] a) X. Sun, X. Tu, C. Dai, X. Zhang, B. Zhang, Q. Zeng, J. Org. Chem.
2012, 77, 4454–4459; b) Q. Zeng, W. Weng, X. Xue, Inorg. Chim.
Comm. 2012, 388, 11-16; c) Q. Zeng, H. Wang, T. Wang, Y Cai, W.
Weng, Y Zhao, Adv. Synth. Catal. 2005, 347, 1933-1936; d) Q. Zeng, H.
Wang, W. Weng, W. Lin, Y. Gao, X. Huang, Y. Zhao, New J. Chem.
2005, 29, 1125-1127; e) Q.-L. Zeng, H.-Y. Tang, S. Zhang, J.-C. Liu,
Chin. J. Chem. 2008, 26, 1435-1439.
Keywords: asymmetric catalysis • enantioselectivity • cyclic
sulfinamide-olefin • addition reaction • rhodium
[15] a) J. Coulomb, V. Certal, L. Fensterbank, E. Lacôte, M. Malacria.
Angew. Chem. Int. Ed. 2006, 45, 633-637; b) J. Coulomb, V. Certal, M.-
H. Larraufie, C. Ollivier, J.-P. Corbet, G. Mignani, L. Fensterbank, E.
Lacôte, M. Malacria. Chem. Eur. J. 2009, 15, 10225-10232.
[16] J. A. Fernández-Salas, M. M. Rodríguez-Fernández, M. C. Maestro, J.
L. García-Ruano. Chem. Commun, 2014, 50, 6046-6048.
[17] Y.-S. Zhao, J.-K. Liu, Z.-T. He, J.-C. Tao, P. Tian, G.-Q. Lin. Org.
Biomol. Chem. 2016, 14, 3686-3689.
[1]
[2]
[3]
a) B. M. Trost, Proc. Natl. Acad. Sci. USA 2004, 101, 5348-5355; b)
Comprehensive Asymmetric Catalysis I–III, ed. E. N. Jacobsen, A.
Pfaltz, H. Yamamoto, Springer-Verlag, New York, 1999.
a) Phosphorus Ligands in Asymmetric Catalysis 1-3, ed. A. Börner,
Wiley-VCH, Weinheim, 2008; b) Privileged Chiral Ligands and
Catalysts, ed. Q.-L. Zhou, Wiley-VCH, Weinheim, 2011.
a) R. Shintani, T. Hayashi, Aldrichimica Acta 2009, 42, 31-38; b) C.
Defieber, H. Grützmacher, E. M. Carreira, Angew. Chem., Int. Ed. 2008,
47, 4482-4502; c) J. B. Johnson, T. Rovis, Angew. Chem., Int. Ed. 2008,
47, 840-871.
[18] T. Yasukawa, H. Miyamura, S. Kobayashi. J. Am. Chem. Soc. 2012,
134, 16963-16966.
[19] J. Dong, Y. Liu, Y. Cui. Chem. Commun. 2014, 50, 14949-14952.
[20] C.-G. Feng, Z.-Q. Wang. Org. Lett. 2008, 10, 4101-4104.
[21] A. Lee, H. Kim, J. Org. Chem. 2016, 81, 3520-3527.
[22] Q. Naeemi, M. Dindaroğlu, D. P. Kranz, J. Velder, H.-G. Schmalz. Eur.
J. Org. Chem. 2012, 6, 1179-1185.
[4]
a) F. Ferreira, C. Botuha, F. Chemla, A. Pérez-Luna, Chem. Soc. Rev.
2009, 38, 1162-1186; c) M. T. Robak, M. A. Herbage, J. A. Ellman,
Chem. Rev. 2010, 110, 3600-3740; d) Mariz, R.; Luan, X. J.; Gatti, M.;
Linden, A.; Dorta, R. J. Am. Chem. Soc. 2008, 130, 2172-2173; f) Chen,
J.; Chen, J. M.; Lang, F.; Zhang, X. Y.; Cun, L. F.; Zhu, J.; Deng, J. G.;
Liao, J. J. Am. Chem. Soc. 2010, 132, 4552-4553.
[23] Y. Otomaru, K. Okamoto, J. Org. Chem. 2005, 70, 2503-2508.
[24] H. Yang, M. Xu. Chin. J. Chem. 2013, 31, 119-122.
[25] C.-C. Liu, D. Janmanchi, C.-C. Chen, H.-L. Wu. Eur. J. Org.
Chem. 2012, 2012, 2503-2507.
[5]
[6]
a) Owens, T. D.; Hollander, F. J.; Oliver, A. G.; Ellman, J. A. J. Am.
Chem. Soc. 2001, 123, 1539-1540; b) Lang, F.; Chen, G. H.; Li, L. C.;
Xing, J. W.; Han, F. Z.; Cun, L. F.; Liao, J. Chem. Eur. J. 2011, 5242-
5245.
[26] T. Gendrineau, O. Chuzel, H. Eijsberg, J.-P. Genet, S. Darses. Angew.
Chem. Int. Ed. 2008, 47, 7669 -7672.
[27] T.-S. Zhu, S.-S. Jin, M.-H. Xu, Angew. Chem. Int. Ed. 2012, 51, 780-
783.
a) C. Fischer, C. Defieber, T. Suzuki, E. M. Carreira, J. Am. Chem. Soc.
2004, 126, 1628-1629; b) N. Tokunaga, Y. Otomaru, K. Okamoto, K.
Ueyama, R. Shintani, T. Hayashi, J. Am. Chem. Soc. 2004, 126,
13584-13585; c) Z.-Q. Wang, C.-G. Feng, M.-H. Xu, G.-Q. Lin, J. Am.
[28] N. Khiar, V. Valdivia, Á. Salvador, A. Chelouan, A. Alcudia, I.
Fernández, Adv. Synth. Catal. 2013, 355, 1303-1307.
This article is protected by copyright. All rights reserved

European Journal of Organic Chemistry
10.1002/ejoc.201601206
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
COMMUNICATION
O
S
N
Quan Wen, Li Zhang, Jing Xiong, Qingle
Zeng*
O
O
Ar
+
ArB(OH)2
(
)
X
(X)
n
n
[Rh(C2H4)2Cl]2
K3PO4, dioxane, 40 o
Page No. – Page No.
C
A New Type of Chiral Cyclic
sulfinamide-Olefin Ligands for
Rhodium-Catalyzed Asymmetric
Addition
Rigid cyclic sulfinamide 2,3-dihydro-1,2-benzoisothiazole 1-oxide acts as chiral
skeleton of a new type of chiral cyclic sulfinamide-olefin ligands, which demonstrate
excellent enantioselective catalytic performance in rhodium-catalyzed asymmetric
1,4-additions of ,-unsaturated cyclic carbonyl compounds and 1,2-addition of
benzil. Both enantiomers of chiral ligands are easily prepared and directly used in
catalysis, and thus both high ee enantiomers of the products are obtained.
This article is protected by copyright. All rights reserved