Asymmetric hydrogenation of β-keto sulfonamides and β-keto sulfones with a chiral cationic ruthenium diamine catalyst

Article abstract of DOI:10.1002/adsc.201300331

Optically active β-hydroxy sulfonamides and β-hydroxy sulfones are very important building blocks for the preparation of bioactive compounds and pharmaceuticals. In this work, a highly efficient asymmetric hydrogenation of β-keto sulfonamides and β-keto s

Full text of DOI:10.1002/adsc.201300331

FULL PAPERS
DOI: 10.1002/adsc.201300331
Asymmetric Hydrogenation of b-Keto Sulfonamides and b-Keto
Sulfones with a Chiral Cationic Ruthenium Diamine Catalyst
Xiao-Fei Huang,a Shao-Yun Zhang,a Zhi-Cong Geng,a Chun-Yuen Kwok,a
Peng Liu,a Hai-Yan Li,a and Xing-Wang Wanga,*
a
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials
Science, Soochow University, Suzhou 215123, Peopleꢀs Republic of China
Fax : (+86)-512-6588-0378; e-mail: wangxw@suda.edu.cn
Received: April 19, 2013; Revised: July 10, 2013; Published online: October 9, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300331.
Abstract: Optically active b-hydroxy sulfonamides hydrogenation/dynamic kinetic resolution (DKR) of
and b-hydroxy sulfones are very important building racemic cyclic b-keto sulfonamides and b-keto sul-
blocks for the preparation of bioactive compounds fones was also realized using the same catalyst, to
and pharmaceuticals. In this work, a highly efficient give the corresponding chiral cyclic b-hydroxy sulfo-
asymmetric hydrogenation of b-keto sulfonamides namides and b-hydroxy sulfones in good yields with
and b-keto sulfones has been developed using excellent enantio- and diastereoselectivities.
the phosphine-free chiral ruthenium complex
RuACHTUNGTRENNUNG(OTf)ACHTUNGTRENNUNG
(TsDPEN)(h6-p-cymene) as the catalyst, to
afford the corresponding b-hydroxy sulfonamides Keywords: asymmetric hydrogenation; chiral dia-
and b-hydroxy sulfones in high yields with excellent mine complexes; b-hydroxy sulfonamides; b-hydroxy
optical purities. In addition, a cascade asymmetric sulfones; phosphine-free
Introduction
cations as well as their synthetic versatility. b-Hydroxy
sulfonamides can be readily converted to correspond-
Compounds bearing a sulfonyl or sulfonamide group ing hydroxy- or aminosulfonic acid derivatives,[6] and
are important building blocks in organic synthesis, can also serve as versatile synthetic intermediates for
and are found in a wide range of pharmaceuticals various biologically active compounds, such as b-sul-
with various biological activities.[1] The sulfonyl and tams[6] and acyclic b-aminosulfonyl derivatives
sulfonamide groups are known to improve the water (sulfon
ACHTUNGTRENNUNG
solubility of target compounds by their ability to form
hydrogen bonds, and can be used to fine tune the pKa
values of the amino groups due to their strong induc-
tive effect.[2] As a result, the research on pharmaceuti-
cal precursors that bear a sulfonyl or a sulfonamide
group has been a focal issue in the study of synthetic
drugs.[3] For instance, flavocristamide A (1) is a natu-
rally occurring sulfonolipid which efficiently inhibits
the enzyme DNA polymerase A.[4] Thiazolone-acyl-
sulfonamide (2) is an HCV NS5B polymerase alloste-
ric inhibitor, and compound (3) has antifungal activity
(Figure 1).[5] According to the World Drug Index,
there are more than 40 drugs carrying either of these
two types of groups.
Specifically, chiral b-hydroxy sulfonamides that
contain both sulfonyl and hydroxy groups in their
structures are very attractive targets for synthetic
Figure 1. Selected natural products and drugs with sulfonyl
studies by virtue of their widespread biological appli- groups.
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Asymmetric Hydrogenation of b-Keto Sulfonamides and b-Keto Sulfones
Scheme 1. Asymmetric hydrogenation (AH) and/or DKR of b-keto sulfonamides and b-keto sulfones.
opment of versatile and efficient synthetic protocols emic cyclic b-keto sulfonamides and b-keto sulfones,
for enantioenriched b-hydroxy sulfonamides and b- to give the corresponding chiral cyclic b-hydroxy sul-
hydroxy sulfones is of great significance. In this con- fonamides and b-hydroxy sulfones in good yields with
text, however, literature examples on the asymmetric excellent
synthesis of chiral b-hydroxy sulfonamides are still (Scheme 1).
rare so far, including the addition of sulfamide to ben-
enantio-
and
diastereoselectivities
zaldehyde,[6,8] as well as asymmetric transfer hydroge-
nation (ATH) of b-keto sulfonamides.[9] Comparing Results and Discussion
with these methods, asymmetric hydrogenation (AH)
of b-keto sulfonamides and b-keto sulfones[10d,e,o,p] rep- The AH of 2-oxo-N,2-diphenylethanesulfonamide
resents a more straightforward approach to generate (4aa)
the corresponding optically active compounds, and is (TsDPEN) catalyst I was first selected as the model
more atom-economic and eco-friendly for practical reaction, and the results are summarized in Table 1.
catalyzed
by
(R,R)-RuACTHUGNRTENNU(G OTf)ACHTUNGTRENN(UNG cymene)-
AHCTUNGTRENNUNG
applications.
Since the Ru-TsDPEN complexes are known to be
Currently, most of the reported catalysts for the
AH of ketones bear at least one phosphine ligand
around the metal center, which are often air sensitive
and tedious to prepare.[10] In 2006, it was discovered
that cationic ruthenium complexes of chiral mono-
tosylated diamines, well-known catalysts for ATH,[11]
can also function as efficient catalysts in the AH of
ketones[12] and imines[13] with a slight functional modi-
Table 1. Optimization of reaction conditions for the AH of
b-keto sulfonamide 4aa.[a]
fication. Recently, we also reported that Ru
ACHTUNGTRENNUNG
ACHTUNGTRNE(NUNG OTf)-
(TsDPEN)(h6-p-cymene) (Cat. I) [TfOÀ =trifluoro-
Entry S/C Solvent
H2 [atm] Yield [%][b] ee [%][c]
methanesulfonate, TsDPEN=N-(p-toluenesulfonyl)-
1,2-diphenylethylenediamine] efficiently catalyzed the
AH of benzils in methanol, to furnish chiral hydro-
benzoins in good yields with excellent enantioselecti-
vities.[12i] The highly polarized catalyst I was found to
easily ionize in methanol solution, to provide the
1
2
3
4
5
6
50
50
50
50
50
50
MeOH
MeOH
EtOH
DCM
toluene
dioxane 40
0
–
–
40
40
40
40
98
79
34
29
<5
98
94
96
92
95
97
95
81
-17
17
n.d.
98
98
96
98
97
98
active Ru cationic species [RuACHTUNGTRNEUNG
(TsDPEN)(h6-p-
7
8
9
10
11
12[d]
100 MeOH
250 MeOH
500 MeOH
250 MeOH
250 MeOH
250 MeOH
40
40
40
30
50
40
cymene)]+ that has been proven to be of crucial im-
portance for the catalytic activity.[12a,b,14] Herein, we
disclose the use of catalyst I as an efficient phos-
phine-free precatalyst for the asymmetric hydrogena-
tion of both b-keto sulfonamides and b-keto sulfones,
to provide a range of chiral b-hydroxy sulfonamides
and b-hydroxy sulfones in high yields with excellent
enantioselectivities. In addition, catalyst I was also
found to be efficient in the cascade asymmetric hy-
drogenation/dynamic kinetic resolution (DKR) of rac-
[a]
Reaction conditions: [4aa]=0.2M, cat. I in 1 mL solvent,
room temperature, 24 h.
Isolated yield.
Determined by chiral HPLC.
[4aa]=0.1M.
[b]
[c]
[d]
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FULL PAPERS
Table 2. Asymmetric hydrogenation (AH) of the b-keto sul-
fonamides 4aa–4ak with N-aryl substituents.[a]
capable of functioning as a potent catalyst for the
asymmetric transfer hydrogenation (ATH) of ketones
in protic solvents such as methanol,[13m] a control reac-
tion was first carried out with 2 mol% of catalyst I in
methanol in the absence of hydrogen gas. In this case,
no reduction product was detected after 24 h
(entry 1). Under otherwise identical conditions, the
reaction proceeded smoothly under 40 atm of H2 in
methanol, affording 5aa in 98% yield with 95% ee
(entry 2), thus indicating that the predominant reac-
tion pathway is AH rather than ATH. Encouraged by
this promising result, some common solvents, includ-
ing ethanol, dichloromethane, toluene and dioxane,
were screened in the reaction. The alcoholic solvents
(MeOH and EtOH) were found to be generally supe-
rior to the aprotic ones (entries 2, 3 vs. 4–6). Metha-
nol turned out to be the optimal reaction medium in
terms of both yield and enantioselectivity, and thus
was employed for subsequent AH reaction studies.
Furthermore, the influence of catalyst loading was
also investigated for the AH of 4aa, with the sub-
strate/catalyst ratio (S/C) ranging from 100/1 to 500/
1 (entries 2 and 7–9). The results showed that the re-
action still proceeded smoothly in the presence of
a relatively low catalyst loading (0.4 mol%, S/C=
250), to give the AH product 5aa in 94% yield with
98% ee (entry 8). In addition, the reactions under dif-
ferent hydrogen pressures were also studied. With the
hydrogen pressure ranging from 30 to 50 atm, the
enantioselectivity remained excellent (97–98% ee),
while the yield of 5aa fluctuated slightly around 92–
96% (entries 9–11). Finally, when the substrate con-
centration was diluted to 0.1M, the yield was en-
hanced slightly to 97% and the enantioselectivity was
Entry Substrates R1
Product/Yield
[%][b]
ee
[%][c]
1
2
3
4
5
6
7
8
4aa
4ab
4ac
4ad
4ae
4af
4ag
4ah
4ai
C6H5
5aa/97
5ab/99
5ac/98
5ad/96
5ae/95
98
97
97
98
97
99
98
97
97
96
4-FC6H4
4-ClC6H4
4-BrC6H4
4-CH3C6H4
4-CH3OC6H4 5af/97
3-ClC6H4 5ag/95
2-CH3OC6H4 5ah/99
2,4-Cl2C6H3 5ai/97
3,5-
9
10
4aj
5aj/92
(CF3)2C6H3
2,6-(i-
11
4ak
5ak/94
96
Pr)2C6H3
[a]
Reaction conditions: [4]=0.1M, 0.4 mol% cat. I in 2 mL
solvent, room temperature, 24 h.
Isolated yield.
[b]
[c]
Determined by chiral HPLC.
Furthermore, several b-keto sulfonamides with N-
retained (entry 12 vs. 8). Thus, the optimal conditions alkyl substituents on sulfonamide motifs were also ex-
for AH of 4aa were finally established as the reaction amined for the AH under optimized reaction condi-
being performed in methanol under 40 atm of H2 at tions (Table 3). Intriguingly, no reaction occurred for
ambient temperature, with a substrate concentration 2-oxo-2-phenylethanesulfonamide (4al), wherein both
of 0.1M in the presence of 0.4 mol% catalyst I.
substituents on the sulfonamide nitrogen are H atoms
Having established the optimal reaction conditions, (entry 1). For the b-keto sulfonamides substrates
we proceeded to explore the substrate scope of the 4am–4ap bearing an ethyl, n-butyl, tert-butyl, or a ben-
present protocol. A variety of b-keto sulfonamides zylsulfonamide group, the corresponding hydrogenat-
bearing N-aryl substituents were first investigated for ed products 5am–5ap were obtained in consistently
this transformation, and the results are shown in excellent enantioselectivities (98–99% ee) and high
Table 2. Excellent yields and enantioselectivities were yields (91–97%), respectively (entries 2–5). The hy-
obtained under optimized reaction conditions, irre- drogenation of 4ap was further tested under lowered
spective of the variations in electronic and steric catalyst loading, which would be of considerable inter-
properties of the substituents attached to the phenyl est from a practical point of view. When the sub-
rings of the sulfonamide motifs. Accordingly, the N- strate/catalyst ratio was increased gradually from 250
aryl substituted sulfamide 4aa–4ak bearing either to 1500, the hydrogenation still proceeded smoothly
electron-donating substituents (Me, OMe, i-Pr) or to give the desired product 5ap in excellent yield (>
electron-withdrawing substituents (F, Cl, Br, CF3) at 95%) and enantioselectivity (>97%) (entries 5–8).
para-, ortho- or meta- positions of the phenyl group Unfortunately, further reducing catalyst loading to
were all well tolerated, leading to the desired prod- 0.05 mol% (S/C=2000) led to a substantial decline of
ucts 5aa–5ak in 92–99% yields with 96–99% ees (en- the yield to 43% even after a prolonged reaction time
tries 1–11).
(48 h), although the enantioselectivity was maintained
(95% ee) (entry 9).
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Asymmetric Hydrogenation of b-Keto Sulfonamides and b-Keto Sulfones
Table 3. Asymmetric hydrogenation (AH) of the b-keto sul-
fonamides 4al–4ap with N-alkyl substituents.[a]
Table 4. Asymmetric hydrogenation (AH) of the b-keto sul-
fonamides 4ac–4mc.[a]
Entry Substrate R2
Product/Yield
[%][b]
ee
Entry Substrates R1
Product/Yield [%][b] ee [%][c]
[%][c]
1
2
3
4
4al
H
Et
–
–
1
2
3
4
5
6
7
4ac
4bc
4cc
4dc
4ec
4fc
4gc
C6H5
5ac/98
5bc/99
5cc/98
5dc/97
97
4am
4an
4ao
4ap
4ap
4ap
4ap
4ap
5am/91
99
99
98
99
99
98
97
95
4-FC6H4
4-ClC6H4
4-BrC6H4
4-NO2C6H4 5ec/98
4-CH3C6H4 5fc/93
>99
>99
98
>99
99
n-Bu 5an/91
t-Bu
Bn
Bn
Bn
Bn
Bn
5ao/92
5ap/97
5ap/97
5ap/96
5ap/95
5ap/43
5
6[d]
7[e]
8[f]
9[g]
4-
5gc/92
>99
CH3OC6H4
2-ClC6H4
3-BrC6H4
3-
CH3OC6H4
3,4-Cl2C6H3 5kc/95
2,4-Cl2C6H3 5lc/98
8
9
10
4hc
4ic
4jc
5hc/97
5ic/92
5jc/98
97
98
99
[a]
Reaction conditions: [4]=0.1M, 0.4 mol% cat. I in 2 mL
solvent, room temperature, 24 h.
Isolated yield.
Determined by chiral HPLC.
S/C=500/1.
S/C=1000/1.
S/C=1500/1.
S/C=2000/1, 48 h.
[b]
[c]
[d]
[e]
[f]
11
12
13
14
4kc
4lc
4mc
4nc
96
95
97
64
furyl
CH3
5mc/93
5nc/92
[g]
[a]
Reaction conditions: [4]=0.1M, 0.4 mol% cat. I in 2 mL
solvent, room temperature, 24 h.
Isolated yield.
[b]
[c]
Encouraged by these results, we further examined
the AH of b-keto sulfonamides bearing various sub-
stituents on ketonic moieties, and the results are
shown in Table 4. For substrates 4ac–4gc carrying
Determined by chiral HPLC analysis.
either electron-withdrawing groups (F, Cl, Br, NO2) crystal X-ray analysis, which revealed its S absolute
or electron-donating substituents (Me, OCH3) at the configuration on the chiral carbon (Figure 2).[15]
para-position of the phenyl ring, all the reactions pro-
Further studies on expansion of the substrate scope
ceeded smoothly to afford the products 5ac–5gc in revealed that b-keto sulfones were also amenable to
92–99% yields with 97 to >99% ees (entries 2–7). For the established AH protocol. As shown in Table 5, for
the reactions of substrates 4hc–4lc bearing mono- or
di-substitution on the other positions of phenyl rings
(2-Cl, 3-Br, 3-OCH3, 2,4-Cl2 and 3,4-Cl2), good yields
and excellent ees (92–98% yields, 95–99% ees) were
achieved, regardless of the stereoelectronic features
of the substituents (entries 8–12). Furthermore, 4mc
containing a furyl group was also proved to be a suita-
ble substrate for this transformation, affording the
corresponding product 5mc in 93% yield with 97% ee
(entry 13). In addition, the sulfonamide 4nc with an
aliphatic ketone moiety (Me) was also investigated
for this transformation, which furnished the desired
product 5nc in 92% yield with a somewhat declined
enantioselectivity (64% ee, entry 14). Fortunately, the
solid state structure of 5aa was determined by single
Figure 2. The solid state structure of 5aa.
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Xiao-Fei Huang et al.
FULL PAPERS
Table 5. Asymmetric hydrogenation (AH) of b-keto sulfones
6a–6l.[a]
AH of phenyl b-keto sulfones 6a–6g bearing either
electron-donating or electron-withdrawing groups at
o-, m-, and p-positions of the phenyl ring, the corre-
sponding products 7a–7g were obtained in excellent
yields (92–97%) with excellent enantioselectivities
(95–98% ee) (entries 1–7). In addition, this methodol-
ogy also proved to be efficient in hydrogenating sub-
strates containing fused aromatic (6h) or heteroaro-
matic rings (6i and 6j), to produce 7h–7j in 94–95%
yields with 96–98% ees, respectively (entries 8–10). Fi-
nally, substrates 6k and 6l with aliphatic ketone moi-
eties were also tested for this transformation under
otherwise identical reaction conditions, which gave
the corresponding products 7k and 7l in excellent
yields (93–94%) with good enantioselectivity (82–
84% ee), respectively (entries 11 and 12).
Entry Substrate R3
Product/Yield
[%][b]
ee
[%][c]
1
2
3
4
5
6a
6b
6c
6d
6e
C6H5
4-FC6H4
4-ClC6H4
4-BrC6H4 7d/97
4-
7a/96
7b/93
7c/94
98
98
96
98
98
The cascade asymmetric hydrogenation/dynamic ki-
netic resolution (DKR) of racemic cyclic b-keto sulfo-
namides and b-keto sulfones was also investigated in
this work. As shown in Scheme 2, cyclic b-keto sulf-
7e/92
CH3C6H4
2-FC6H4
3-FC6H4
2-naphthyl 7h/94
furyl
thienyl
CH3
CH3CH2
AHCTUNGTREGaNNUN mides derived from a-tetralone (4oc) or a-indanone
6
7
8
9
10
11
12
6f
6g
6h
6i
6j
6k
6l
7f/95
7g/97
95
96
96
98
98
82
84
(4pc), as well as the cyclic b-keto sulfone (6m) were
hydrogenated smoothly in the presence of 0.4 mol%
of catalyst I, to give the desired products 5oc, 5pc and
7m in high yields (92–97%) with extremely high ee
values (98–99%) and excellent diastereoselectivities
(>99:1), respectively. Finally, the AH of 4ap was per-
formed on a gram-scale without any difficulty at a cat-
alyst loading of 0.2 mol%, leading to the targeted
product 5ap (1.43 g) in 98% yield with 99% ee
(Scheme 3), thus attesting the practical utility of the
catalytic protocol.
7i/95
7j/94
7k/93
7l/94
[a]
Reaction conditions: [6]=0.1M, 0.4 mol% cat. I in 2 mL
solvent, room temperature, 24 h.
Isolated yield.
[b]
[c]
Determined by chiral HPLC.
Scheme 2. Asymmetric hydrogenation/dynamic kinetic resolution of cyclic b-keto sulfamides and b-keto sulfone.
Scheme 3. Gram-scale asymmetric synthesis of 5ap.
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Asymmetric Hydrogenation of b-Keto Sulfonamides and b-Keto Sulfones
Conclusions
General Procedure for the Asymmetric
Hydrogenation of b-Keto Sulfonamides
In summary, we have developed an efficient method-
ology for the synthesis of optically active b-hydroxy
sulfonamides and b-hydroxy sulfones via asymmetric
hydrogenation of b-keto sulfonamides and b-keto sul-
fones catalyzed by the phosphine-free h6-p-arene/
TsDPEN-Ru(II) complex I. A wide range of chiral
chain b-hydroxy sulfonamides and b-hydroxy sulfones
were obtained in high yields and excellent enantiose-
lectivities. The cascade asymmetric hydrogenation/dy-
namic kinetic resolution (DKR) of cyclic b-keto sulfo-
namides and b-keto sulfones was also successful using
the same catalyst, affording the corresponding chiral
b-hydroxy sulfonamides and b-hydroxy sulfones in
high yields with excellent enantioselectivities and dia-
stereoselectivities. Further study on the utilization of
the protocol for synthesis of biologically important
molecules is underway in our laboratory.
b-Keto sulfonamides or b-keto sulfones (0.2 mmol), catalyst
I (0.8 mmol), and degassed MeOH (2 mL) were added to
a glass tube under nitrogen. The tube was then placed into
a stainless steel autoclave, which was purged with hydrogen
gas for three times before being pressurized with H2 to
40 atm. Subsequently, the mixture was stirred under this H2
pressure at room temperature for 24 h. After careful release
of the hydrogen, methanol was concentrated to afford the
crude product. Purification was performed with a silica gel
column eluted with petroleum ether/ethyl acetate (2:1, v/v)
to give the pure product. The enantiomeric excess was de-
termined by chiral HPLC analysis.
2-Hydroxy-N,2-diphenylethanesulfonamide (5aa): White
solid; yield: 97%; 98% ee. The enantiomeric excess was de-
termined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (90:10) as the eluent; flow: 1.0 mLminÀ1; l=210 nm]:
t
minor =22.479 min, tmajor =26.241 min; [a]2D7: +17.2 (c 1.00 in
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.37–7.31 (m,
9H), 7.22 (t, J=6.8 Hz, 1H), 7.05 (s, 1H), 5.35 (d, J=
10.4 Hz, 1H), 3.36 (dd, J=14.8, 10.8 Hz, 1H), 3.33 (s, 1H),
3.22 (d, J=14.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
140.93, 136.74, 129.78, 129.14, 128.82, 126.10, 125.86, 122.43,
70.05, 57.47; IR (film): nmax =3467.6, 3282.7, 2892.1, 1596.8,
1492.0, 1399.9, 1334.9, 1142.1, 1062.1, 992.3, 892.2, 752.5,
699.4 cmÀ1; ESI-MS: m/z=300.0 [M+Na]+; HR-MS: m/z=
300.0666 [M+Na]+, calcd. for C14H15NNaO3S: 300.0665.
N-(4-Fluorophenyl)-2-hydroxy-2-phenylethanesulfonam-
ide (5ab): White solid; yield: 99%; 97% ee. The enantiomer-
ic excess was determined by HPLC [Daicel Chiralpak AD-
Experimental Section
General Remarks
Unless otherwise noted, all reagents were purchased from
commercial suppliers and used without further purification.
Methanol was freshly distilled from sodium. Column chro-
matography purifications were performed using 200–300
1
mesh silica gel. H and 13C NMR spectra were recorded on
H
with hexane/i-PrOH (90:10) as the eluent, flow:
a
Varian-Inova-400 spectrometer. Solvent for NMR is
1.0 mLminÀ1
;
l=210 nm]:
tminor =20.880 min,
tmajor =
CDCl3 or DMSO, unless the otherwise noted. Chemical
shifts are reported in delta (d) units in parts per million
(ppm) relative to the singlet (0 ppm) for tetramethylsilane
(TMS). Data are reported as follows: chemical shift, multi-
plicity (s=single, d=doublet, t=triplet, m=multiplet, dd=
doublet of doublets), coupling constants (Hz), and integra-
tion. 13C NMR spectra were recorded on 100 MHz or
75 MHz. Chemical shifts are reported in parts per million
relative to the central line of the multiplet at 77.0 ppm for
CDCl3, 39.5 ppm for DMSO. Mass spectra were recorded
using an Agilent 6120 Quadrupole LC/MS system with ESI
resource. High-resolution mass spectra (HR-MS) for all the
compounds were determined on a Micromass GCT-TOF
mass spertrometer with an ESI source. High-performance
liquid chromatography (HPLC) was performed on an Agi-
lent 1200 Series chromatograph using a Chiralpak AD-H/or
Chiralcel OD-H/or OJ-H column using 2-propanol/hexane
as the eluent. Infrared spectra were obtained on a Varian-
1000 FT-IR spectrometer. Optical rotations were measured
at 589 nm (Na D line) on a Autopol IV automatic polarime-
ter.
23.421 min; [a]D27: +14.4 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.34–7.26 (m, 7H), 7.18 (s, 1H), 7.04
(t, J=8.4 Hz, 2H), 5.35 (d, J=10.0 Hz, 1H), 3.49 (s, 1H),
3.38 (dd, J=14.4, 10.8 Hz, 1H), 3.16 (d, J=14.4 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=161.12 (d, 1JC,F =245 Hz),
4
140.94, 132.62 (d, JC,F =3 Hz), 129.18, 128.89, 125.84, 125.22
(d, 3JC,F =6 Hz), 116.52 (d, 2JC,F =23 Hz), 70.07, 56.99; IR
(film): nmax =3472.7, 3284.9, 2891.4, 1605.0, 1504.3, 1453.9,
1382.9, 1331.7, 1204.7, 1141.4, 1162.3, 993.1, 898.9, 758.0,
705.6 cmÀ1; ESI-MS: m/z=318.0 [M+Na]+; HRMS: m/z=
318.0568 [M+Na]+, calcd. for C14H14FNNaO3S: 318.0571.
N-(4-Chlorophenyl)-2-hydroxy-2-phenylethanesulfonam-
ide (5ac): White solid; yield: 98%; 97% ee. The enantiomer-
ic excess was determined by HPLC [Daicel Chiralpak AD-
H
with hexane/i-PrOH (90:10) as the eluent, flow:
1.0 mLminÀ1
;
l=210 nm]: minor =23.052 min, tmajor =
t
25.684 min; [a]D27: +17.1 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.33–7.24 (m, 9H), 7.22 (s, 1H), 5.33
(d, J=10.4 Hz, 1H), 3.46 (s, 1H), 3.37 (dd, J=14.4, 10.8 Hz,
1H), 3.17 (d, J=14.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d=140.83, 135.38, 131.70, 129.82, 129.19, 128.92, 125.84,
123.85, 70.05, 57.27; IR (film): nmax =3440.9, 3290.4,
2919.5,1637.7, 1491.6, 1452.3, 1325.6, 1216.8, 1145.2, 1056.6,
997.2, 910.0, 827.7, 742.9, 697.2 cmÀ1; ESI-MS: m/z=334.0
[M+Na]+; HR-MS: m/z=334.0288 [M+Na]+, calcd. for
C14H14ClNNaO3S: 334.0275.
Synthesis of Substrate and Catalyst
All b-carbonyl sulfonamides and b-keto sulfones were pre-
pared according to the known methods.[16] The catalyst was
prepared using the known procedure.[12b]
N-(4-Bromophenyl)-2-hydroxy-2-phenylethanesulfonam-
ide (5ad): White solid; yield: 96%; 98% ee. The enantiomer-
Adv. Synth. Catal. 2013, 355, 2860 – 2872
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2865

Xiao-Fei Huang et al.
FULL PAPERS
ic excess was determined by HPLC [Daicel Chiralcel OD-H
meric excess was determined by HPLC [Daicel Chiralpak
with hexane/i-PrOH (92:8) as the eluent, flow: 1.0 mLminÀ1
;
AD-H with hexane/i-PrOH (90:10) as the eluent, flow:
t
major =32.189 min; [a]2D7:
1.0 mLminÀ1
;
l=210 nm]:
tminor =23.753 min,
tmajor =
l=210 nm]:
t
minor =24.451 min,
1
30.875 min; [a]D27: +36.2 (c 0.50 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.55(d, J=9.6 Hz, 1H), 7.32–7.28 (m,
5H), 7.19 (s, 1H), 7.15 (d, J=8.0 Hz, 1H), 6.99–6.92 (m,
2H), 5.30 (d, J=10.0 Hz, 1H), 3.88 (s, 3H), 3.71 (s, 1H),
3.41 (dd, J=14.4, 10.4 Hz, 1H), 3.29 (d, J=14.4 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=149.88, 141.00, 128.97,
128.49, 126.23, 125.82, 125.71, 121.68, 121.65, 111.15, 69.28,
59.17, 56.09; IR (film): nmax =3503.0, 3215.7, 2927.1, 1599.1,
1501.5, 1452.7, 1400.0, 1337.1, 1254.7, 1145.6, 1050.2, 923.7,
750.9 cmÀ1; ESI-MS: m/z=330.1 [M+Na]+; HR-MS: m/z=
330.0778 [M+Na]+, calcd. for C15H17NNaO4S: 330.0770.
N-(2,4-Dichlorophenyl)-2-hydroxy-2-phenylethanesulfon-
amide (5ai): White solid; yield: 97%; 97% ee. The enantio-
meric excess was determined by HPLC [Daicel Chiralpak
AD-H with hexane/i-PrOH (90:10) as the eluent, flow:
+14.5 (c 0.40 in CH3COCH3); H NMR (400 MHz, CDCl3):
d=7.46 (d, J=8.4 Hz, 2H), 7.37–7.29 (m, 5H), 7.18 (d, J=
8.4 Hz, 2H), 7.07 (s, 1H), 5.34 (d, J=10.4 Hz, 1H), 3.40 (dd,
J=14.8, 10.4 Hz, 1H), 3.24 (s, 1H), 3.21–3.17 (m, 1H);
13C NMR (100 MHz, CDCl3): d=140.77, 135.94, 132.78,
129.24, 129.00, 125.84, 124.12, 119.44, 70.19, 57.23; IR (film):
nmax =3463.2, 3268.1, 2925.9, 1489.9, 1391.0, 1323.1, 1145.4,
1052.3, 999.5, 911.1, 824.2, 700.5 cmÀ1; ESI-MS: m/z=376.3,
378.1 [M+Na]+; HR-MS: m/z=377.9775, 379.9753 [M+
Na]+, calcd. for C14H14BrNNaO3S: 377.9775, 379.9755.
2-Hydroxy-2-phenyl-N-p-tolylethanesulfonamide
(5ae):
White solid; yield: 95%; 97% ee. The enantiomeric excess
was determined by HPLC [Daicel Chiralpak AD-H with
hexane/i-PrOH (90:10) as the eluent; flow: 1.0 mLminÀ1
;
l=210 nm]:
t
minor =22.066 min,
t
major =23.417 min; [a]2D7:
1
1.0 mLminÀ1
;
l=210 nm]:
tminor =16.130 min,
tmajor =
+16.2 (c 1.00 in CH3COCH3); H NMR (400 MHz, CDCl3):
d=7.33–7.30 (m, 5H), 7.20(d, J=7.6 Hz, 2H), 7.14 (d, J=
8.4 Hz, 2H), 7.08 (s, 1H), 5.34 (d, J=10.0 Hz, 1H), 3.51 (s,
1H), 3.40 (dd, J=14.8, 11.6 Hz, 1H), 3.19 (d, J=14.4 Hz,
18.256 min; [a]D27: +24.5 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.62 (d, J=8.8 Hz, 1H), 7.43 (s, 1H),
7.35–7.24 (m, 6H), 7.20 (s, 1H), 5.33 (d, J=10.0 Hz, 1H),
3.49 (dd, J=14.4, 10.4 Hz, 1H), 3.33 (s, 1H), 3.28 (d, J=
7.2 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=140.60,
132.46, 131.32, 129.76, 129.16, 128.88, 128.60, 125.87, 123.34,
69.63, 59.90; IR (film): nmax =3502.8, 3305.5, 2989.6, 1485.6,
1387.9, 1135.0, 1063.2, 1000.6, 939.6, 856.0, 811.3, 753.4,
692.7 cmÀ1; ESI-MS: m/z=368.0 [M+Na]+; HR-MS: m/z=
363.0332 [M+NH4]+, calcd. for C14H17Cl2N2O3S: 363.0331.
N-[3,5-Bis(trifluoromethyl)phenyl]-2-hydroxy-2-phenyl-
ethanesulfonamide (5aj): White solid; yield: 92%; 96% ee.
The enantiomeric excess was determined by HPLC [Daicel
Chiralcel OD-H with hexane/i-PrOH (92:8) as the eluent,
1H), 2.33ACHTUNGTRENNUNG
(s, 3H); 13C NMR (100 MHz, CDCl3): d=141.06,
136.12, 134.03, 130.31, 129.09, 128.72, 125.89, 122.99, 69.94,
57.25, 21.11; IR (film): nmax =3457.6, 3304.7, 3034.3, 1662.9,
1511.4, 1451.5, 1390.6, 1322.9, 1215.5, 1144.9, 1058.2, 999.6,
916.3, 809.7, 765.7, 698.8, 646.6 cmÀ1; ESI-MS: m/z=314.1
[M+Na]+; HR-MS: m/z=314.0817 [M+Na]+, calcd. for
C15H17NNaO3S: 314.0821.
2-Hydroxy-N-(4-methoxyphenyl)-2-phenylethanesulfon-
amide (5af): White solid; yield: 97%; 99% ee. The enantio-
meric excess was determined by HPLC [Daicel Chiralpak
AD-H with hexane/i-PrOH (90:10) as the eluent, flow:
1.0 mLminÀ1
;
l=210 nm]:
tminor =31.477 min,
tmajor =
flow: 1.0 mLminÀ1; l=210 nm]: tminor =9.827 min, tmajor
=
33.698 min; [a]D27: +13.4 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.34–7.32 (m, 5H), 7.26(d, J=8.4 Hz,
2H), 6.87 (d, J=8.8 Hz, 2H), 6.84 (s, 1H), 5.34 (d, J=
10.4 Hz, 1H), 3.79 (s, 3H), 3.39 (dd, J=14.8, 11.2 Hz, 1H),
3.35 (s, 1H), 3.15 (d, J=14.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=158.40, 141.07, 129.14, 128.79, 125.88, 125.73,
114.90, 70.09, 56.91, 55.71; IR (film): nmax =3486.8, 3284.9,
2835.5, 1611.8, 1511.3, 1455.6, 1395.4, 1327.3, 1252.5, 1156.6,
1056.1, 903.8, 830.7, 772.3, 663.6, 526.8 cmÀ1; ESI-MS: m/z=
330.0 [M+Na]+; HR-MS: m/z=330.0778 [M+Na]+, calcd.
for C15H17NNaO4S: 330.0770.
12.038 min; [a]D27: +18.1 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.72 (d, J=9.2 Hz, 3H), 7.46 (s, 1H),
7.34–7.31 (m, 5H), 5.38 (d, J=10.0 Hz, 1H), 3.41 (dd, J=
14.4, 10.4 Hz, 1H), 3.26 (d, J=14.8 Hz, 1H), 3.20 (s, 1H);
2
13C NMR (100 MHz, CDCl3): d=140.42, 133.13 (q, JC,F
=
34 Hz), 129.38, 129.28, 125.79, 123.15 (q, 1JC,F =272 Hz),
121.94 (br-s), 119.34 (m), 70.39, 57.73; IR (film): nmax
=
3557.9, 3432.4, 3280.8, 1621.6, 1424.3, 1377.6, 1341.5, 1280.6,
1183.1, 1141.2, 1052.0, 995.5, 979.5, 744.3, 701.6 cmÀ1; ESI-
MS: m/z=436.0 [M+Na]+; HR-MS: m/z=431.0866 [M+
NH4]+, calcd. for C16H17F6N2O3S: 431.0859.
N-(3-Chlorophenyl)-2-hydroxy-2-phenylethanesulfonam-
ide (5ag): White solid; yield: 95%; 98% ee. The enantiomer-
ic excess was determined by HPLC [Daicel Chiralpak AD-
N-(2,6-Diisopropylphenyl)-2-hydroxy-2-phenylethanesul-
fonamide (5ak): White solid; yield: 94%; 96% ee. The enan-
tiomeric excess was determined by HPLC [Daicel Chiralcel
OD-H with hexane/i-PrOH (92:8) as the eluent; flow:
H
with hexane/i-PrOH (90:10) as the eluent; flow:
1.0 mLminÀ1
l=210 nm]: minor =17.933 min, tmajor
21.305 min; [a]D27: +19.1 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.34–7.25 (m, 8H), 7.18(s, 1H), 7.16
;
t
=
1.0 mLminÀ1
;
l=210 nm]:
t
minor =9.877 min,
tmajor =
15.044 min; [a]D27: +19.7 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.41 (d, J=4.0 Hz, 4H), 7.37–7.30
AHCTUNGTRENNUNG
(s, 1H), 5.34 (d, J=10.0 Hz, 1H), 3.47–3.40 (m, 2H), 3.25–
3.21 (m, 1H); 13C NMR (100 MHz, CDCl3): d=140.77,
138.08, 135.29, 130.74, 129.21, 128.95, 126.06, 125.87, 122.09,
120.15, 70.06, 57.58; IR (film): nmax =3487.1, 3110.7, 3037.5,
2862.3, 1593.6, 1473.3, 1398.9, 1319.4, 1252.3, 1223.1, 1142.6,
950.9, 866.2, 783.2, 698.4, 567.3 cmÀ1; ESI-MS: m/z=312.1
[M+H]+; HR-MS: m/z=329.0720 [M+NH4]+, calcd. for
C14H18ClN2O3S: 329.0721.
(m, 2H), 7.20 (d, J=7.6 Hz, 2H), 6.15ACTHNUTRGNE(NUG s, 1H), 5.44 (d, J=
10.0 Hz, 1H), 3.60 (dd, J=14.0, 10.4 Hz, 1H), 3.57–3.48 (m,
2H), 3.46 (s, 1H), 3.41 (d, J=6.0 Hz, 1H), 1.24 (q, J=
2.8 Hz, 12H); 13C NMR (100 MHz, CDCl3): d=148.38,
141.05, 129.25, 129.17, 128.78, 125.88, 124.34, 70.05, 61.59,
28.91, 24.24; IR (film): nmax =3495.3, 3287.2, 2972.8, 1626.4,
1457.6, 1385.7, 1318.9, 1152.8, 1052.9, 986.6, 780.6, 761.4,
698.5 cmÀ1; ESI-MS: m/z=384.1 [M+Na]+; HR-MS: m/z=
362.1789 [M+H]+, calcd. for C20H28NO3S: 362.1784.
2-Hydroxy-N-(2-methoxyphenyl)-2-phenylethanesulfon-
amide (5ah): colorless oil; yield: 99%; 97% ee. The enantio-
2866
asc.wiley-vch.de
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 2860 – 2872

Asymmetric Hydrogenation of b-Keto Sulfonamides and b-Keto Sulfones
N-Ethyl-2-hydroxy-2-phenylethanesulfonamide
(5am):
enantiomeric excess was determined [HPLC on Daicel Chir-
Colorless oil; yield: 91%; 99% ee. The enantiomeric excess
was determined by HPLC [Daicel Chiralcel OD-H with
hexane/i-PrOH (92:8) as the eluent, flow: 1.0 mLminÀ1; l=
210 nm]: tminor =18.524 min, tmajor =20.664 min; [a]2D7: +40.5
(c 0.50 in CH3COCH3); 1H NMR (400 MHz, CDCl3): d=
7.37–7.31 (m, 5H), 5.25 (d, J=9.2 Hz, 1H), 4.83 (s, 1H),
3.59 (s, 1H), 3.39 (dd, J=14.4, 10.4 Hz, 1H), 3.23 (d, J=
14.4 Hz 1H), 3.18–3.12 (m, 2H), 2.88 (s, 1H), 1.19 (t, J=
6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=141.37,
129.08, 128.63, 125.88, 69.76, 59.07, 38.68, 37.60, 15.75; IR
(film): nmax =3457.8, 2981.4, 1632.4, 1454.0, 1317.6, 1136.7,
1060.3, 954.2, 785.6, 749.4, 701.9, 558.1 cmÀ1; ESI-MS: m/z=
252.1 [M+Na]+; HR-MS: m/z=252.0668 [M+H]+, calcd.
for C10H15NNaO3S: 252.0665.
alcel OD-H with hexane/i-PrOH (90:10) as the eluent, flow:
1.0 mLminÀ1
;
l=210 nm]:
tminor =16.834 min,
tmajor =
18.811 min; [a]D27: +20.4 (c 0.50 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.29 (d, J=8.8 Hz, 2H), 7.24–7.20
(m, 4H), 7.00 (t, J=8.4 Hz, 2H), 6.96 (s, 1H), 5.30 (d, J=
10.0 Hz, 1H), 3.36 (dd, J=14.8, 10.8 Hz, 1H), 3.17 (s, 1H),
3.12 (d, J=14.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
162.73 (d, 1JC,F =246 Hz), 136.69, 135.20, 131.65, 129.82,
127.65 (d, 3JC,F =8 Hz), 123.67, 115.97 (d, 2JC,F =22 Hz),
69.13, 57.39; IR (film): nmax =3491.6, 3296.1, 1605.5, 1489.6,
1311.8, 1223.2, 1128.5, 1053.1, 998.1, 835.9, 759.3 cmÀ1; ESI-
MS: m/z=352.0 [M+Na]+; HR-MS: m/z=352.0196 [M+
Na]+, calcd. for C14H13ClFNNaO3S: 352.0189.
N,2-Bis(4-chlorophenyl)-2-hydroxyethanesulfonamide
(5cc): White solid; yield: 99%; >99% ee. The enantiomeric
excess was determined by HPLC [Daicel Chiralpak AD-H
N-Butyl-2-hydroxy-2-phenylethanesulfonamide
(5an):
White solid; yield: 91%; 99% ee. The enantiomeric excess
was determined by HPLC [Daicel Chiralcel OJ-H with
hexane/i-PrOH (92:8) as the eluent, flow: 1.0 mLminÀ1; l=
210 nm]: tminor =16.410 min, tmajor =17.347 min; [a]2D7: +32.3
(c 1.00 in CH3COCH3); 1H NMR (400 MHz, CDCl3): d=
7.37–7.31 (m, 5H), 5.26 (d, J=9.6 Hz, 1H), 4.92 (s, 1H),
with hexane/i-PrOH (92:8) as the eluent, flow: 1.0 mLminÀ1
;
l=210 nm]:
t
minor =32.376 min,
t
major =30.101 min; [a]2D7:
1
+27.2 (c 1.00 in CH3COCH3); H NMR (400 MHz, CDCl3):
d=7.31–7.27 (m, 5H), 7.21 (t, J=8.0 Hz, 4H), 5.31 (d, J=
10.4 Hz, 1H), 3.61 (s, 1H), 3.36 (dd, J=14.4, 11.2 Hz, 1H),
3.16 (d, J=14.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
139.28, 135.17, 134.68, 131.87, 129.90, 129.33, 127.21, 123.77,
69.34, 57.26; IR (film): nmax =3443.6, 3281.4, 1489.3, 1330.3,
1142.2, 1064.3, 831.3, 778.4, 540.6 cmÀ1; ESI-MS: m/z=368.0
[M+Na]+; HR-MS: m/z=367.9880 [M+Na]+, calcd. for
C14H13Cl2NNaO3S 367.9885.
3.64ACHTUNGTRENNUNG(s, 1H), 3.40 (dd, J=15.2, 10.4 Hz, 1H), 3.22 (d, J=
14.4 Hz, 1H), 3.08 (q, J=7.2 Hz, 2H), 1.55–1.48 (m, 2H)
1.38–1.33 (m, 2H), 0.92 (t, J=7.6 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=141.41, 129.07, 128.61, 125.90, 69.75,
58.97, 43.38, 32.24, 19.96, 13.81; IR (film): nmax =3457.2,
2959.6, 2058.9, 1638.2, 1424.3, 1306.0, 1127.9, 1079.8, 997.9,
743.0, 699.3, 547.7 cmÀ1; ESI-MS: m/z=280.1 [M+Na]+;
2-(4-Bromophenyl)-N-(4-chlorophenyl)-2-hydroxyethane-
sulfonamide (5dc): White solid; yield: 97%; 98% ee. The
enantiomeric excess was determined by HPLC [Daicel Chir-
alpak AD-H with hexane/i-PrOH (90:10) as the eluent,
HR-MS:
m/z=280.0980
[M+Na]+,
calcd.
for
C12H19NNaO3S: 280.0978.
N-tert-Butyl-2-hydroxy-2-phenylethanesulfonamide (5ao):
White solid; yield: 92%; 98% ee. The enantiomeric excess
was determined by HPLC [Daicel Chiralpak AD-H with
hexane/i-PrOH (90:10) as the eluent, flow: 1.0 mLminÀ1; l=
210 nm]: tminor =13.842 min, tmajor =13.767 min; [a]2D7: +28.6
(c 1.00 in CH3COCH3); 1H NMR (400 MHz, CDCl3): d=
7.38 (d, J=4.0, 4H), 7.33–7.31 (m, 1H), 5.27 (d, J=9.6 Hz,
1H), 4.70 (d, J=9.2 Hz, 1H), 3.73 (s, 1H), 3.43 (dd, J=14.4,
10.0 Hz, 1H), 3.30 (d, J=14.0 Hz 1H); 13C NMR (100 MHz,
CDCl3): d=141.34, 129.04, 128.51, 125.93, 69.82, 63.62,
55.33, 30.51; IR (film): nmax =3434.8, 3190.7, 2973.8, 1458.1,
1394.5, 1310.4, 1229.6, 1130.7, 1011.2, 878.5, 762.5, 701.7,
563.0 cmÀ1; ESI-MS: m/z=280.1 [M+Na]+; HR-MS: m/z=
280.0979 [M+Na]+, calcd. for C12H19NNaO3S: 280.0978.
flow: 1.0 mLminÀ1; l=210 nm]: tminor =26.399 min, tmajor
=
23.762 min; [a]D27: +26.8 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.45 (d, J=7.6 Hz, 2H), 7.31 (d, J=
7.6 Hz, 2H), 7.22 (d, J=8.0 Hz, 2H), 7.15 (d, J=7.6 Hz,
2H), 5.29 (d, J=10.0 Hz, 1H), 3.49 (s, 1H), 3.35 (dd, J=
14.0, 10.8 Hz, 1H), 3.17 (d, J=14.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=139.76, 135.13, 132.30, 131.91, 129.92,
127.52, 123.79, 122.83, 69.43, 57.18; IR (film): nmax =3448.8,
3297.2, 1490.0, 1388.1, 1326.7, 1142.1, 1064.9, 1002.0, 915.7,
834.4, 587.6 cmÀ1; ESI-MS: m/z=411.9 [M+Na]+; HR-MS:
m/z=411.9371 [M+Na]+, calcd- for C14H13BrClNNaO3S:
411.9380.
N-(4-Chlorophenyl)-2-hydroxy-2-(4-nitrophenyl)-ethane-
sulfonamide (5ec): White solid; yield: 98%; >99% ee. The
enantiomeric excess was determined by HPLC [Daicel Chir-
alpak AD-H with hexane/i-PrOH (90:10) as the eluent,
N-Benzyl-2-hydroxy-2-phenylethanesulfonamide
(5ap):
White solid; yield: 97%; 99% ee. The enantiomeric excess
was determined by HPLC [Daicel Chiralpak AD-H with
hexane/i-PrOH (90:10) as the eluent; flow: 1.0 mLminÀ1
;
flow: 1.0 mLminÀ1 major =44.095 min; [a]D27:
; l=210 nm]: t
1
l=210 nm]:
t
minor =20.033 min,
t
major =22.279 min; [a]2D7:
+29.8 (c 0.50 in CH3COCH3); H NMR (400 MHz, CDCl3):
d=8.07 (d, J=8.0 Hz, 2H), 7.41 (d, J=8.0 Hz, 2H), 7.23 (d,
J=8.0 Hz, 2H), 7.13 (s, 1H), 5.37 (d, J=10.0 Hz, 1H), 3.67
(s, 1H), 3.28 (dd, J=14.4 10.4 Hz, 1H), 3.15 (d, J=14.4 Hz,
1H); 13C NMR (100 MHz, DMSO-d6): d=155.99, 153.10,
152.25, 142.50, 134.49, 132.91, 128.78, 126.78, 73.04, 63.48;
IR (film): nmax =3453.3, 3287.5, 1603.0, 1515.6, 1350.0,
1144.7, 1002.3, 920.9, 852.0,696.2,532.8 cmÀ1; ESI-MS: m/z=
379.0 [M+Na]+; HR-MS: m/z=379.0123 [M+Na]+, calcd.
for C14H13ClN2NaO5S: 379.0126.
1
+40.7 (c 1.00 in CH3COCH3). H NMR (400 MHz, CDCl3):
d=7.34–7.22 (m, 10H), 5.18 (d, J=9.6 Hz, 1H), 5.15–5.08
(m, 1H), 4.32 (d, J=5.6 Hz, 2H), 3.33 (dd, J=14.8, 9.6 Hz,
2H), 3.16 (d, J=14.4 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d=141.12, 136.78, 129.11, 129.05, 128.66, 128.40, 128.32,
125.84, 69.82, 59.73, 47.62; IR (film): nmax =3401.5, 3247.0,
1605.3, 1494.4, 1447.4, 1423.4, 1310.5, 1138.9, 1060.8, 993.6,
875.3, 752.4, 605.2, 559.8 cmÀ1; ESI-MS: m/z=314.0 [M+
Na]+; HR-MS: m/z=314.0812 [M+Na]+, calcd- for
C15H17NNaO3S: 314.0821.
N-(4-Chlorophenyl)-2-hydroxy-2-p-tolylethanesulfonam-
ide (5fc): White solid; yield: 93%; 99% ee. The enantiomer-
ic excess was determined by HPLC [Daicel Chiralpak AD-
N-(4-Chlorophenyl)-2-(4-fluorophenyl)-2-hydroxyethane-
sulfonamide (5bc): White solid; yield: 99%; >99% ee. The
Adv. Synth. Catal. 2013, 355, 2860 – 2872
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2867

Xiao-Fei Huang et al.
flow: 1.0 mLminÀ1; l=210 nm]: tminor =31.424 min, tmajor
=
FULL PAPERS
H
with hexane/i-PrOH (90:10) as the eluent, flow:
1.0 mLminÀ1
;
l=210 nm]: minor =20.680 min, tmajor
t
=
34.240 min; [a]D27: +12.0 (c 0.50 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.36 (s, 1H), 7.29 (d, J=8.8 Hz, 2H),
7.23 (d, J=8.4 Hz, 3H), 6.84–6.81 (m, 3H), 5.30 (d, J=
10.0 Hz, 1H), 3.75 (s, 3H), 3.67 (s, 1H), 3.40 (dd, J=14.4
10.8 Hz, 1H), 3.21 (d, J=14.4 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=160.12, 142.55, 135.39, 131.61, 130.28, 129.80,
123.77, 117.99, 114.06, 111.59, 69.85, 57.29, 55.48; IR (film):
nmax =3474.7, 3275.1, 1600.4, 1491.8, 1326.9, 1263.6, 1149.7,
1046.0, 924.3, 728.7, 697.5 cmÀ1; ESI-MS: m/z=364.1 [M+
Na]+; HR-MS: m/z=364.0385 [M+Na]+, calcd. for
C15H16ClNNaO4S: 364.0381.
23.234 min; [a]D27: +21.5 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.29 (d, J=8.8 Hz, 3H), 7.24 (d, J=
8.8 Hz, 2H), 7.14 (dd, J=13.2 8.0 Hz, 4H), 5.29 (d, J=
10.0 Hz, 1H), 3.42 (s, 1H), 3.40–3.36 (m, 1H), 3.17 (d, J=
13.6 Hz, 1H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3):
d=138.81, 137.90, 135.44, 131.63, 129.82, 129.79, 125.81,
123.85, 69.88, 57.26, 21.35; IR (film): nmax =3447.4, 3295.1,
1493.2, 1316.8, 1134.1, 1090.3, 1004.4, 823.9, 594.7 cmÀ1; ESI-
MS: m/z=348.0 [M+Na]+; HR-MS: m/z=348.0421 [M+
Na]+, calcd. for C15H16ClNNaO3S: 348.0432.
N-(4-Chlorophenyl)-2-hydroxy-2-(4-methoxyphenyl)-eth-
anesulfonamide (5gc): White solid; yield: 92%; >99% ee.
The enantiomeric excess was determined by HPLC [Daicel
Chiralpak AD-H with hexane/i-PrOH (90:10) as the eluent,
N-(4-Chlorophenyl)-2-(3,4-dichlorophenyl)-2-hydroxyeth-
anesulfonamide (5kc): White solid; yield: 95%; 96% ee. The
enantiomeric excess was determined by HPLC [Daicel Chir-
alcel OD-H with hexane/i-PrOH (92:8) as the eluent, flow:
flow: 1.0 mLminÀ1; l=210 nm]: tminor =35.086 min, tmajor
=
1.0 mLminÀ1
;
l=210 nm]:
tminor =24.197 min,
tmajor =
31.594 min; [a]D27: +21.4 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.21 (d, J=7.2 Hz, 2H), 7.17–7.11
(m, 5H), 6.77 (d, J=7.6 Hz, 2H), 5.21 (d, J=10.4 Hz, 1H),
3.67 (s, 3H), 3.31 (dd, J=14.0 10.8 Hz, 1H), 3.19 (s, 1H),
3.07 (d, J=14.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
160.02, 135.48, 132.92, 131.64, 129.79, 127.21, 123.86, 114.52,
69.74, 57.19, 55.54; IR (film): nmax =3444.0, 3114.1, 1611.4,
1493.2, 1397.0, 1333.8, 1222.0, 1128.1, 1045.9, 944.1, 837.1,
538.7 cmÀ1; ESI-MS: m/z=364.0 [M+Na]+; HR-MS: m/z=
364.0380 [M+Na]+, calcd. for C15H16ClNNaO4S: 364.0381.
2-(2-Chlorophenyl)-N-(4-chlorophenyl)-2-hydroxyethane-
sulfonamide (5hc): White solid; yield: 97%; 97% ee. The
enantiomeric excess was determined by HPLC [Daicel Chir-
alpak AD-H with hexane/i-PrOH (90:10) as the eluent,
26.996 min; [a]D27: À25.4 (c 0.80 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.40 (d, J=7.6 Hz, 2H), 7.32 (d, J=
8.4 Hz, 2H), 7.22 (d, J=8.4 Hz, 2H), 7.18 (s, 1H), 7.11 (d,
J=8.0 Hz, 1H), 5.31 (d, J=10.0 Hz, 1H), 3.58 (s, 1H), 3.35
(dd, J=14.4, 10.8 Hz, 1H), 3.18 (d, J=14.4 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=140.91, 134.94, 133.38,
132.94, 132.07, 131.15, 129.99, 127.87, 125.11, 123.79, 68.89,
57.24; IR (film): nmax =3436.6, 32843, 1491.7, 1386.5, 1329.7,
1147.3, 1074.9, 1007.6, 909.5, 773.0, 624.7 cmÀ1; ESI-MS:
m/z=402.0 [M+Na]+; HR-MS: m/z=401.9505 [M+Na]+,
calcd. for C14H12Cl3NNaO3S: 401.9496.
N-(4-Chlorophenyl)-2-(2,4-dichlorophenyl)-2-hydroxyeth-
anesulfonamide (5lc): White solid; yield: 98%; 95% ee. The
enantiomeric excess was determined by HPLC [Daicel Chir-
alpak AD-H with hexane/i-PrOH (90:10) as the eluent,
flow: 1.0 mLminÀ1; l=210 nm]: tminor =21.667 min, tmajor
=
26.282 min; [a]D27: +35.6 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.55 (d, J=7.2 Hz, 1H), 7.45 (s, 1H),
7.28–7.24 (m, 7H), 5.71 (d, J=10.0 Hz, 1H), 3.84 (s, 1H),
3.42 (d, J=14.8 Hz, 1H), 3.27 (dd, J=14.8 10.4 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=138.14, 135.31, 131.47,
131.36, 129.86, 129.80, 127.74, 127.24, 123.30, 66.73, 55.76;
IR (film): nmax =3537.8, 3276.5, 1632.9, 1492.3, 1394.7,
1324.2, 1291.6, 1105.2, 1044.3, 919.2, 827.5, 765.3,
702.7,559.4 cmÀ1; ESI-MS: m/z=368.0 [M+Na]+; HR-MS:
m/z=367.9891 [M+Na]+, calcd- for C14H13Cl2NNaO3S:
367.9885.
flow: 1.0 mLminÀ1; l=210 nm]: tminor =28.958 min, tmajor
=
34.207 min; [a]D27: +37.3 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.48 (d, J=7.6 Hz 1H), 7.27–7.22 (m,
7H), 5.62 (d, J=9.2 Hz, 1H), 3.66 (s, 1H), 3.37 (d, J=
14.4 Hz, 1H), 3.23–3.18 (m, 1H); 13C NMR (100 MHz,
CDCl3): d=136.67, 135.06, 131.95, 131.72, 129.89, 129.64,
128.27, 128.10, 123.27, 66.42, 55.76; IR (film): nmax =3522.8,
3256.2, 1590.2, 1491.9, 1388.9, 1321.5, 1143.2, 1072.2, 924.1,
826.6, 737.3, 570.3 cmÀ1; ESI-MS: m/z=402.0 [M+Na]+;
HR-MS:
m/z=401.9510
[M+Na]+,
calcd.
for
C14H12Cl3NNaO3S: 401.9496.
2-(3-Bromophenyl)-N-(4-chlorophenyl)-2-hydroxyethane-
sulfonamide (5ic): White solid; yield: 92%; 98% ee. The
enantiomeric excess was determined by HPLC [Daicel Chir-
alpak AD-H with hexane/i-PrOH (90:10) as the eluent,
N-(4-Chlorophenyl)-2-(furan-2-yl)-2-hydroxyethanesulfon-
amide (5mc): White solid; yield: 93%; 97% ee. The enantio-
meric excess was determined by HPLC [Daicel Chiralpak
AD-H with hexane/i-PrOH (90:10) as the eluent, flow:
flow: 1.0 mLminÀ1; l=210 nm]: tminor =22.329 min, tmajor
=
1.0 mLminÀ1
;
l=210 nm]:
tminor =26.901 min,
tmajor =
26.168 min; [a]27: +26.1 (c 0.50 in CH3COCH3); 1H NMR
(400 MHz, CDDCl3): d=7.48–7.44 (m, 2H), 7.34 (d, J=
8.8 Hz, 2H), 7.24 (dd, J=11.6 3.6 Hz, 4H), 5.33 (d, J=
10.0 Hz, 1H), 3.37 (dd, J=14.4 10.4 Hz, 1H), 3.25 (s, 1H),
3.18 (d, J=13.2 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
143.02, 135.04, 131.88, 130.71, 129.87, 128.87, 124.42, 123.77,
123.17, 69.25, 57.2; IR (film): nmax =3503.3, 3270.2, 1490.8,
1318.6, 1287.4, 1135.1, 1088.0, 833.3, 789.8, 593.9 cmÀ1; ESI-
MS: m/z=411.9 [M+Na]+; HR-MS: m/z=411.9385 [M+
Na]+, calcd. for C14H13BrClNNaO3S: 411.9380.
29.079 min; [a]D27: +78.0 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.32 (s, 1H), 7.27 (d, J=8.8 Hz, 2H),
7.20 (d, J=8.8 Hz, 2H), 7.12 (s, 1H), 7.30–6.27 (m, 2H),
5.34 (d, J=10.0 Hz, 1H), 3.58 (dd, J=14.8, 6.4 Hz, 1H),
3.32 (d, J=14.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
152.65, 143.16, 135.24, 131.72, 129.82, 123.79, 110.78, 107.75,
63.80, 54.22; IR (film): nmax =3432.6, 3284.0, 1493.1, 1391.7,
1320.0, 1138.4, 1089.6, 1018.6, 818.6, 747.3, 529.4 cmÀ1; ESI-
MS: m/z=324.0 [M+Na]+; HR-MS: m/z=324.0062 [M+
Na]+, calcd. for C12H12ClNNaO4S: 324.0068.
N-(4-Chlorophenyl)-2-hydroxy-2-(3-methoxyphenyl)-eth-
anesulfonamide (5jc): Colorless oil; yield: 98%; 99% ee.
The enantiomeric excess was determined by HPLC [Daicel
Chiralpak AD-H with hexane/i-PrOH (90:10) as the eluent,
N-(4-Chlorophenyl)-2-hydroxypropane-1-sulfonamide
(5nc): White solid; yield: 92%; 64% ee. The enantiomeric
excess was determined by HPLC [Daicel Chiralpak AD-H
with hexane/i-PrOH (70:30) as the eluent, flow:
2868
asc.wiley-vch.de
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 2860 – 2872

Asymmetric Hydrogenation of b-Keto Sulfonamides and b-Keto Sulfones
1.0 mLminÀ1
;
l=210 nm]:
t
minor =5.516 min,
tmajor
=
t
minor =9.996 min, tmajor =11.015 min; [a]2D7: +37.6 (c 0.50 in
5.031 min; [a]D27: À15.2 (c 0.50 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=7.29 (d, J=8.4 Hz, 2H), 7.21 (d, J=
8.4 Hz, 2H), 4.47–4.41 (m, 1H), 3.24 (s, 1H), 3.18 (dd, J=
14.4, 10 Hz, 1H), 3.09 (dd, J=14.4, 2.0 Hz, 1H), 1.26 (d, J=
6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=135.30,
131.41, 129.77, 123.25, 69.75, 63.74, 57.54, 23.04; IR (film):
nmax =3474.4, 3431.6, 1444.9, 1304.4.1, 1284.3, 1137.8, 1063.5,
1024.1, 754.8, 691.1, 654.3, 628.5 cmÀ1; ESI-MS: m/z=372.0
[M+Na]+; HR-MS: m/z=272.0119 [M+Na]+, calcd. for
C9H12ClNNaO3S: 272.0119.
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.95–7.93 (m,
2H), 7.71–7.67 (m, 1H), 7.59 (t, J=8.0 Hz, 2H), 7.29–7.25
(m, 2H), 7.01–6.97 (m, 2H), 5.27 (d, J=9.6, 1H), 3.80 (s,
1H), 3.48 (dd, J=14.4, 10.0 Hz, 1H), 3.31 (dd, J=14.4,
2.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=162.58 (d,
1JC,F =246 Hz), 139.17, 136.60, 134.29, 129.60, 128.05, 127.56
(d, 3JC,F =9 Hz), 115.74 (d, 2JC,F =21 Hz), 67.92, 63.97; IR
(film): nmax =3478.3, 1604.2, 1509.8, 1446.2, 1281.7, 1224.9,
1168.1, 1135.9, 1065.4, 843.2, 768.7, 743.6, 682.1 cmÀ1; ESI-
MS: m/z=303.0 [M+Na]+; HR-MS: m/z=303.0471 [M+
Na]+, calcd. for C14H13FNaO3S: 303.0462.
1
N-(4-Chlorophenyl)-1-hydroxy-1,2,3,4-tetrahydronaphtha-
lene-2-sulfonamide (5oc): White solid; yield: 94%; 98% ee,
>99:1 dr. The enantiomeric excess was determined by
HPLC [Daicel Chiralpak AD-H with hexane/i-PrOH
1-(4-Chlorophenyl)-2-(phenylsulfonyl)ethanol (7c): White
solid; yield: 93%; 98% ee. The enantiomeric excess was de-
termined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
(90:10) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]: tminor
=
25.708 min,
t
major =31.198 min; [a]2D7: +21.8 (c 0.80 in
t
minor =11.071 min, tmajor =11.650 min; [a]2D7: +42.2 (c 0.50 in
1
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.30 (d, J=
7.2 Hz, 1H), 7.38–7.20 (m, 6H), 7.11 (d, J=6.8 Hz, 1H),
6.91 (s, 1H), 5.28 (s, 1H), 3.45–3.42 (m, 1H), 2.99–2.94 (m,
1H), 2.55 (s, 1H), 2.25–2.16 (m, 2H); 13C NMR (100 MHz,
DMSO-d6): d=137.78, 137.68, 134.97, 130.02, 129.08, 128.47,
127.80, 127.53, 125.92, 121.29, 65.25, 61.92, 27.85, 17.84; IR
(film): nmax =3453.5, 3376.9, 3294.4, 1491.9, 1391.8, 1324.6,
1271.4, 1131.8, 967.6, 834.5, 778.8, 737.7, 602.1 cmÀ1; ESI-
MS: m/z=360.8 [M+Na]+; HR-MS: m/z=360.8105 [M+
Na]+, calcd. for C16H16ClNNaO3S: 360.8109.
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.94 (d, J=
7.6 Hz, 2H), 7.69 (t, J=7.2 Hz, 1H), 7.59 (t, J=7.6 Hz, 2H),
7.28 (d, J=8.4 Hz, 2H), 7.23 (d, J=8.4 Hz, 2H), 5.26 (d, J=
10.0, 1H), 3.80 (s, 1H), 3.46 (dd, J=14.4 10.0 Hz, 1H), 3.31
(dd, J=14.4 0.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
139.28, 139.13, 134.33, 134.18, 129.63, 129.01, 128.06, 127.19,
67.92, 63.88; IR (film): nmax =3475.8, 1489.9, 1284.1, 1133.8,
1083.4, 1073.3, 995.7, 835.7, 782.2, 751.8, 684.4 cmÀ1; ESI-
MS: m/z=346.0 [M+Na]+; HR-MS: m/z=319.0166 [M+
Na]+, calcd. for C14H13ClNaO3S: 319.0166.
N-(4-Chlorophenyl)-1-oxo-2,3-dihydro-1H-indene-2-sul-
fonamide (5pc): White solid; yield: 92%; 98% ee; >99:1 dr.
The enantiomeric excess was determined by HPLC [Daicel
Chiralpak AD-H with hexane/i-PrOH (90:10) as the eluent,
1-(4-Bromophenyl)-2-(phenylsulfonyl)ethanol (7d): White
solid; yield: 97%; 98% ee. The enantiomeric excess was de-
termined by HPLC [Daicel Chiralpak OJ-H with hexane/i-
PrOH (60:40) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
flow: 1.0 mLminÀ1; l=210 nm]: tminor =30.437 min, tmajor
=
t
minor =13.091 min, tmajor =16.323 min; [a]2D7: +32.1 (c 1.00 in
1
25.587 min; [a]27: À9.5 (c 1.00 in CH3COCH3); 1H NMR
(400 MHz, CDDCl3): d=7.42–7.40 (m, 1H), 7.29 (t, J=
3.6 Hz, 2H), 7.24 (s, 2H), 7.16–7.14 (m, 3H), 6.95 (s, 1H),
5.44 (t, J=7.2 Hz, 1H), 4.05 (dd, J=15.2, 6.8 Hz, 1H), 3.54
(dd, J=17.2, 6.8 Hz, 1H), 3.23 (dd, J=16.8, 8.8 Hz, 1H),
2.91 (s, 1H); 13C NMR (100 MHz, DMSO-d6): d=143.29,
139.81, 137.60, 129.08, 128.40, 127.63, 126.97, 124.65, 124.51,
121.33, 73.60, 63.59, 31.93; IR (film): nmax =3397.8, 3231.6,
1492.8, 1395.1, 1326.4, 1135.7, 1017.3, 957.1, 828.9, 751.8,
567.2 cmÀ1; ESI-MS: m/z=346.0 [M+Na]+; HR-MS: m/z=
346.0278 [M+Na]+, calcd. for C15H14ClNNaO3S: 346.0281.
Phenyl-2-(phenylsulfonyl)ethanol (7a): White solid; yield:
96%; 98% ee. The enantiomeric excess was determined by
HPLC [Daicel Chiralpak AD-H with hexane/i-PrOH
CH3COCH3); H NMR (300 MHz, CDCl3): d=7.92 (d, J=
7.5 Hz, 2H), 7.68 (t, J=7.2 Hz, 1H), 7.58 (t, J=7.5 Hz, 2H),
7.41 (t, J=8.1 Hz, 2H), 7.16 (d, J=8.7 Hz, 2H), 5.23 (d, J=
9.6, 1H), 3.83 (s, 1H), 3.46 (dd, J=14.1, 9.9 Hz, 1H), 3.29
(dd, J=14.4, 1.8 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=
139.81, 139.11, 134.29, 131.91, 129.59, 128.03, 127.50, 122.26,
67.94, 63.78; IR (film): nmax =3474.8, 1469.9, 1282.5, 1133.8,
1087.4, 1079.3, 995.7, 835.7, 772.2, 753.8, 674.4 cmÀ1; ESI-
MS: m/z=363.0 [M+Na]+; HR-MS: m/z=362.9648 [M+
Na]+, calcd. for C14H13BrNaO3S: 362.9661.
2-(Phenylsulfonyl)-1-p-tolylethanol (7e): White solid;
yield: 92%; 98% ee. The enantiomeric excess was deter-
mined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
(90:10) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]: tminor
28.651 min,
major =32.484 min; [a]2D7: +32.0 (c 0.50 in
=
t
minor =10.429 min, tmajor =11.103 min; [a]2D7: +37.4 (c 0.50 in
1
t
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.95 (d, J=
7.6 Hz, 2H), 7.68 (t, J=7.6 Hz, 1H), 7.58 (t, J=7.6 Hz, 2H),
7.17 (d, J=8.4 Hz, 2H), 7.12 (d, J=8.0 Hz, 2H), 5.23 (d, J=
10.0, 1H), 3.63 (d, J=1.6, 1H), 3.50 (dd, J=14.4, 10.0 Hz,
1H), 3.32 (dd, J=14.4, 1.2 Hz, 1H), 2.32 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=139.28, 138.27, 137.80, 134.17, 129.54,
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.95 (d, J=
7.6 Hz, 2H), 7.68 (t, J=7.2 Hz, 1H), 7.58 (t, J=7.6 Hz, 2H),
7.31–7.29 (m, 5H), 5.27 (d, J=10.0 Hz, 1H), 3.72 (s, 1H),
3.51 (dd, J=14.4 10.4 Hz, 1H), 3.33 (dd, J=14.4, 2.0 Hz,
1H); 13C NMR (100 MHz, CDCl3): d=140.76, 139.25,
134.19, 129.54, 128.84, 128.42, 128.06, 125.74, 68.53, 64.00;
IR (film): nmax =3481.1, 1447.3, 1281.9, 1135.3, 1135.7,
1084.3, 1062.2, 966.2, 829.6, 785.4, 762.1, 744.8, 704.9,
681.4 cmÀ1; ESI-MS: m/z=285.1 [M+Na]+; HR-MS: m/z=
285.0553 [M+Na]+, calcd. for C14H14NaO3S: 285.0556.
129.51, 128.08, 125.69, 68.41, 64.00, 21.22; IR (film) nmax
:
3485.2, 1447.8, 1286.6 1132.8, 1067.2, 997.8, 820.6, 788.4,
764.2, 741.4,720.8, 682.3 cmÀ1; ESI-MS: m/z=299.1 [M+
Na]+; HR-MS: m/z=299.0701 [M+Na]+, calcd. for
C15H16NaO3S: 299.0712.
1-(4-Fluorophenyl)-2-(phenylsulfonyl)ethanol (7b): White
solid; yield: 93%; 98% ee. The enantiomeric excess was de-
termined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
1-(2-Fluorophenyl)-2-(phenylsulfonyl)ethanol (7f): White
solid; yield: 95%; 95% ee. The enantiomeric excess was de-
termined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
Adv. Synth. Catal. 2013, 355, 2860 – 2872
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
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Xiao-Fei Huang et al.
FULL PAPERS
t
minor =9.022 min, tmajor =11.641 min; [a]2D7: +27.0 (c 0.50 in
734.0,683.7 cmÀ1; ESI-MS: m/z=275.0 [M+Na]+; HR-MS:
m/z=275.0348 [M+Na]+, calcd. for C12H12NaO4S: 275.0349.
2-(Phenylsulfonyl)-1-(thiophen-2-yl)ethanol (7j): White
solid; yield: 94%; 98% ee. The enantiomeric excess was de-
termined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.99 (d, J=
7.6 Hz, 2H), 7.73 (t, J=7.6 Hz, 1H), 7.64–7.56 (m, 3H),
7.31–7.26 (m, 1H), 7.18 (d, J=7.6 Hz, 1H), 6.98(d,
J=9.6 Hz, 1H), 5.50 (d, J=8.0 Hz, 1H), 3.90 (s, 1H), 3.54–
3.52ACHTUNGTRENNUNG
(m, 2H); 13C NMR (100 MHz, CDCl3): d=159.10 (d,
t
minor =10.870 min, tmajor =13.183 min; [a]2D7: +16.8 (c 1.00 in
1JC,F =245 Hz), 138.97, 134.24, 129.87 (d, JC,F =8 Hz), 129.55,
3
1
128.08, 127.71 (d, 3JC,F =12 Hz), 127.40 (d, 4JC,F =4 Hz),
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.93 (d, J=
7.6 Hz, 2H), 7.68 (t, J=7.6 Hz, 1H), 7.57 (t, J=8.0 Hz, 2H),
7.24–7.22 (m, 1H), 6.92–6.90 (m, 2H), 5.55–5.53 (m, 1H),
3.83 (d, J=2.4 Hz, 1H), 3.62 (dd, J=14.4, 9.6 Hz, 1H), 3.46
(dd, J=14.4, 2.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
144.25, 139.13, 134.27, 129.55, 128.09, 126.89, 125.65, 124.32,
64.99, 63.82; IR (film): nmax =3479.9, 1447.3, 1390.5, 1284.3,
1135.6, 1083.9, 1061.0, 793.6, 762.2, 722.4, 683.6 cmÀ1; ESI-
MS: m/z=291.0 [M+Na]+; HR-MS: m/z=291.0111 [M+
Na]+, calcd. for C12H12NaO3S2: 291.0120.
4
2
124.70 (d, JC,F =3 Hz), 115.38 (d, JC,F =21 Hz), 63.15, 62.31;
IR (film): nmax =3491.0, 1583.8, 1492.9, 1449.9, 1285.8,
1225.6, 1165.5, 1135.4, 1065.4, 949.5, 812.6, 767.2, 748.1,
730.3, 681.5 cmÀ1; ESI-MS: m/z=303.0 [M+Na]+; HR-MS:
m/z=303.0462, [M+Na]+, calcd. for C14H13FNaO3S:
303.0462.
1-(3-Fluorophenyl)-2-(phenylsulfonyl)ethanol (7g): White
solid; yield: 97%; 96% ee. The enantiomeric excess was de-
termined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
1-(Phenylsulfonyl)propan-2-ol (7k): Colorless oil; yield:
93%; 82% ee. The enantiomeric excess was determined by
HPLC [Daicel Chiralpak AD-H with hexane/i-PrOH
t
minor =8.046 min, tmajor =9.221 min; [a]2D7: +33.6 (c 0.50 in
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.97–7.95 (m,
2H), 7.72–7.68 (m, 1H), 7.60 (t, J=7.2 Hz, 2H), 7.06–7.03
(m, 2H), 6.98–6.94 (m, 1H), 5.29 (d, J=10.0 Hz, 1H), 3.81
(d, J=2.0 Hz, 1H), 3.47 (dd, J=14.4, 10.0 Hz, 1H), 3.31 (dd,
J=14.4, 2.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
163.06 (d, 1JC,F =246 Hz), 143.30 (d, 3JC,F =7 Hz), 139.11,
(70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]: tminor
14.051 min,
=
t
major =8.809 min; [a]2D7: +8.4 (c 0.25 in
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.92 (d, J=
7.6 Hz, 2H), 7.67 (t, J=7.6 Hz, 1H), 7.58 (t, J=8.0 Hz, 2H),
4.33–4.29 (m, 1H), 3.44 (s, 1H), 3.23 (dd, J=14.4, 9.2 Hz,
1H), 3.16 (dd, J=14.4, 2.0 Hz, 1H), 1.23 (d, J=6.4 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=139.24, 134.19, 129.58,
128.00, 63.44, 62.45, 22.68; IR (film): nmax =3499.5, 1447.3,
3
134.37, 130.48 (d, JC,F =8 Hz), 129.66, 128.08, 121.31, 115.32
(d, 2JC,F =21 Hz), 112.89 (d, 1JC,F =22 Hz), 67.94, 63.91; IR
(film): nmax =3468.9, 1614.4, 1591.5, 1448.3, 1287.9, 1240.4,
1289.4, 1140.6, 1082.4, 1043.5, 938.2, 744.5, 687.2, 637.3 cmÀ1
;
1138.5, 1071.6, 919.5, 873.9, 785.4, 744.2, 687.6, 695.1 cmÀ1
;
ESI-MS: m/z=223.0 [M+Na]+; HR-MS: m/z=201.0586
ESI-MS: m/z=303.0 [M+Na]+; HR-MS: m/z=303.0466
[M+H]+, calcd. for C9H13O3S: 201.0580.
[M+Na]+, calcd. for C14H13FNaO3S: 303.0462.
1-(Phenylsulfonyl)butan-2-ol (7l): Colorless oil; yield:
94%; 84% ee. The enantiomeric excess was determined by
HPLC [Daicel Chiralpak AD-H with hexane/i-PrOH
1-(Naphthalen-2-yl)-2-(phenylsulfonyl)ethanol
(7h):
White solid; yield: 94%; 96% ee. The enantiomeric excess
was determined by HPLC [Daicel Chiralpak AD-H with
hexane/i-PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=
210 nm]: tminor =12.380 min, tmajor =13.349 min; [a]2D7: +44.6
(c 1.00 in CH3COCH3); 1H NMR (400 MHz, CDCl3): d=
7.97–7.95 (m, 2H), 7.80–7.77 (m, 4H), 7.68–7.64 (m, 2H),
7.56 (t, J=8.0 Hz, 2H), 7.49–7.45 (m, 2H), 7.36–7.34 (m,
1H), 5.45 (d, J=10.0 Hz, 1H), 3.84 (d, J=1.6 Hz, 1H), 3.59
(dd, J=14.8, 10.0 Hz, 1H), 3.43 (dd, J=14.4, 2.0 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=139.25, 138.02, 134.20,
133.23, 129.54, 128.80, 128.09, 127.78, 126.55, 126.41, 124.88,
123.35, 68.70, 63.95; IR (film): nmax =3502.7, 1445.9, 1389.6,
1282.8, 1239.7, 1163.7, 1135.9, 1082.9, 1058.3, 878.0, 841.9,
827.5, 800.4, 763.2, 681.6, 625.6 cmÀ1; ESI-MS: m/z=335.1
[M+Na]+; HR-MS: m/z=335.0706 [M+Na]+, calcd. for
C18H16NaO3S: 335.0712.
(70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]: tminor
=
12.019 min,
t
major =9.024 min; [a]2D7: +8.5 (c 0.50 in
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.91 (d, J=
7.6 Hz, 2H), 7.68–7.64 (m, 1H), 7.57 (t, J=7.6 Hz, 2H),
4.08–4.06 (m, 1H), 3.36 (s, 1H), 3.25–3.15 (m, 2H), 1.58–
1.45 (m, 2H), 0.89 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=139.35, 134.11, 129.53, 127.97, 67.20, 62.01,
29.55, 9.40; IR (film): nmax =3506.3, 1447.2, 1290.6, 1140.1,
977.9, 790.3, 745.4, 687.4 cmÀ1; ESI-MS: m/z=215.1 [M+
H]+; HR-MS: m/z=215.0734 [M+Na]+, calcd. for
C10H15O3S: 215.0736.
2-(Phenylsulfonyl)-2,3-dihydro-1H-inden-1-ol (7m): White
solid; yield: 97%; 98% ee, >99:1 dr. The enantiomeric
excess was determined by HPLC [Daicel Chiralpak AD-H
with hexane/i-PrOH (70:30) as the eluent, flow:
1.0 mLminÀ1
;
l=210 nm]:
tminor =11.421 min,
tmajor =
1-(Furan-2-yl)-2-(phenylsulfonyl)ethanol (7i): White solid;
yield: 95%; 98% ee. The enantiomeric excess was deter-
mined by HPLC [Daicel Chiralpak AD-H with hexane/i-
PrOH (70:30) as the eluent, flow: 1.0 mLminÀ1; l=210 nm]:
9.323 min; [a]D27: +7.2 (c 0.50 in CH3COCH3); 1H NMR
(400 MHz, CDCl3): d=8.05 (d, J=8.0 Hz, 2H), 7.70 (t, J=
7.2 Hz, 1H), 7.61 (t, J=7.6 Hz, 2H), 7.41 (d, J=6.8 Hz,
1H), 7.33–7.26 (m, 3H), 5.34 (t, J=6.0 Hz, 1H), 4.01–3.96
(m, 1H), 3.71 (dd, J=16.4, 7.6 Hz, 1H), 3.37 (d, J=6.8 Hz,
1H), 3.19 (dd, J=16.0, 8.0 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=141.84, 139.76, 139.31, 133.96, 129.55, 129.28,
128.61, 127.86, 125.08, 124.93, 74.67, 67.01, 31.46; IR (film):
nmax =3474.4, 1444.9, 1304.4, 1284.3, 1137.8, 1084.8, 1063.5,
754.8, 724.2, 691.2, 654.3 cmÀ1; ESI-MS: m/z=297.1 [M+
H]+; HR-MS: m/z=297.0550 [M+Na]+, calcd. for
C15H14NaO3S: 297.0556.
t
minor =9.484 min, tmajor =10.180 min; [a]2D7: +17.2 (c 0.50 in
1
CH3COCH3); H NMR (400 MHz, CDCl3): d=7.91 (d, J=
7.6 Hz, 2H), 7.66 (t, J=7.6 Hz, 1H), 7.56 (t, J=8.0 Hz, 2H),
7.28–7.26 (m, 1H), 6.28–6.26 (m, 2H), 5.28–5.24 (m, 1H),
3.67 (dd, J=14.4, 4.8 Hz, 1H), 3.59 (d, J=3.6 Hz, 1H), 3.53
(dd, J=14.4, 9.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
152.58, 142.72, 139.13, 134.18, 129.52, 128.10, 110.55, 107.49,
62.79, 60.66; IR (film): nmax =3482.2, 1448.3, 1397.3, 1285.3,
1136.1, 1083.4, 1055.2, 997.7, 923.6, 798.5, 755.3,
2870
asc.wiley-vch.de
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 2860 – 2872

Asymmetric Hydrogenation of b-Keto Sulfonamides and b-Keto Sulfones
Kabuto, R. Noyori, J. Am. Chem. Soc. 2002, 124, 6508–
Acknowledgements
6509; g) K. Abdur-Rashid, S. E. Clapham, A. Hadzovic,
J. N. Harvey, A. J. Lough, R. H. Morris, J. Am. Chem.
Soc. 2002, 124, 15104–15118; h) J.-H. Xie, L.-X. Wang,
Y. Fu, S.-F. Zhu, B.-M. Fan, H.-F. Duan, Q.-L. Zhou, J.
Am. Chem. Soc. 2003, 125, 4404–4405; i) A. Lei, S. Wu,
M. He, X. Zhang, J. Am. Chem. Soc. 2004, 126, 1626–
1627; j) Y. Liang, Q. Jing, X. Li, L. Shi, K. Ding, J. Am.
Chem. Soc. 2005, 127, 7694–7695; k) Q. Jing, X. Zhang,
J. Sun, K. Ding, Adv. Synth. Catal. 2005, 347, 1193–
1197; l) D. Liu, W. Gao, C. Wang, X. Zhang, Angew.
Chem. 2005, 117, 1715–1717; Angew. Chem. Int. Ed.
2005, 44, 1687–1689; m) Y.-Q. Wang, S.-M. Lu, Y.-G.
Zhou, Org. Lett. 2005, 7, 3235–3238; n) Y. Sun, X. Wan,
J. Wang, Q. Meng, H. Zhang, L. Jiang, Z. Zhang, Org.
Lett. 2005, 7, 5425–5427; o) H. Huang, T. Okuno, K.
Tsuda, M. Yoshimura, M. Kitamura, J. Am. Chem. Soc.
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Dai, Z.-B. Luo, Tetrahedron: Asymmetry 2007, 18, 224–
228; q) X. Wan, Q. Meng, H. Zhang, Y. Sun, W. Fan, Z.
Zhang, Org. Lett. 2007, 9, 5613–5616; r) Y. Li, Y. Zhou,
Q. Shi, K. Ding, R. Noyori, C. A. Sandoval, Adv. Synth.
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7467–7470; Angew. Chem. Int. Ed. 2011, 50, 7329–7332;
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Li, X. Ma, X. Li, W. Fan, L. Zhu, X. Xie, Z. Zhang, J.
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We are grateful for financial support of the National Natural
Science Foundation of China (21072145, 21272166), the pro-
gram for New Century Excellent Talents in University
(NCET-12-0743), the Scientific Research Foundation for Re-
turned Scholars, the Ministry of Education of China
(ACHTUNGTRENNUNG[2010]1174). This project was also funded by the Priority
Academic Program Development of Jiangsu Higher Educa-
tion Institutions (PAPD) and the Major Basic Research Proj-
ect of the Natural Science Foundation of the Jiangsu Higher
Education Institutions (13KJA15004).
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[15] Crystal structure of 5aa: C14H15NO3 S, M =277.33;
a block crystal (0.60ꢃ0.60ꢃ0.40 mmmm), T=293(2),
l (Mo-Ka)=0.71070 ꢄ, monoclinic, space group: P 21,
a=7.3822(17) ꢄ, b=13.429(3) ꢄ, c=13.736(3) ꢄ, V=
1361.8(6) ꢄ3, 11502 total reflections, 2475 unique,
R
int =0.0426, R1=0.0225 (I> 2 s), wR2=0.0869, Abso-
lute structure parameter: 0.02(9). CCDC 876361 con-
tains the supplementary crystallographic 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.
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2872
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Adv. Synth. Catal. 2013, 355, 2860 – 2872