Preparation of novel N-sulfonylated (S,S)-2,3-diaminosuccinate-type chiral auxiliaries and application to an asymmetric 1,3-dipolar cycloaddition reaction of nitrile oxides to allyl alcohol

Article abstract of DOI:10.1016/j.tetasy.2006.11.031

Novel N-sulfonylated (S,S)-2,3-diaminosuccinate-type chiral auxiliaries, which have the tartaric acid-like framework with a sulfonamide group instead of a hydroxyl group, were synthesized from l-aspartic acid. The synthesized (S,S)-2,3-diaminosuccinate de

Full text of DOI:10.1016/j.tetasy.2006.11.031

Tetrahedron: Asymmetry 17 (2006) 3075–3083
Preparation of novel N-sulfonylated (S,S)-2,3-diaminosuccinate-
type chiral auxiliaries and application to an asymmetric
1,3-dipolar cycloaddition reaction of nitrile oxides to allyl alcohol
Masakazu Serizawa, Yutaka Ukaji* and Katsuhiko Inomata*
Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University,
Kakuma, Kanazawa, Ishikawa 920-1192, Japan
Received 20 September 2006; accepted 17 November 2006
Abstract—Novel N-sulfonylated (S,S)-2,3-diaminosuccinate-type chiral auxiliaries, which have the tartaric acid-like framework with
a sulfonamide group instead of a hydroxyl group, were synthesized from L-aspartic acid. The synthesized (S,S)-2,3-diaminosuccinate
derivatives were applied to an asymmetric 1,3-dipolar cycloaddition reaction of nitrile oxides to allyl alcohol to afford the corresponding
optically active 2-isoxazolines, with the enantioselectivities of up to 73% ee. The enantiofacial differentiation was intriguingly opposite to
that by using diisopropyl tartrate as a chiral auxiliary.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
constructed according to the reported procedure from
L-aspartic acid via its N-9-phenylfluorenylated ester deriv-
ative 1 to give a diastereomeric mixture of (2S,3S)-2 and
(2R,3S)-2.5a Diastereomerically pure (2S,3S)-2 was
obtained by recrystallization. Catalytic hydrogenolysis of
the 9-phenylfluorenyl and azide groups afforded (S,S)-
2,3-diaminosuccinate 3, followed by sulfonylation with
various sulfonylating reagents to give the desired chiral
auxiliaries 4a–f having the tartaric acid framework with a
sulfonamide group instead of a hydroxyl group. Hydrolysis
of the methyl ester by aqueous NaOH solution followed by
Enantiomerically pure vicinal diamines and their deriva-
tives have recently attracted a great deal of attention in
asymmetric synthesis, as chiral auxiliaries.1,2 In particular,
chiral vicinal bis-sulfonamides play significant roles due to
their acidic protons and ready formation of metal
amides.1,3 Recently, we have developed new asymmetric
reactions utilizing tartaric acid ester as a chiral auxiliary.4
If the two hydroxyl groups in tartaric acid esters are re-
placed by nitrogen functional groups, an alternative affinity
for metals and different stereocontrols by substituents on
nitrogen atoms are anticipated. Herein we wish to describe
a synthesis of new (S,S)-2,3-diaminosuccinate-type chiral
auxiliaries5 that have the tartaric acid framework with a
sulfonamide group instead of a hydroxyl group, and their
application to the asymmetric 1,3-dipolar cycloaddition
reaction of nitrile oxides to allyl alcohol.
i
t
esterification furnished the Pr ester 6 and Bu esters 7a–f
without racemization.
The ability of chiral induction of compounds 4a, 6 and
7a–f prepared above was probed by an asymmetric 1,3-
dipolar cycloaddition of a nitrile oxide to allyl alcohol 8
(Scheme 2),6 that is, treatment of allyl alcohol with 1.0
molar amount of diethylzinc, 1.0 molar amount of chiral
sulfonamide, 1.1 molar amounts of the second diethylzinc
and 1.1 molar amounts of p-(methoxy)benzohydroximoyl
chloride; this may form the bis-zinc containing intermedi-
ate 9, in which the nitrile oxide generated coordinates to
zinc metal(s). The following 1,3-dipolar cycloaddition
was expected to proceed enantioselectively within this
complex to afford the corresponding optically active 2-
isoxazoline 10A.
2. Results and discussion
The synthesis of chiral auxiliaries was accomplished as out-
lined in Scheme 1. The 2,3-diaminosuccinate backbone was
*
Corresponding authors. Tel.: +81 76 264 5700; fax: +81 76 264 5742;
e-mail: inomata@cacheibm.s.kanazawa-u.ac.jp
0957-4166/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2006.11.031

3076
M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
O
NH2
O
O
HN Ph
OMe
OH
HO
MeO
O
1
1) KHMDS
2) Trisyl azide
3) AcOH
O
HN Ph
OMe
Recrystallization
(2S,3S)-2
MeO
THF
40%
N3
)-2, (2
O
(2S
,3S
R,3S)-2; 87%
SO2R
OMe
O
HN
RSO2Cl
Et3N, THF
(R = CF3)
MeO
RO2S
R = Tol 4a; 83%
H2
O
NH2
NH
O
cat. Pd(OH)2/C
OMe
MeO
MeOH
or Tf2O
Et3N, CH2Cl2
(R = CF3)
NH2
O
2-naphthyl 4b; 67%
1-naphthyl 4c; 75%
2,4,6-trimethylphenyl 4d; 74%
Me 4e; 73%
3
CF3 4f; 87%
iPrOH
HCl
SO2Tol
O
HN
OiPr
i
O
Pr
(R = Tol)
SO2R
OH
O
NH
O
O
HN
TolO2S
NaOHaq
6; 68%
HO
RO2S
SO2R
NH
O
tBuO
HN
cat. H2SO4
CH2Cl2
OtBu
5a-f; 95% - quant.
NH
O
RO2S
R = Tol 7a; 91%
2-naphthyl 7b; 95%
1-naphthyl 7c; 90%
2,4,6-trimethylphenyl 7d; 95%
Me 7e; 83%
CF3 7f; 92%
Scheme 1.
SO2R
HN
CO2R'
Zn (1.0 eq.)
1) Et2
2)
OH
R'O2C
CO2R'
O Zn
N
CO2R'
8
SO2R
RO2S NH HN SO2R
4a, 6, 7a-f (1.0 eq.)
in CHCl3, 0 o
C
SO2R
O
Cl
Zn
3) Et2Zn (1.1 eq.)
N
N O
An
C
N O
OR'
OR'
OH
Time
4) ArC(Cl)=NOH (1.1 eq.)
Ar
RO2S
O
N
10A
Zn
O
(Ar =
p-methoxyphenyl)
9
Scheme 2.

M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
3077
Table 1.
Entry
R
R0
Chiral sulfonamide
Time (h)
Yield of 10A (%)
ee (%)
1
2
3
4
5
6
7
8
Tol
Tol
Tol
Me
iPr
4a
6
24
24
23
23
24
24
24
24
67
70
60
56
56
63
67
67
24
37
40
37
11
13
18
50
tBu
tBu
tBu
tBu
tBu
tBu
7a
7b
7c
7d
7e
7f
2-Naphthyl
1-Naphthyl
2,4,6-Trimethylphenyl
Me
CF3
First in order to investigate the influence of the ester groups
in the chiral auxiliaries, the chiral auxiliaries with the tosyl
group on the nitrogen atom were used for the 1,3-dipolar
cycloaddition (Table 1, entries 1–3). Although the use of
methyl ester 4a afforded cycloadduct 10A with poor enantio-
selectivity (entry 1), bulkier esters enhanced the enantio-
selectivity. In the case of t-butyl ester 7a, enantioselectivity
was improved to 40% ee (entry 3).
withdrawing trifluoromethanesulfonyl (Tf) group was
found to be more effective than 7a and the enantioselecti-
vity was improved to 50% ee (entry 8).
The effect of solvent was also examined (Scheme 3) and the
results are listed in Table 2. Dichloromethane afforded a
comparable result with CHCl3 (entry 2). Coordinative sol-
vents, such as MeCN or ethers, decreased the enantioselec-
tivity (entries 3–6). Enantioselectivity in toluene was similar
to that in halogenated solvents (entry 7), even though 7f
was almost insoluble and the reaction mixture was hetero-
geneous throughout the reaction. In order to dissolve 7f, a
small amount of etheral solvent was added as a co-solvent.
It was found that the enantioselectivity was varied by the
type of added ethers (entries 8–12). Strongly coordinative
ethers, such as THF and DME, considerably lowered the
enantioselectivity. When weakly coordinative tBuOMe
was used, the enantiomeric excess was further improved
to 65% ee (entry 12). Furthermore, other aromatic solvents
were examined (entries 12–19), and it was found that
substituted benzenes afforded product 10A with slightly
enhanced enantioselectivity. Especially, ethylbenzene was
the solvent of choice to furnish 2-isoxazoline 10A in 73%
Next, the effect of the substituents on the nitrogen in the
chiral auxiliaries was investigated (entries 3–8). Sulfon-
amides 7b–d with bulkier groups and 7e with a smaller
Me group were less effective than 7a. A smaller electron-
Table 2.
Entry
Solvent
Yield (%)
ee (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15c
16
17
18
19
CHCl3
CH2Cl2
MeCN
THF
Et2O
tBuOMe
Toluene
Toluene/THFa
Toluene/DMTHFa,b
Toluene/DMEa
Toluene/Et2Oa
Toluene/tBuOMea
Benzene/tBuOMea
Ethylbenzene/tBuOMea
Ethylbenzene/tBuOMea
n-Propylbenzene/tBuOMea
Cumene/tBuOMea
Xylene/tBuOMea,d
Mesitylene/tBuOMea
67
56
35
24
31
67
49
46
53
53
53
63
73
73
74
73
67
73
73
50
45
0
1
28
33
52
2
˚
ee (entry 14). It was found that the presence of MS 3 A
in the reaction mixture was effective to realize reproducibile
enantioselectivity (entry 15), probably to avoid the influ-
ence of moisture.
11
14
39
65
61
73
71
67
69
68
67
The asymmetric 1,3-dipolar cycloaddition of benzonitrile
oxide, pivalonitrile oxide, 4-bromobenzonitrile oxide and
4-cyanobenzonitrile oxide was carried out under the
optimized reaction conditions (Scheme 4, Table 3). The
corresponding 2-isoxazolines 10B–E were obtained with
moderate enantioselectivity.
The absolute configurations of 2-isoxazolines 10B and 10C
were determined to be (R) by comparison of their specific
rotations with the reported data, respectively.7 The abso-
lute configurations of 10A,D,E were tentatively determined
to be (R). Interestingly, based on these results, the enantio-
a Solvent/co-solvent ratio was 13/1.
b DMTHF is 2,5-dimethyltetrahydrofuran.
c
˚
MS 3 A was added.
d A mixture of xylene isomers was used.
1) Et2Zn (1.0 eq.)
tBuO2C
CO2
2)
tBu
7f (1.0 eq.)
N
O
Tf NH HN Tf
OH
OH
3) Et2Zn (1.1 eq.)
Ar
8
10A
4) ArC(Cl)=NOH (1.1 eq.)
Solvent, 0 oC, 24 h
Scheme 3.

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M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
1) Et2Zn (1.0 eq.)
tBuO2C
CO2t Bu
2)
N
O
7f (1.0 eq.)
Tf NH HN Tf
OH
OH
3) Et2Zn (1.1 eq.)
4) R1C(Cl)=NOH (1.1 eq.)
R1
8
10A-E
MS 3Å, Ethylbenzene/tBuOMe = 13/1, 0 oC, 24 h
Scheme 4.
facial differentiation of the present system was found to be
opposite to the case utilizing diisopropyl tartrate (DIPT) as
a chiral auxiliary. (S,S)-2,3-Diaminosuccinate 7f afforded
the (R)-2-isoxazoline, whereas (R,R)-DIPT gave the
(R)-2-isoxazoline, which means that (S,S)-DIPT would
produce the (S)-2-isoxazoline.6
We had proposed that the stereochemical course in asym-
metric 1,3-dipolar cycloadditions using (S,S)-DIPT could
be explained by using a bimetallic transition state model
as depicted in Figure 1, in which a rigid 5/5-fused bicyclic
structure was formed by zinc bridging. The nitrile oxide
coordinating to the two zinc metals was well-activated
and added from the si-face of allyl alcohol to give the
(S)-2-isoxazoline.
Table 3.
On the other hand, in the present case using a chiral sulfon-
amide, such as 7f, the asymmetric 1,3-dipolar cycloaddition
might proceed through the two zinc bridging transition
states as depicted in Figure 2. The reversal of enantioselec-
tion might be due to the influence of the substituents on
nitrogen atoms which are absent in the case of DIPT
(Fig. 1). Nitrile oxide coordinates to the two zinc metals
Zn1 and Zn2 in a similar manner to the case of DIPT; how-
ever, the substituents on nitrogen atoms influence the steric
relationship between nitrile oxide and allyl alcohol moiety.
The allyl alcohol moiety might be bound to Zn2 as shown
in Figure 4, rather than Zn1 to avoid the steric interaction
with the bulky sulfonamide on N1 (Fig. 3). Nitrile oxide
would approach the re-face of the allyl alcohol (Fig. 4),
which is opposite to that in the case of DIPT. The strongly
electron-withdrawing Tf group makes zinc metals more
Lewis acidic, and the interaction between the zinc metals
and a nitrile oxide may become more effective to enhance
the stereoselectivity.
Entry
R1
10
Yield (%)
ee (%)
1
2
3
4
5
4-MeOC6H4 (Ar)
Ph
tBu
4-BrC6H4
4-NCC6H4
A
B
C
D
E
74
72
78
82
79
71
55
50
57
49
OiPr
CO2iPr
H
H
O
O
O
Zn1
N
Zn2
O
O
R
Cl
H
3. Conclusion
H
H
In conclusion, a series of new (S,S)-2,3-diaminosuccinate-
type chiral auxiliaries were prepared from L-aspartic acid,
and their asymmetric induction properties were investi-
gated for the asymmetric 1,3-dipolar cycloaddition reaction
of nitrile oxides to allyl alcohol. The corresponding 2-isox-
azolines were obtained with an enantioselectivity of upto
73% ee, whose enantiofacial differentiation was opposite
to the case utilizing DIPT as a chiral auxiliary.
Figure 1.
OtBu
O
CO2tBu
H
H
O
O
N1
S
4. Experimental
4.1. General
N2
F3C
Zn1
N
Zn2
O
O
Cl
S
O
F3C
Ar
All of the melting points were determined by a micro
melting apparatus (Yamagimoto-Seisakusho) and are
uncorrected. The 1H NMR spectra were recorded on JEOL
Lambda 400, JEOL Lambda 300 (only for (2S,3S)-2),
and JEOL JNM-GX 400 spectrometers. The chemical
shifts were determined in the d-scale relative to tetrameth-
O
H
H
H
Figure 2.

M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
3079
tBu
tBu
O
O
H
H
t
t
O2C
H
O2C
H
O Bu
O Bu
N1
N1
O
O
O
O
S
S
N2
N2
Figure 2
Zn1
Zn2
Cl
Zn1
Zn2
F3C
SO CF
2
SO CF
2
F3C
3
3
Cl
O
O
O
O
N
N
C
C
Ar
Ar
Figure 4.
Figure 3.
ylsilane (d = 0) as an internal standard. The IR spectra
were measured by a JASCO FT/IR-230 spectrometer. The
optical rotations were recorded on a JASCO DIP-370 spec-
trometer. CHCl3 was treated with Merck’s aluminum oxide
90 active basic (0.063–0.200 mm, activity stage I, Art.
20% Pd) and the mixture was stirred under an H2 atmo-
sphere for 11 h at room temperature. The resulting suspen-
sion was filtered and the filtrate was evaporated under
reduced pressure to give crude diamine 3. To crude 3 was
added a catalytic amount of DMAP (31 mg, 0.25 mmol)
and replaced with N2 atmosphere. THF (45 ml), Et3N
(2.03 ml, 14.6 mmol) and a THF (15 ml) solution of p-
toluenesulfonyl chloride (2.39 g, 12.5 mmol) were added
and the solution was stirred for 24 h at room temperature.
The reaction was quenched by the addition of water and
extracted with AcOEt. The combined extracts were washed
with brine, dried over Na2SO4, and condensed under re-
duced pressure. The residue was purified by recrystalliza-
tion from hexane/AcOEt to give 4a (1.28 g, 63%). The
mother liquor was condensed and the residue was sepa-
rated by column chromatography on SiO2 (hexane/
AcOEt = 5/1 and then hexane/AcOEt = 2/1) to give the
almost pure 4a. The product was purified by recrystalliza-
tion from hexane/AcOEt to give 4a (284 mg, 14%). The
mother liquor was condensed and the residue was purified
by TLC (SiO2, CHCl3/MeCN = 5/1) to give additional 4a
˚
101076) and dried over MS 4 A just before use. THF and
Et2O were freshly distilled from sodium diphenylketyl.
All other solvents were distilled and stored over drying
agents. Flash column chromatography and thin-layer chro-
matography (TLC) were performed on Cica-Merck’s silica
gel 60 (No. 9385-5B) and Merck’s silica gel 60 PF254 (Art.
107749), respectively.
4.2. Preparation of chiral auxiliaries
4.2.1. Dimethyl (2S,3S)-2-azido-3-(9-phenyl-9H-fluoren-9-
ylamino)succinate (2S,3S)-2.5a To a THF (35 ml) solu-
tion of dimethyl (S)-N-(9-phenyl-9H-fluoren-9-yl)aspartate
1 (1.27 g, 3.16 mmol) was added KHMDS (4.10 mmol,
4.6 ml of 20% solution (ca. 0.9 M) in toluene) at ꢀ78 °C
under a nitrogen atmosphere and the reaction mixture
was kept at ꢀ78 °C for 1 h. A precooled (ꢀ78 °C) THF
(12 ml) solution of (2,4,6-triisopropyl)benzenesulfonyl
azide (1.27 g, 4.10 mmol) was added to the above enolate
solution. After stirring for 6 min, the reaction was
quenched with AcOH (15.2 mmol, 0.87 ml) and the result-
ing mixture was stirred for 2 h at 25 °C, and then extracted
with AcOEt. The combined extracts were washed with
brine, dried over Na2SO4, and condensed under reduced
pressure. The residue was purified by column chromato-
graphy (SiO2, hexane/AcOEt = 6/1) to give a mixture of
(2S,3S)-2 and (2R,3S)-2 (1.22 g, 87%, (2S,3S)-2:(2R,3S)-
2 = ca. 2:1). Recrystallization of the mixture from
(112 mg, 6%). Mp 207–208 °C (from hexane/AcOEt);
25
½aꢁD ¼ þ123 (c 0.23, CHCl3); IR (KBr) 3261, 3231, 3069,
2960, 2921, 1740, 1718, 1597, 1496, 1458, 1343, 1283,
1214, 1169, 1125, 1088, 1019, 982, 956, 915, 861, 817,
1
802, 790, 717, 704, 665 cmꢀ1; H NMR (CDCl3): d = 2.42
(s, 6H), 3.61 (s, 6H), 4.38 (d, J = 8.05 Hz, 2H), 5.56 (d,
J = 8.05 Hz, 2H), 7.29 (d, J = 7.81 Hz, 4H), 7.69 (d,
J = 7.81 Hz, 4H). Found: C, 49.35; H, 5.00; N, 5.70. Calcd
for C20H24N2O8S2: C, 49.57; H, 4.99; N, 5.78.
In a similar manner, dimethyl 2,3-diaminosuccinates 4b–e
hexane/AcOEt gave pure (2S,3S)-2 (0.56 g, 40%). Mp 150.5–
were prepared using the corresponding sulfonyl chloride.
25
151.5 °C (from hexane/AcOEt); ½aꢁD ¼ ꢀ324 (c 0.22,
CHCl3); IR (KBr) 3309, 3064, 2952, 2844, 2142, 2109,
1749, 1598, 1543, 1489, 1436, 1353, 1340, 1301, 1272,
1213, 1182, 1141, 1060, 1022, 984, 931, 908, 889, 835,
4.2.3. Dimethyl (S,S)-2,3-bis(naphthalene-2-sulfonamido)-
succinate 4b. Mp 190–191 °C (from hexane/AcOEt);
1
25
805, 757, 734, 700 cmꢀ1; H NMR (CDCl3): d = 3.19 (dd,
½aꢁD ¼ þ138 (c 0.26, CHCl3); IR (KBr) 3260, 3055, 2958,
J = 3.12, 10.09 Hz, 1H), 3.37 (d, J = 10.09 Hz, 1H), 3.40
(s, 3H), 3.52 (s, 3H), 3.76 (d, J = 3.12 Hz, 1H), 7.18–7.42
(m, 11H), 7.65 (d, J = 7.52 Hz, 1H), 7.70 (d, J = 7.52 Hz,
1H). Found: C, 67.83; H, 5.08; N, 12.55. Calcd for
C25H22N4O4: C, 67.86; H, 5.01; N, 12.66.
1737, 1713, 1626, 1591, 1504, 1438, 1345, 1283, 1213,
1166, 1132, 1105, 1075, 1017, 967, 910, 864, 819, 783,
1
746, 708, 660 cmꢀ1; H NMR (CDCl3): d = 3.47 (s, 6H),
4.46 (d, J = 8.54 Hz, 2H), 5.72 (d, J = 8.54 Hz, 2H), 7.61
(dd, J = 6.83, 8.54 Hz, 2H), 7.66 (dd, J = 6.83, 8.05 Hz,
2H), 7.77 (d, J = 8.54 Hz, 2H), 7.90 (d, J = 8.05 Hz, 2H),
7.94 (d, J = 8.54 Hz, 4H), 8.36 (s, 2H). Found: C, 55.95;
H, 4.41; N, 5.04. Calcd for C26H24N2O8S2: C, 56.10; H,
4.35; N, 5.03.
4.2.2. Dimethyl (S,S)-2,3-bis(4-methylphenylsulfonamido)-
succinate 4a. To a suspension of (2S,3S)-2 (1.85 g, 4.18
mmol) in MeOH (35 ml) was added Pd(OH)2/C (350 mg,

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M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
4.2.4. Dimethyl (S,S)-2,3-bis(naphthalene-1-sulfonamido)-
succinate 4c. Mp 172–173 °C (from hexane/AcOEt);
768 cmꢀ1 1H NMR (CDCl3): d = 3.91 (s, 6H), 4.71 (s,
;
2H), Signals of the amide protons were not observed
clearly.. Found: C, 22.04; H, 2.36; N, 6.65. Calcd for
C8H10N2O8F6S2: C, 21.82; H, 2.29; N, 6.36.
25
½aꢁD ¼ þ146 (c 0.23, CHCl3); IR (KBr) 3366, 3267, 3055,
2957, 2849, 1765, 1736, 1594, 1507, 1437, 1340, 1267,
1218, 1202, 1166, 1133, 1104, 1049, 1026, 985, 951, 893,
866, 828, 808, 770, 703, 676 cmꢀ1
;
1H NMR (CDCl3):
4.2.8.
Diisopropyl
(S,S)-2,3-bis(4-methylphenylsulfon-
d = 3.18 (s, 6H), 4.26 (d, J = 8.54 Hz, 2H), 5.80 (d,
J = 8.54 Hz, 2H), 7.50 (dd, J = 7.32, 8.29 Hz, 2H), 7.61
(dd, J = 6.83, 8.05 Hz, 2H), 7.70 (dd, J = 6.83, 8.78 Hz,
2H), 7.92 (d, J = 8.05 Hz, 2H), 8.06 (d, J = 8.29 Hz, 2H),
8.14 (d, J = 7.32 Hz, 2H), 8.57 (d, J = 8.78 Hz, 2H).
Found: C, 55.99; H, 4.39; N, 5.03. Calcd for
C26H24N2O8S2: C, 56.10; H, 4.35; N, 5.03.
amido)succinate 6. Sulfonamide 4a (700 mg, 1.14 mmol)
was treated with 0.6 M aq NaOH solution (40 ml,
24 mmol) at room temperature and the mixture was stirred
for 13 h. The solution was neutralized to pH 8 by the addi-
tion of 1 M aq HCl solution and washed with AcOEt. The
aqueous phase was acidified to pH 3 by the addition of 1 M
aq HCl solution and extracted with AcOEt. The combined
extracts were washed with brine, dried over Na2SO4, and
condensed under reduced pressure to give crude 5a
(670 mg, quant.). Dry HCl gas was bubbled into the i-
PrOH (10 ml) solution of 5a (20 mg, 0.0438 mmol) for
10 min and the mixture was stirred for 98 h at room
temperature. The resulting solution was condensed under
reduced pressure. The residue was purified by column
chromatography (SiO2, hexane/AcOEt = 2/1) to give 6
4.2.5. Dimethyl (S,S)-2,3-bis(2,4,6-trimethylphenylsulfon-
amido)succinate 4d. Mp 198.5–199.5 °C (from hexane/
25
AcOEt); ½aꢁD ¼ þ81 (c 0.31, CHCl3); IR (KBr) 3349,
3332, 3306, 3288, 2978, 1767, 1757, 1603, 1561, 1427,
1380, 1343, 1263, 1212, 1194, 1165, 1139, 1109, 1056,
977, 938, 882, 861, 780, 721, 697 cmꢀ1; 1H NMR (CDCl3):
d = 2.28 (s, 6H), 2.60 (s, 12H), 3.55 (s, 6H), 4.26 (d,
J = 8.54 Hz, 2H), 5.57 (d, J = 8.54 Hz, 2H), 6.94 (s, 4H).
Found: C, 53.24; H, 5.97; N, 5.25. Calcd for
C24H32N2O8S2: C, 53.31; H, 5.97; N, 5.18.
(16 mg, 68%). Mp 175.5–176.5 °C (from hexane/AcOEt);
25
½aꢁD ¼ þ63 (c 0.15, EtOH); IR (KBr) 3272, 3219, 3069,
3029, 2985, 2933, 2767, 1728, 1709, 1599, 1471, 1458,
1441, 1343, 1309, 1283, 1170, 1104, 1087, 970, 952, 909,
1
4.2.6. Dimethyl (S,S)-2,3-di(methylsulfonamido)succinate
817, 804, 779, 700, 663 cmꢀ1; H NMR (CDCl3): d = 1.08
25
4e. Mp 162–163 °C (from hexane/AcOEt); ½aꢁD ¼ þ32
(d, J = 6.10 Hz, 6H), 1.18 (d, J = 6.10 Hz, 6H), 2.40 (s,
6H), 4.27 (d, J = 8.78 Hz, 2H), 4.86 (hep, J = 6.10 Hz,
2H), 5.39 (d, J = 8.78 Hz, 2H), 7.28 (d, J = 8.05 Hz, 4H),
7.68 (d, J = 8.05 Hz, 4H). Found: C, 53.19; H, 5.96; N,
5.24. Calcd for C24H32N2O8S2: C, 53.31; H, 5.97; N, 5.18.
(c 0.20, CHCl3); IR (KBr) 3327, 3292, 3021, 2985, 2942,
1746, 1440, 1337, 1309, 1279, 1229, 1207, 1184, 1165,
1108, 984, 924, 887, 790, 750, 698 cmꢀ1; 1H NMR (CDCl3):
d = 2.98 (s, 6H), 3.88 (s, 6H), 4.74 (d, J = 8.54 Hz, 2H),
5.68 (d, J = 8.54 Hz, 2H). Found: C, 29.02; H, 4.90; N,
8.37. Calcd for C8H16N2O8S2: C, 28.91; H, 4.85; N, 8.43.
4.2.9. Di-tert-butyl (S,S)-2,3-bis(4-methylphenylsulfon-
amido)succinate 7a. In the same manner for the prepara-
tion of 6, the hydrolysis of 4a was carried out to give crude
5a. After cooling a solution of 5a (850 mg, 1.86 mmol) in
CH2Cl2 (40 ml) to ꢀ40 °C in a pressure bottle, isobutene
(ca. 3.4 g, 60.6 mmol) was bubbled and a catalytic amount
of H2SO4 was added. The mixture was stirred for 74 h at
room temperature. The reaction was quenched by the addi-
tion of water and neutralized to pH 8 by the addition of
saturated aq NaHCO3 solution. The mixture was extracted
with AcOEt and the combined extracts were washed with
brine, dried over Na2SO4, and condensed under reduced
pressure. The residue was purified by recrystallizing from
hexane/AcOEt to give 7a (894 mg, 84%). The mother
liquor was condensed and the residue was purified by
TLC (SiO2, CHCl3/MeCN = 10/1) to give additional 7a
4.2.7. Dimethyl (S,S)-2,3-bis(trifluoromethylsulfonamido)-
succinate 4f. In a similar manner for the preparation of
4a, crude 3 was obtained by the reduction of (2S,3S)-2
(1.00 g, 1.81 mmol). Then, to the crude 3 was added a cat-
alytic amount of DMAP (34 mg, 0.28 mmol) under an N2
atmosphere. After the addition of CH2Cl2 (25 ml) and
Et3N (0.786 ml, 5.65 mmol), the mixture was cooled to
0 °C, and then trifluoromethanesulfonic anhydride
(0.779 ml, 4.75 mmol) was added, followed by stirring for
1 h at 0 °C and for 17 h at room temperature. The reaction
was quenched by the addition of water and stirred for
30 min and extracted with AcOEt. The combined extracts
were washed with brine, dried over Na2SO4, and condensed
under reduced pressure. The residue was dissolved in a
small amount of EtOH, and the solution was adjusted to
pH 11 by the addition of 1 M aq NaOH solution and stir-
red for 1 min. The mixture was washed with Et2O. The
aqueous layer was acidified to pH 4 by the addition of
1 M aq HCl solution and extracted with Et2O. The com-
bined extracts were washed with brine, dried over Na2SO4,
and condensed under reduced pressure to give crude 4f
(866 mg, 87%). Crude 4f was used in the following reaction
without further purification. A small amount of 4f was
(69 mg, 7%). Mp 179.5–180.5 °C (decomp., recrystallized
25
from toluene/hexane); ½aꢁD ¼ þ103 (c 0.21, CHCl3); IR
(KBr) 3271, 3245, 3066, 2992, 2928, 1728, 1710, 1685,
1473, 1458, 1438, 1396, 1373, 1365, 1352, 1301, 1260,
1171, 1087, 964, 917, 845, 815, 802, 768, 699, 664 cmꢀ1
;
1H NMR (CDCl3): d = 1.30 (s, 18H), 2.40 (s, 6H), 4.22
(d, J = 9.03 Hz, 2H), 5.26 (d, J = 9.03, 2H), 7.29 (d,
J = 8.05, 4H), 7.69 (d, J = 8.05 Hz, 4H). Found: C,
54.86; H, 6.34; N, 4.91. Calcd for C26H36N2O8S2: C,
54.91; H, 6.38; N, 4.93.
recrystallized for characterization and analysis. Mp 85.5–
25
86.5 °C (from hexane/Et2O); ½aꢁD ¼ þ26 (c 0.22, EtOH);
IR (KBr) 3257, 3156, 2984, 2968, 2928, 2856, 2799, 1751,
1724, 1685, 1654, 1636, 1483, 1454, 1439, 1391, 1296,
1266, 1236, 1200, 1139, 1095, 1018, 977, 917, 870, 799,
In a similar manner, di-tert-butyl N-sulfonylated 2,3-diami-
nosuccinates 7b–d were prepared from the corresponding
dimethyl 2,3-diaminosuccinates 4b–d.

M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
3081
4.2.10. Di-tert-butyl (S,S)-2,3-bis(naphthalene-2-sulfon-
amido)succinate 7b. Mp 175.5–176.5 °C (decomp., recrys-
crude 5f. After cooling a solution of 5f (1.44 g, 1.86 mmol)
in CH2Cl2 (60 ml) to –40 °C in a pressure bottle, isobutene
(ca. 12.1 g, 216 mmol) was bubbled into the above solution
and a catalytic amount of H2SO4 was added. The mixture
was stirred for 95 h at room temperature. The reaction
mixture was quenched by the addition of water and
adjusted to pH 4 by the addition of saturated aq NaHCO3
solution. The mixture was extracted with AcOEt and the
combined extracts were washed with brine, dried over
Na2SO4, and condensed under reduced pressure. The
remaining 5f and monoester in the residue were separated
by column chromatography (SiO2, hexane/EtOH = 4/1).
Most of the solvent of the eluent containing 7f was evapo-
rated under reduced pressure. After hexane was added to
the residue, the precipitated 7f was filtered off (877 mg,
48%). The filtrate was condensed and the residue was
dissolved in a small amount of MeOH. The solution was
adjusted to pH 11 by the addition of 1 M aq NaOH solu-
tion and stirred for 1 min. After being washed with Et2O,
the aqueous layer was acidified to pH 4 by the addition
of 1 M aq HCl solution and extracted with Et2O. The com-
bined extracts were washed with brine, dried over Na2SO4,
and condensed under reduced pressure to give the almost
pure 7f. Compound 7f obtained was once dissolved in a
small amount of MeOH, and most of the MeOH was evap-
orated under reduced pressure. To the residue was added
hexane and the precipitated 7f was filtered off (597 mg,
33%). The filtrate was condensed and the residue was puri-
fied by TLC (SiO2, hexane/i-PrOH = 8/1, twice) to give 7f
25
tallized from hexane/AcOEt); ½aꢁD ¼ þ131 (c 0.20, CHCl3);
IR (KBr) 3274, 3060, 2983, 2965, 2929, 1728, 1713, 1590,
1505, 1455, 1395, 1366, 1352, 1295, 1259, 1168, 1132,
1095, 1076, 966, 916, 868, 855, 828, 794, 768, 746, 697,
1
661 cmꢀ1; H NMR (CDCl3): d = 1.13 (s, 18H), 4.31 (d,
J = 8.54 Hz, 2H), 5.40 (d, J = 8.54 Hz, 2H), 7.61 (dd,
J = 6.83, 7.81 Hz, 2H), 7.65 (dd, J = 6.83, 8.54 Hz, 2H),
7.76 (d, J = 8.54 Hz, 2H), 7.89 (d, 7.81 Hz, 2H), 7,94 (d,
J = 8.54 Hz, 4H), 8.36 (s, 2H). Found: C, 59.73; H, 5.67;
N, 4.47. Calcd for C32H36N2O8S2: C, 59.98; H, 5.66; N, 4.37.
4.2.11. Di-tert-butyl (S,S)-2,3-bis(naphthalene-1-sulfon-
amido)succinate 7c. Mp 137.5–138.5 °C (from toluene/
25
hexane); ½aꢁD ¼ þ104 (c 0.20, EtOH); IR (KBr) 3304,
3060, 2980, 2932, 2871, 1737, 1594, 1508, 1457, 1395,
1370, 1350, 1298, 1259, 1231, 1201, 1167, 1104, 1027,
980, 934, 890, 837, 805, 771, 712, 679 cmꢀ1 1H NMR
;
(CDCl3): d = 1.03 (s, 18H), 4.16 (d, J = 8.54 Hz, 2H),
5.62 (d, J = 8.54 Hz, 2H), 7.51 (dd, J = 7.32, 8.30 Hz,
2H), 7.61 (dd, J = 7.08, 7.81 Hz, 2H), 7.70 (dd, J = 7.08,
8.54 Hz, 2H), 7.93 (d, J = 7.81 Hz, 2H), 8.06 (d,
J = 8.30 Hz, 2H), 8.16 (d, J = 7.32 Hz, 2H), 8.64 (d,
J = 8.54 Hz, 2H). Found: C, 59.86; H, 5.74; N, 4.38. Calcd
for C32H36N2O8S2: C, 59.98; H, 5.66; N, 4.37.
4.2.12. Di-tert-butyl (S,S)-2,3-bis(2,4,6-trimethylphenylsulfon-
amido)succinate 7d. Mp 171–172 °C (from hexane/
25
AcOEt); ½aꢁD ¼ þ89 (c 0.24, CHCl3); IR (KBr) 3328,
(210 mg, 11%). Mp 155–156 °C (decomp., recrystallized
25
2976, 2940, 2876, 1758, 1743, 1604, 1564, 1457, 1429,
1370, 1344, 1313, 1282, 1222, 1188, 1169, 1153, 1109,
from hexane/EtOH); ½aꢁD ¼ þ10 (c 0.22, CHCl3); IR
(KBr) 3210, 2988, 2921, 1719, 1465, 1388, 1339, 1285,
1235, 1200, 1148, 1102, 984, 947, 829, 793, 772,
1056, 1037, 966, 937, 851, 784, 753, 720, 709, 657 cmꢀ1
;
1H NMR (CDCl3): d = 1.29 (s, 18H), 2.27 (s, 6H), 2.63
(s, 12H), 4.07 (d, J = 8.78 Hz, 2H), 5.49 (d, J = 8.78 Hz,
2H), 6.93 (s, 4H). Found: C, 57.41; H, 7.17; N, 4.51. Calcd
for C30H44N2O8S2: C, 57.66; H, 7.10; N, 4.48.
713 cmꢀ1; H NMR (CDCl3): d = 1.52 (s, 18H), 4.48 (s,
1
2H), 6.16 (br, 2H). Found: C, 32.09; H, 4.30; N, 5.62.
Calcd for C14H22N2O8F6S2: C, 32.06; H, 4.23; N, 5.34.
4.3. Asymmetric 1,3-dipolar cycloaddition
4.2.13. Di-tert-butyl (S,S)-2,3-di(methylsulfonamido)succi-
nate 7e. In a similar manner for the preparation of 6, the
hydrolysis of 4e (128 mg, 0.386 mmol) was carried out. The
solution was neutralized to pH 8 by the addition of 1 M aq
HCl solution and washed with AcOEt. The aqueous phase
was acidified to pH 3 by the addition of 1 M aq HCl solu-
tion and the water was evaporated under reduced pressure,
since product 5e is water soluble. The residual oil was
extracted with AcOEt and the combined extracts were
condensed under reduced pressure to give crude 5e
(118 mg, quant.). In a similar manner for the preparation
4.3.1. Representative procedure for asymmetric 1,3-dipolar
cycloaddition of a nitrile oxide to allyl alcohol (Table 2,
entry 15). To a suspension of ethylbenzene (3.75 ml) solu-
tion of allyl alcohol 8 (20 mg, 0.344 mmol) with powdered
˚
MS 3A (200 mg) was added diethylzinc (0.344 mmol,
0.344 ml of 1.00 M solution in hexane) at 0 °C under an
argon atmosphere, and the mixture was stirred for
10 min. After adding a solution of chiral sulfonamide 7f
(181 mg, 0.345 mmol) in ethylbenzene (6.0 ml) and
tBuOMe (1.25 ml), the mixture was stirred for 1 h at
0 °C. To the solution, diethylzinc (0.379 mmol, 0.379 ml
of 1.00 M solution in hexane) was added and the mixture
was stirred for 10 min at 0 °C. A precooled (0 °C) ethylben-
zene (6.5 ml) solution of p-methoxybenzohydroximoyl
chloride (70 mg, 0.377 mmol) was then added all at once
and the mixture was stirred for 24 h at 0 °C. The reaction
was quenched by the addition of a saturated aq NH4Cl
solution. After filtration of the precipitate, the filtrate was
extracted with AcOEt. The combined extracts were washed
with brine, dried over Na2SO4, and condensed under
reduced pressure. The residue was separated by TLC on
SiO2. The chiral auxiliary was separated first (hexane/
i-PrOH/AcOH = 6/1/0.03), then the part containing
of 7a, the esterification was carried out. Mp 149–150 °C
25
(from hexane/AcOEt); ½aꢁD ¼ ꢀ5 (c 0.20, CHCl3); IR
(KBr) 3329, 3274, 2977, 2939, 2880, 2779, 1733, 1716,
1652, 1645, 1634, 1505, 1454, 1396, 1370, 1349, 1328,
1284, 1261, 1158, 1109, 1043, 987, 940, 840, 785, 773,
1
670 cmꢀ1; H NMR (CDCl3): d = 1.54 (s, 18H), 2.97 (s,
6H), 4.61 (d, J = 9.27 Hz, 2H), 5.48 (d, J = 9.27 Hz, 2H).
Found: C, 40.16; H, 6.80; N, 6.73. Calcd for
C14H28N2O8S2: C, 40.37; H, 6.78; N, 6.73.
4.2.14. Di-tert-butyl (S,S)-2,3-bis(trifluoromethylsulfon-
amido)succinate 7f. In a similar manner for the prepara-
tion of 6, the hydrolysis of 4f was carried out to give

3082
M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
1
product 10A was eluted and again developed on TLC to
separate 10A (CHCl3/MeCN = 7/1) in 74% (53 mg)
yield. The enantioselectivity was determined by HPLC
(Daicel Chiralcel OD-H, hexane/EtOH = 15/1, detected
at 254 nm) analysis to be 71% ee.
908, 864, 828, 808, 707 cmꢀ1; H NMR (CDCl3): d = 1.84
(dd, J = 5.37, 7.32 Hz, 1H), 3.26 (dd, J = 8.05, 16.59 Hz,
1H), 3.36 (dd, J = 10.73, 16.59 Hz, 1H), 3.69 (ddd,
J = 4.39, 7.32, 12.20 Hz, 1H), 3.89 (ddd, J = 3.17, 5.37,
12.20 Hz, 1H), 4.89 (dddd, J = 3.17, 4.39, 8.05, 10.73 Hz,
1H), 7.54 (s, 4H). Found: C, 46.73; H, 3.96; N, 5.43. Calcd
for C10H10NO2Br: C, 46.90; H, 3.94; N, 5.47%. The enantio-
selectivity was determined by HPLC (Daicel Chiralcel
OD-H, hexane/EtOH = 15/1, detected at 254 nm).
4.3.2. Recovery of the chiral auxiliary. The part of TLC
containing chiral auxiliary 7f was eluted and condensed
under reduced pressure to give the almost pure 7f quantita-
tively. Compound 7f obtained was washed with a small
amount of benzene/hexane (1/1) and dissolved in a small
amount of MeOH. After evaporation of most of the
MeOH, hexane was added and the resulting precipitate
was filtered off and washed with benzene to recover the
enantiomerically pure 7f (66 %).
4.3.7. (R)-5-(Hydroxymethyl)-3-(4-cyanophenyl)-2-isoxazo-
25
line 10E. Mp 128–129 °C (from hexane/EtOH); ½aꢁD
¼
ꢀ75 (c 0.22, MeOH, 49% ee); IR (KBr) 3422, 3075, 3048,
2952, 2935, 2871, 2224, 1608, 1595, 1508, 1433, 1410,
1398, 1361, 1283, 1251, 1104, 1049, 990, 969, 939, 909,
852, 838, 812, 776 cmꢀ1; H NMR (CDCl3): d = 1.85 (dd,
1
4.3.3. (R)-5-(Hydroxymethyl)-3-(4-methoxyphenyl)-2-isox-
J = 5.37, 7.81 Hz, 1H), 3.31 (dd, J = 8.05, 16.59 Hz, 1H),
3.38 (dd, J = 10.73, 16.59 Hz, 1H), 3.71 (ddd, J = 4.15,
7.81, 12.44 Hz, 1H), 3.93 (ddd, J = 3.17, 5.37, 12.44 Hz,
1H), 4.94 (dddd, J = 3.17, 4.15, 8.05, 10.73 Hz, 1H), 7.70
(d, J = 8.54 Hz, 2H), 7.77 (d, J = 8.54 Hz, 2H). Found:
C, 65.13; H, 5.03; N, 13.74. Calcd for C11H10N2O2: C,
65.33; H, 4.98; N, 13.86%. The enantioselectivity was deter-
mined by HPLC (Daicel Chiralcel OD-H, hexane/
i-PrOH = 7/1, detected at 254 nm).
25
azoline 10A. Mp 166–167 °C (from EtOH); ½aꢁD ¼ ꢀ94
(c 0.53, MeOH, 71% ee); IR (KBr) 3380, 3010, 2950,
2850, 1600, 1510, 1450, 1440, 1410, 1360, 1300, 1290,
1250, 1170, 1100, 1040, 1010, 990, 950, 920, 900, 860,
820, 800, 780 cmꢀ1
;
1H NMR (CDCl3): d = 1.88 (t,
J = 7.02 Hz, 1H), 3.25 (dd, J = 7.63, 16.48 Hz, 1H), 3.27
(dd, J = 10.68, 16.48 Hz, 1H), 3.68 (ddd, J = 4.88, 7.02,
12.51 Hz, 1H), 3.84 (s, 3H), 3.86 (m, 1H), 4.84 (m, 1H),
6.92 (d, J = 8.85 Hz, 2H), 7.61 (d, J = 8.85 Hz, 2H).
Found: C, 63.57; H, 6.40; N, 6.72. Calcd for C11H13NO3:
C, 63.76; H, 6.32; N, 6.76%. The enantioselectivity was
determined by HPLC (Daicel Chiralcel OD-H, hexane/
EtOH = 15/1, detected at 254 nm).
Acknowledgements
The present work was financially supported in part by
Grant-in-Aid for Scientific Research on Priority Areas ‘Ad-
vanced Molecular Transformations of Carbon Resources’
from The Ministry of Education, Culture, Sports, Science,
and Technology (MEXT), Grant-in-Aid for Scientific Re-
search (C) from Japan Society for the Promotion of Science
(JSPS), and NOVARTIS Foundation (Japan) for the Pro-
motion of Science.
4.3.4. (R)-5-(Hydroxymethyl)-3-phenyl-2-isoxazoline 10B.7
25
Mp 67–68 °C (from hexane/AcOEt); ½aꢁD ¼ ꢀ92 (c 0.44,
25
CHCl3, 55% ee) [lit.,7b ½aꢁD ¼ ꢀ161 (c 1.0, CHCl3, 100%
ee)]; IR (KBr) 3360, 3060, 2920, 2840, 1580, 1490, 1460,
1440, 1350, 1100, 1040, 1010, 910, 880, 800, 740,
1
680 cmꢀ1; H NMR (CDCl3): d = 2.12 (br, 1H), 3.28 (dd,
J = 7.81, 16.59 Hz, 1H), 3.39 (dd, J = 10.73, 16.59 Hz,
1H), 3.69 (dd, J = 4.88, 12.20 Hz, 1H), 3.88 (dd, J = 3.17,
12.20 Hz, 1H), 4.82–4.94 (m, 1H), 7.37–7.44 (m, 3H),
7.63–7.71 (m, 2H). The enantioselectivity was determined
by HPLC (Daicel Chiralcel OB-H, hexane/EtOH = 2/1,
detected at 254 nm).
References
1. For reviews, see: (a) Bennani, Y. L.; Hanessian, S. Chem. Rev.
1997, 97, 3161–3195; (b) Lucet, D.; Gall, T. L.; Mioskowski,
C. Angew. Chem., Int. Ed. 1998, 37, 2580–2627; (c) Viso, A.;
´
´
Fernandez-Pradilla, R.; Garcıa, A.; Flores, A. Chem. Rev.
4.3.5.
azoline 10C.7 An oil; ½aꢁD ¼ ꢀ53 (c 0.17, CHCl3, 50%
(R)-3-(1,1-Dimethylethyl)-5-hydroxymethyl-2-isox-
25
2005, 105, 3167–3196.
25
2. Recent examples of preparation of chiral vicinal diamines: (a)
Alexakis, A.; Tomassini, A.; Chouillet, C.; Roland, S.;
Mangeney, P.; Bernardinelli, G. Angew. Chem., Int. Ed.
2000, 39, 4093–4095; (b) Prakash, G. K. S.; Mandal, M. J.
ee) [lit.,7b ½aꢁD ¼ ꢀ127 (c 1.0, CHCl3, 100% ee)]; IR (neat)
3400, 2967, 2933, 2871, 1647, 1613, 1479, 1462, 1436, 1396,
1366, 1337, 1257, 1219, 1206, 1168, 1086, 1051, 950, 879,
1
827, 808 cmꢀ1; H NMR (CDCl3): d = 1.21 (s, 9H), 2.38
´
Am. Chem. Soc. 2002, 124, 6538–6539; (c) Viso, A.; Fernandez-
(br, 1H), 2.87 (dd, J = 7.32, 16.83 Hz, 1H), 3.02 (dd,
J = 10.49, 16.83 Hz, 1H), 3.56 (dd, J = 4.88, 11.95 Hz,
1H), 3.76 (dd, J = 3.17, 11.95 Hz, 1H), 4.67 (dddd,
J = 3.17, 4.88, 7.32, 10.49 Hz, 1H). The enantioselectivity
was determined by HPLC (Daicel Chiralcel OB-H,
hexane/EtOH = 30/1, detected at 220 nm).
´
Pradilla, R.; Garcıa, A.; Guerrero-Strachan, C.; Alonso, M.;
´
Tortosa, M.; Flores, A.; Martınez-Ripoll, M.; Fonseca, I.;
´
´
Andre, I.; Rodrıguez, A. Chem. Eur. J. 2003, 9, 2867–2876; (d)
Westermann, B. Angew. Chem., Int. Ed. 2003, 42, 151–153; (e)
Bunnage, M. E.; Burke, A. J.; Davies, S. G.; Millican, N. L.;
Nicholson, R. L.; Roberts, P. M.; Smith, A. D. Org. Biomol.
Chem. 2003, 1, 3708–3715; (f) Zhong, Y.-W.; Xu, M.-H.; Lin,
G.-Q. Org. Lett. 2004, 6, 3953–3956; (g) Zhong, Y.-W.; Izumi,
K.; Xu, M.-H.; Lin, G.-Q. Org. Lett. 2004, 6, 4747–4750; (h)
Rondot, C.; Zhu, J. Org. Lett. 2005, 7, 1641–1644; (i) Nadir,
U. K.; Krishna, R. V.; Singh, A. Tetrahedron Lett. 2005, 46,
479–482; (j) Chowdari, N. S.; Ahmad, M.; Albertshofer, K.;
Tanaka, F.; Barbas, C. F., III. Org. Lett. 2006, 8, 2839–2842;
4.3.6. (R)-5-(Hydroxymethyl)-3-(4-bromophenyl)-2-isoxazo-
line 10D. Mp 122.5–123.5 °C (from hexane/EtOH);
25
½aꢁD ¼ ꢀ61 (c 0.29, MeOH, 57% ee); IR (KBr) 3388,
2937, 2923, 2866, 1593, 1490, 1438, 1400, 1375, 1358,
1307, 1248, 1184, 1105, 1070, 1050, 1008, 995, 959, 937,

M. Serizawa et al. / Tetrahedron: Asymmetry 17 (2006) 3075–3083
3083
(k) Fukuta, Y.; Mita, T.; Fukuda, N.; Kanai, M.; Shibasaki,
M. J. Am. Chem. Soc. 2006, 128, 6312–6313.
S.; Ukaji, Y.; Inomata, K. Bull. Chem. Soc. Jpn. 2006, 79,
1069–1083.
3. Recent reports of enantioselective reactions using chiral mono-
and disulfonamide derived from chiral vicinal diamines: (a)
Walsh, P. J. Acc. Chem. Res. 2003, 36, 739–749; (b) Ooi, T.;
Saito, A.; Maruoka, K. J. Am. Chem. Soc. 2003, 125, 3220–
3221; (c) Akiyama, K.; Mikami, K. Tetrahedron Lett. 2004, 45,
7217–7220; (d) Hamada, T.; Torii, T.; Izawa, K.; Ikariya, T.
Tetrahedron 2004, 60, 7411–7417; (e) Arseniyadis, S.; Subhash,
P. V.; Valleix, A.; Mathew, S. P.; Blackmond, D. G.; Wagner,
A.; Mioskowski, C. J. Am. Chem. Soc. 2005, 127, 6138–6139;
(f) Blid, J.; Panknin, O.; Somfai, P. J. Am. Chem. Soc. 2005,
127, 9352–9353; (g) Honjo, T.; Sano, S.; Shiro, M.; Nagao, Y.
Angew. Chem., Int. Ed. 2005, 44, 5838–5841; (h) Tonoi, T.;
Mikami, K. Tetrahedron Lett. 2005, 46, 6355–6358; (i) Ikariya,
T.; Murata, K.; Noyori, R. Org. Biomol. Chem. 2006, 4, 393–
406; (j) Arakawa, Y.; Haraguchi, N.; Itsuno, S. Tetrahedron
Lett. 2006, 47, 3239–3243.
5. Asymmetric syntheses of 2,3-diaminosuccinate derivatives
´
´
were reported: (a) Fernandez-Megıa, E.; Paz, M. M.; Sardina,
F. J. J. Org. Chem. 1994, 59, 7643–7652; (b) Alvarez-Ibarra,
´
C.; Csaky, A. G.; Colmenero, B.; Quiroga, M. L. J. Org.
¨
Chem. 1997, 62, 2478–2482; (c) Muniz, K.; Nieger, M. Synlett
˜
2003, 211–214; (d) Bernardi, L.; Gothelf, A. S.; Hazell, R. G.;
Jørgensen, K. A. J. Org. Chem. 2003, 68, 2583–2591; (e) Chen,
Y.; Yudin, A. K. Tetrahedron Lett. 2003, 44, 4865–4868; (f)
Ooi, T.; Kameda, M.; Fujii, J.; Maruoka, K. Org. Lett. 2004,
6, 2397–2399.
6. (a) Ukaji, Y.; Sada, K.; Inomata, K. Chem. Lett. 1993, 1847–
1850; (b) Shimizu, M.; Ukaji, Y.; Inomata, K. Chem. Lett.
1996, 455–456; (c) Yoshida, Y.; Ukaji, Y.; Fujinami, S.;
Inomata, K. Chem. Lett. 1998, 1023–1024; (d) Ukaji, Y.; Ima,
M.; Yamada, T.; Inomata, K. Heterocycles 2000, 52, 563–566;
(e) Tsuji, M.; Ukaji, Y.; Inomata, K. Chem. Lett. 2002, 1112–
1113.
7. (a) Curran, D. P.; Kim, B. H.; Piyasena, H. P.; Loncharich, R.
J.; Houk, K. N. J. Org. Chem. 1987, 52, 2137–2141; (b)
Curran, D. P.; Kim, B. H.; Daugherty, J.; Haffner, T. A.
Tetrahedron Lett. 1988, 29, 3555–3558; (c) Kanemasa, S.;
Onimura, K. Tetrahedron 1992, 48, 8645–8658.
4. (a) Ukaji, Y.; Inomata, K. Synlett 2003, 1075–1087; (b) Xia,
D.; Ukaji, Y.; Fujinami, S.; Inomata, K. Chem. Lett. 2003, 32,
582–583; (c) Wei, W.; Kobayashi, M.; Ukaji, Y.; Inomata, K.
Chem. Lett. 2006, 35, 176–177; (d) Takinami, M.; Ukaji, Y.;
Inomata, K. Tetrahedron: Asymmetry 2006, 17, 1554–1560; (e)
Xia, D.; Taniguchi, K.; Hamamoto, Y.; Sada, K.; Fujinami,