Enantioselective intramolecular C-H amidation of sulfamate esters catalyzed by chiral dirhodium(II) carboxylates

Article abstract of DOI:10.3987/com-06-s(o)49

The chiral dirhodium(II) carboxylate-catalyzed enantioselective intramolecular C-H amidation reaction of sulfamate esters via in situ generated iminoiodinanes is described. The use of dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh₂(S-TFPTTL)₄, as a catalyst and PhI(OAc)₂ as an oxidant provides cyclic sulfamidates in up to 48% ee.

Full text of DOI:10.3987/com-06-s(o)49

HETEROCYCLES, Vol. 69, 2006
527
HETEROCYCLES, Vol. 69, 2006, pp. 527 - 537. © The Japan Institute of Heterocyclic Chemistry
Received, 30th August, 2006, Accepted, 6th October, 2006, Published online, 10th October, 2006. COM-06-S(O)49
ENANTIOSELECTIVE INTRAMOLECULAR C–H AMIDATION OF
SULFAMATE ESTERS CATALYZED BY CHIRAL DIRHODIUM(II)
†
CARBOXYLATES
Minoru Yamawaki, Shinji Kitagaki, Masahiro Anada, and
Shunichi Hashimoto*
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812,
Japan
e-mail: hsmt@pharm.hokudai.ac.jp
Abstract – The chiral dirhodium(II) carboxylate-catalyzed enantioselective
intramolecular C–H amidation reaction of sulfamate esters via in situ generated
iminoiodinanes
is
described.
The
use
of
dirhodium(II)
tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh2(S-TFPTTL)4, as a catalyst
and PhI(OAc)2 as an oxidant provides cyclic sulfamidates in up to 48% ee.
The transition metal-catalyzed intramolecular C–H amidation of iminoiodinanes, which features C–N
bond formation at an unactivated carbon atom, offers a potentially powerful strategy for the synthesis of
heterocycles.1*While the pioneering work of Breslow and Gellman in 1983 demonstrated that the
Rh2(OAc)4-catalyzed
intramolecular
C–H
amidation
of
[(2,5-diisopropyl)phenylsulfonylimino]phenyliodinane provided cyclic sulfonamide in high yield,2 it was
not until several years ago that an efficient and general intramolecular C–H amidation procedure with in
situ generated iminoiodinanes was developed.3-5 Du Bois and co-workers demonstrated that the oxidation
of carbamates and sulfamate esters by PhI(OAc)2 in the presence of MgO gives only low concentrations
of iminoiodinanes, which undergo rapid C-H insertion under the influence of a dirhodium(II) catalyst to
produce oxazolidinones and cyclic sulfamidates, respectively, with high regioselectivity and good to
excellent diastereoselectivity.3,4 Since then, remarkable progress has been achieved in the development of
intramolecular C–H amidations with effective metal catalysts derived from Ru(II),6 Mn(III),7 and Ag(I).8
Consequently, a great deal of effort has been directed toward the development of an enantioselective
version of these catalytic processes. Che and co-workers demonstrated the first successful examples of
†
Dedicated to Professor Satoshi Ōmura on the occasion of his 70th birthday.

528
HETEROCYCLES, Vol. 69, 2006
the enantioselective intramolecular C–H amidation of sulfamate esters (up to 88% ee), using a chiral
ruthenium(II) porphyrin-catalyst.6 Thereafter, Fruit and Müller reported enantioselective intramolecular
C–H amidation reactions of sulfamate esters and sulfonamides catalyzed by chiral dirhodium(II)
carboxylates, Rh2(S-NTTL)4 (1g) and Rh2(R-NTV)4 (1h), in up to 52% ee and 66% ee, respectively.9
More recently, the Che group explored the intramolecular C–H amidation of sulfamate esters in the
presence of chiral manganese(III)-salen-catalysts, in which moderate to good enantioselectivities (up to
79% ee) were obtained.7
We recently reported that the enantioselective intermolecular benzylic C–H amidation of aromatic
hydrocarbons (2) with [(4-nitrophenyl)sulfonylimino]phenyliodinane (3) catalyzed by chiral
dirhodium(II) carboxylates provides sulfonamides in up to 84% ee [eqn. (1)].10 In this process,
Rh2(S-TCPTTL)4 (1a), characterized by the substitution of chlorine atoms for four hydrogen atoms on the
phthalimido group in the parent dirhodium(II) complex, Rh2(S-PTTL)4 (1c),11,12 proved to be the catalyst
of choice in terms of product yield and enantioselectivity as well as catalyst activity. As a logical
extension of our studies, we now address the issue of enantiocontrol in the intramolecular C–H amidation
of sulfamate esters.
Rh2(S-TCPTTL)4 (1a)
(2 mol %)
NHpNs
( )n
R
+
pNsN=IPh
( )n
R
(1)
CH2Cl2, –23 °C
3
R
R
pNs = 4-NO2C6H4SO2
4
2
up to 84% ee
n = 1 or 2
R = H or Me
X
O
N
O
X
X
O
O
N
H
R
N
N
X
H
H
H
O
O
O
O
O
O
O
O
O
O
O
O
Rh Rh
Rh Rh
Rh Rh
Rh Rh
X = Cl: Rh2(S-TCPTTL)4 (1a) R = Me: Rh2(S-PTA)4 (1d)
Rh2(S-NTTL)4 (1g)
Rh2(R-NTV)4 (1h)
X = F: Rh2(S-TFPTTL)4 (1b)
X = H: Rh2(S-PTTL)4 (1c)
R = Bn: Rh2(S-PTPA)4 (1e)
R = iPr: Rh2(S-PTV)4 (1f)
In an extension of our previous work, we initially explored the C–H amidation of indan-2-yl sulfamate
(5a) using 2 mol % of Rh2(S-TCPTTL)4 (1a), in the presence of 1.1 equiv. of PhI(OAc)2 and 2.3 equiv. of
MgO. The reaction in dichloromethane at 23 °C proceeded smoothly to give the cyclic sulfamidate (6a),
25
[α]D +31.3° (c 0.87, THF), in 81% yield with complete cis selectivity (Table 1, Entry 1). The
enantioselectivity of this reaction was determined to be 22% ee by HPLC analysis (Daicel Chiralcel
OD-H). The preferred absolute stereochemistry of 6a was established as (3aR,8aS) by comparing the sign

HETEROCYCLES, Vol. 69, 2006
529
Table 1. Enantioselective Intramolecular C–H Amidation of Indan-2-yl Sulfamate (5a) Catalyzed by
a)
Chiral Dirhodium(II) Carboxylates
Rh(II) catalyst (2 mol %)
PhI(OAc)2 (1.1 equiv.)
O
H
N
SO2NH2
S O
O
R
O
MgO (2.3 equiv.)
solvent, 23 °C
S
5a
6a
Cyclic sulfamidate 6a
b)
c)
Entry
Rh(II) catalyst
Solvent
Time (h)
Yield (%)
[!]D (c, THF) Ee (%)
e)
01
Rh2(S-TCPTTL)4 (1a)
Rh2(S-TCPTTL)4 (1a)
Rh2(S-TCPTTL)4 (1a)
Rh2(S-TFPTTL)4 (1b)
Rh2(S-PTTL)4 (1c)
Rh2(S-PTA)4 (1d)
CH2Cl2
benzene
toluene
benzene
benzene
benzene
benzene
benzene
benzene
benzene
3
1
81
79
37
98
75
61
70
79
98
51
+31.3° (0.87)
+48.9° (1.05)
+30.0° (0.63)
+68.3° (1.03)
+52.0° (1.13)
+15.7° (1.01)
+21.5° (0.86)
+16.8° (1.20)
+64.2° (0.93)
+56.3° (0.75)
22
35
23
48
43
15
18
19
45
38
e)
e)
e)
e)
e)
e)
e)
e)
e)
02
03
1
04
1
05
2
06
1
07
Rh2(S-PTPA)4 (1e)
Rh2(S-PTV)4 (1f)
1.5
2
08
09d)
10d)
Rh2(S-TFPTTL)4 (1b)
Rh2(S-PTTL)4 (1c)
1
0.5
a)
b)
c)
All reactions were performed on a 0.2 mmol scale. Isolated yield. Determined by HPLC (Daicel Chiralcel
OD-H column). d) The reaction was carried out in the absence of MgO.
24
of the optical rotation with (3aR,8aS)-6a [[α]D
+141° (c 0.82, THF)], prepared from
(1R,2S)-1-aminoindan-2-ol according to the procedure of Harwood (SO2Cl2, Et3N, CH2Cl2, 0 °C, 1 h,
67%).13 A survey of solvents revealed that benzene was the optimal solvent for this transformation,
improving the enantioselectivity to 35% ee (Entry 2). Toluene was inferior to benzene in terms of both
product yield and enantioselectivity (Entry 3).14 Using benzene as the solvent, we next evaluated the
performance of other chiral dirhodium(II) carboxylate catalysts. While a uniform sense of asymmetric
induction was observed in all cases, the ee values were dependent on the catalyst. As might be expected
from the results for the enantioselective intermolecular amidation of indan, chiral dirhodium(II)
carboxylate catalysts, Rh2(S-PTA)4 (1d), Rh2(S-PTPA)4 (1e), and Rh2(S-PTV)4 (1f) were less effective
than Rh2(S-TCPTTL)4 (Entries 6–8).15 Somewhat surprisingly, Rh2(S-TFPTTL)4 (1b)16 and Rh2(S-PTTL)4
(1c) proved to be the catalysts of choice for this process, displaying higher enantioselectivities than
Rh2(S-TCPTTL)4 (48% and 43% ee, Entries 4 and 5). Although the enantioselectivities are modest, these
ee values exceed those (22% and 30% ee)9b reported previously by Fruit and Müller, using Rh2(S-NTTL)4
(1g) and Rh2(R-NTV)4 (1h). It is noteworthy that the isolated yield (98%) obtained using
Rh2(S-TFPTTL)4 is the highest ever reported for the intramolecular C–H amidation of 5a. In this respect,
it is interesting to note that the reaction with Rh2(S-TFPTTL)4 in the absence of MgO as an AcOH
scavenger gave nearly the same result as that in the presence of MgO (Entry 4 vs. 9), which is in marked

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HETEROCYCLES, Vol. 69, 2006
Table 2. Enantioselective Intramolecular C–H Amidation of Sulfamate Esters (5b-d)a)
Yield (%)b)
Rh(II) catalyst
Time (h)
Product
Ee (%)
Entry Sulfamate ester
1
H
N
O
O
1
1
+27c)
+14c)
Rh2(S-TFPTTL)4 (1b)
Rh2(S-PTTL)4 (1c)
30
34
OSO2NH2
S
O
2
5b
6b
O
O
S
OSO2NH2
+10d)
+21d)
HN
O
Rh2(S-TFPTTL)4 (1b)
Rh2(S-PTTL)4 (1c)
87
67
10
30
3
4
Ph
Ph
5c
6c
O
O
S
OSO2NH2
HN
O
49(39)e)
09(45)e)
2
2
+14f)
–16f)
Rh2(S-TFPTTL)4 (1b)
Rh2(S-PTTL)4 (1c)
5
6
6d
5d
a) All reactions were performed on a 0.2 mmol scale with 2 mol % of Rh(II) catalyst, 1.1 equiv. of PhI(OAc)2 and 2.3 equiv.
of MgO in benzene at 23 °C. b) Isolated yield. c) Determined by HPLC (Daicel Chiralpak AD column) after conversion to the
corresponding benzyl carbamate. d) Determined by HPLC (Daicel Chiralcel OD column). e) Values in parentheses refer to the
yields of sulfamate esters recovered. f) Determined by HPLC (Daicel Chiralpak IA column).
contrast with the results for Rh2(S-PTTL)4 (Entry 5 vs. 10). These results demonstrate the robust nature
and high reactivity of Rh2(S-TFPTTL)4.
We then investigated the applicability of the present catalytic system to sulfamate esters other than 5a.
Some representative results are presented in Table 2. To our disappointment, the method was found to be
highly sensitive to the structure of the substrate. The reaction of cyclopentyl sulfamate ester (5b) under
the influence of Rh2(S-TFPTTL)4 or Rh2(S-PTTL)4 gave the cyclic sulfamidate (6b) in low yields with
complete cis selectivity, wherein ee values were significantly lower than those in the case of 5a (Entries 1
and 2). These results strongly suggest that the presence of a phenyl ring is required for both product yield
and enantioselectivity in the five-membered ring insertion process. It was also found that the formation of
the six-membered cyclic sulfamidate (6c), the preferred pathway in the C–H amidation of acyclic,
conformationally mobile sulfamate esters, resulted in disappointing enantioselectivities (Entries 3 and 4).
In this reaction, Rh2(S-PTTL)4 exhibited a higher enantioselectivity than Rh2(S-TFPTTL)4. The
intramolecular insertion of aromatic sulfamate ester (5d) into a benzylic C–H bond provided the tricyclic
sulfamidate (6d) in low to moderate yields with ca. 60% substrate conversion and only a poor
enantioselectivity (Entries 5 and 6).
In summary, we have reported one-pot enantioselective C–H amidation of sulfamate esters with the use of
chiral dirhodium(II) carboxylate catalysts and PhI(OAc)2 as an oxidant. Rh2(S-TFPTTL)4 is the most
effective catalyst for this process (up to 48% ee). In contrast to the enantioselective intermolecular
amidation of benzylic C–H bonds, there is considerable room for improvement in the intramolecular

HETEROCYCLES, Vol. 69, 2006
531
amidation of sulfamate esters catalyzed by chiral dirhodium(II) complexes. The design and synthesis of a
new class of chiral bridging ligands to further enhance enantioselectivity is currently in progress.
EXPERIMENTAL
General. Melting points were determined on a Büchi 535 digital melting point apparatus and are
uncorrected. IR spectra were recorded on a JASCO FT/IR-5300 spectrometer and absorbance bands are
1
reported in wavenumber (cm-1). H NMR spectra were recorded on JEOL JNM-AL 400 (400 MHz)
spectrometer. Chemical shifts are reported relative to internal standard (tetramethylsilane; δH 0.00 or
acetone-d6; δH 2.04). Data are presented as follows: chemical shift (δ, ppm), multiplicity (s = singlet, d =
13
doublet, t = triplet, m = multiplet, br = broad), coupling constant and integration. C NMR spectra were
recorded on JEOL JNM-AL 400 (100 MHz) spectrometer. Chemical shifts are reported relative to internal
standard (CDCl3; δ 77.0, acetone-d6; δ 29.8). Optical rotations were measured on a JASCO P-1030
digital polarimeter at the sodium D line (589 nm). EI-MS spectra were obtained on a JEOL JMS-HX 110
spectrometer. Column chromatography was carried out on Kanto silica gel 60 N (63-210 mesh).
Analytical thin layer chromatography (TLC) was carried out on Merck Kieselgel 60 F254 plates with
visualization by ultraviolet, anisaldehyde stain solution or phosphomolybdic acid stain solution.
Analytical high performance liquid chromatography (HPLC) was performed on JASCO PU-1580
intelligent HPLC pump with JASCO UV-1575 intelligent UV/VIS detector. Detection was performed at
254 nm. Chiralcel OD, OD-H, Chiralpak IA and AD columns (0.46 cm × 25 cm) from Daicel were used.
Retention times (tR) and peak ratio were determined with Shimadzu C-R8A chromatopac integrator or
JASCO-Borwin analysis system.
All non-aqueous reactions were carried out in flame-dried glassware under argon atmosphere. Reagents
and solvents were purified by standard means. Dehydrated THF, CH2Cl2 and toluene were purchased
from Kanto Chemical Co., Inc. Benzene was distilled from Na/benzophenone ketyl. Sulfamoyl chloride
was prepared according to the procedure of Appel and Berger.17
General procedure for sulfamate ester preparation: indan-2-yl sulfamate (5a).3b,9b The sulfamate
ester (5a) was prepared according to the procedure of Okada.18 Sulfamoyl chloride (2.25 g, 15.0 mmol,
1.5 equiv) was added to a solution of 2-indanol (1.3 g, 10 mmol) in N,N-dimethylacetamide (40 mL, 0.25
M) at 0 °C. The mixture was stirred at 23 °C for 1 h and poured into cold brine (100 mL). The whole
mixture was extracted with EtOAc (2 × 100 mL), and the combined organic layers were washed with H2O
(50 mL) and brine (2 × 50 mL), and dried over Na2SO4. Filtration and evaporation gave the crude product
(2.4 g), which was purified by column chromatography (silica gel, 2:1 hexane/EtOAc) followed by
recrystallization from benzene to provide 5a (1.8 g, 84%) as colorless needles; Rf = 0.54 (5:1

532
HETEROCYCLES, Vol. 69, 2006
1
CH2Cl2/EtOAc); mp 99.5-100.5 °C (lit.,9b mp 89 °C); IR (KBr) ν 3370, 3281, 1346, 1179 cm-1; H NMR
(400 MHz, CDCl3) δ 3.26 (dd, J = 3.6, 17.0 Hz, 2H, C1-H and C3-H), 3.33 (dd, J = 5.8, 17.0 Hz, 2H,
13
C1-H and C3-H), 4.94 (br-s, 2H, NH2), 5.40 (tt, J = 3.6, 5.8 Hz, 1H, C2-H), 7.17-7.24 (m, 4H, ArH); C
NMR (100 MHz, CDCl3) δ 39.81 (CH2), 83.58 (CH), 124.54 (CH), 127.04 (CH), 139.14 (C); HRMS (EI)
calcd for C9H11NO3S (M+) 213.0460, found 213.0445; Anal. Calcd for C9H11NO3S: C, 50.69; H, 5.20; N,
6.57; S, 15.04. Found: C, 50.60; H, 5.15; N, 6.64; S, 15.20.
Cyclopentyl sulfamate (5b).19 The sulfamate ester (5b) was prepared according to the general procedure,
using cyclopentanol (861.4 mg, 10 mmol) and sulfamoyl chloride (4.50 g, 30 mmol). The crude product
(1.9 g) was purified by column chromatography (3:1 hexane/EtOAc) followed by recrystallization from
i
1:1 PrOH/hexane to afford 5b (1.51 g, 67%) as colorless plates; Rf = 0.60 (1:1 hexane/EtOAc); mp
181.5-182.5 °C (dec.) (lit.,19 mp 58-60 °C); IR (KBr) ν 3360, 3264, 1345, 1181, 1155 cm-1; 1H NMR (400
MHz, CDCl3) δ 1.60-1.68 (m, 2H, CH2), 1.77-1.81 (m, 2H, CH2), 1.84-1.94 (m, 2H, CH2), 1.99-2.03 (m,
13
2H, CH2), 4.68 (br-s, 2H, NH2), 5.10 (quintet, J = 2.8 Hz, 1H, CHOSO2NH2); C NMR (100 MHz,
CDCl3) δ 23.24 (CH2), 33.11 (CH2), 86.45 (CH); HRMS (EI) calcd for C5H12NO3S (MH+) 166.0538,
found 166.0534.
3-Phenylpropyl sulfamate (5c).3b According to the general procedure, 5c was prepared from
3-phenylpropanol (1 g, 7.3 mmol) and sulfamoyl chloride (1.64 g, 11 mmol). The crude product (1.5 g)
was purified by column chromatography (silica gel, 3:1 hexane/EtOAc) followed by recrystallization
from 3:1 ether/hexane to afford 5c (1.3 g, 82%) as colorless needles; Rf = 0.53 (1:1 hexane/EtOAc); mp
56.5-57.0 °C; IR (KBr) ν 3370, 3285, 1350, 1184 cm-1; 1H NMR (400 MHz, CDCl3) δ 2.02-2.19 (m, 2H,
CH2CH2CH2), 2.74 (t, J = 7.5 Hz, 2H, PhCH2), 4.20 (t, J = 6.4 Hz, 2H, OCH2), 4.92 (br-s, 2H, NH2),
13
7.17-7.31 (m, 5H, ArH); C NMR (100 MHz, CDCl3) δ 30.28 (CH2), 31.55 (CH2), 70.52 (CH2), 126.14
(CH), 128.37 (CH), 128.44 (CH), 140.32 (C); HRMS (EI) calcd for C9H13NO3S (M+) 215.0616, found
215.0609; Anal. Calcd for C9H13NO3S: C, 50.21; H, 6.09; N, 6.51; S, 14.90. Found: C, 50.15; H, 5.98; N,
6.47; S, 15.19.
1,2,3,4-Tetrahydronaphthalen-8-yl sulfamate (5d).3e According to the general procedure, 5d was
prepared from 1,2,3,4-tetrahydronaphthalen-8-ol (1.5 g, 10 mmol) and sulfamoyl chloride (2.25 g, 15
mmol). The crude product (3.0 g) was purified by column chromatography (silica gel, 5:1 hexane/EtOAc)
followed by recrystallization from benzene to afford 5d (2.2 g, 98%) as colorless needles; Rf = 0.50 (2:1
hexane/EtOAc); mp 87.5-88 °C; IR (KBr) ν 3387, 3279, 1346, 1175 cm-1; 1H NMR (400 MHz, CDCl3) δ
1.77-1.80 (m, 4H, C1-H, C4-H), 2.79-2.81 (m, 4H, C2-H, C3-H), 5.03 (br-s, 2H, NH2), 7.02 (d, J = 7.8

HETEROCYCLES, Vol. 69, 2006
533
13
Hz, 1H, ArH), 7.11 (dd, J = 7.8, 7.8 Hz, 1H, ArH), 7.18 (d, J = 7.8 Hz, 1H, ArH); C NMR (100 MHz,
CDCl3) δ 22.36 (CH2), 22.55 (CH2), 23.70 (CH2), 29.44 (CH2), 118.35 (CH), 125.95 (CH), 127.94 (CH),
130.56 (C), 139.98 (C), 148.45 (C); HRMS (EI) calcd for C10H13NO3S (M+) 227.0616, found 227.0612;
Anal. Calcd for C10H13NO3S: C, 52.85; H, 5.77; N, 6.16; S, 14.11. Found: C, 52.93; H, 5.66; N, 6.06; S,
14.16.
General procedure for the enantioselective intramolecular C–H amidation reaction (Table 1, Entry
4): (3aR,8aS)-3,3a,8,8a-tetrahydroindeno[1,2-d]-1,2,3-oxathiazole 2,2-dioxide (6a).3b,6a,9b To a
suspension of 5a (42.6 mg, 0.2 mmol), MgO (18.5 mg, 0.46 mmol, 2.3 equiv.) and
Rh2(S-TFPTTL)4·2EtOAc (6.8 mg, 0.004 mmol, 2 mol %) in benzene (5 mL) was added PhI(OAc)2 (70.9
mg, 0.22 mmol, 1.1 equiv.) in one portion at 23 °C. After stirring at this temperature for 1 h, the whole
mixture was filtered through a pad of Celite. The filter cake was rinsed with EtOAc and the combined
filtrates were evaporated under reduced pressure. The residue (113 mg) was purified by column
chromatography (silica gel, 5:1 hexane/EtOAc) to provide (3aR,8aS)-6a (40.9 mg, 98%) as a white solid;
Rf = 0.32 (2:1 hexane/EtOAc); mp 169-170 °C; [α]D22 +68.3° (c 1.03, THF) for 48% ee; IR (KBr) ν 3283,
1350, 1187 cm-1;1H NMR (400 MHz, acetone-d6) δ 3.29 (d, J = 18.1 Hz, 1H, C8-CH), 3.46 (dd, J = 6.2,
18.1 Hz, 1H, C8-CH), 5.44 (t, J = 6.2 Hz, 1H, C3a-CH), 5.61 (m, 1H, C8a-CH), 7.03 (br-d, J = 6.2 Hz,
13
1H, NH), 7.29-7.32 (m, 3H, ArH), 7.39-7.41 (m, 1H, ArH); C NMR (100 MHz, acetone-d6) δ 38.07
(CH2), 65.12 (CH), 86.95 (CH), 125.77 (CH), 126.29 (CH), 128.19 (CH), 129.90 (CH), 139.56 (C),
140.63 (C); HRMS (EI) calcd for C9H9NO3S (M+) 211.0303, found 211.0294. The enantiomeric excess of
6a was determined to be 48% by HPLC with a Chiralcel OD-H column (9:1 hexane/i-PrOH, 1.0
mL/min): tR (minor)= 26.5 min for (3aS,8aR)-enantiomer; tR (major) = 31.5 min for (3aR,8aS)-enantiomer.
The absolute configuration of 6a was determined to be 3aR, 8aS by chemical correlation (vide infra).
Determination of absolute configuration of 6a: (3aR,8aS)-3,3a,8,8a-tetrahydroindeno[1,2-d]-1,2,3-
oxathiazole 2,2-dioxide (6a) from (1R,2S)-1-aminoindan-2-ol. The cyclic sulfamidate (6a) was
prepared according to the procedure of Harwood.13 To a solution of (1R,2S)-1-amino-2-indanol (>99% ee,
purchased from Aldrich, 100 mg, 0.67 mmol) and Et3N (102 mg, 1.0 mmol) in CH2Cl2 (3 mL) was added
SO2Cl2 (136 mg, 1.0 mmol) at 0 °C. After stirring at this temperature for 1 h, the reaction mixture was
poured into cold water (10 mL), and the whole was extracted with EtOAc (3 × 10 mL). The combined
organic layers were washed with saturated NaHCO3 solution (10 mL), water (10 mL) and brine (2 × 10
mL), and dried over Na2SO4. Filtration and evaporation gave the crude product (118.7 mg), which was
purified by column chromatography (silica gel, 3:1 hexane/EtOAc) followed by recrystallizations from
i
1:1 PrOH/hexane to furnish (3aR,8aS)-6a (94.5 mg, 67%) as colorless needles; mp 187–188 °C (dec);

534
HETEROCYCLES, Vol. 69, 2006
[α]D24 +141.2° (c 0.82, THF) for >99% ee of (3aR,8aS)-6a; Anal. Calcd for C9H9NO3S: C, 51.17; H, 4.29;
N, 6.63; S, 15.18. Found: C, 51.15; H, 4.33; N, 6.53; S, 15.29. The enantiomeric excess was determined
to be >99% by HPLC.
Tetrahydro-3(3aH)-cyclopent-1,2,3-oxathiazole (6b). According to the general procedure for C–H
amidation, 6b was prepared from 5b (33.0 mg, 0.20 mmol), PhI(OAc)2 (70.9 mg, 0.22 mmol), MgO (18.5
mg, 0.46 mmol), and Rh2(S-TFPTTL)4·2EtOAc (6.8 mg, 0.004 mmol, 2 mol %). The crude product (76
mg) was purified by column chromatography (silica gel, 2:1 hexane/EtOAc) to provide 6b (9.7 mg, 30%)
24
as a colorless oil; Rf = 0.38 (2:1 hexane/EtOAc); [α]D +1.21° (c 0.58, CHCl3) for 27% ee; IR (neat) ν
1
3268, 1354, 1188 cm-1; H NMR (400 MHz, CDCl3) δ 1.75 (m, 1H), 1.83-2.05 (m, 4H), 2.17 (m, 1H),
4.28 (ddt J = 3.2, 9.6, 6.4 Hz, 1H, C3a-H), 4.40 (br-s, 1H, NH), 5.17 (dt, J = 1.9, 6.4 Hz, 1H, C6a-H); 13C
NMR (100 MHz, CDCl3) δ 22.58 (CH2), 32.70 (CH2), 33.15 (CH2), 59.77 (CH), 86.84 (CH); HRMS (EI)
calcd for C5H9NO3S (M+) 163.0303, found 163.0299. The enantiomeric excess of 6b was determined to
be 27% by HPLC after conversion to the corresponding benzyl carbamate (vide infla). The absolute
stereochemistry of 6b was not determined.
Benzyl tetrahydro-3(3aH)-cyclopent-1,2,3-oxathiazole-3-carboxylate. A solution of 6b (8.1 mg, 0.05
mmol) in THF (0.4 mL) was added to a solution of sodium tert-butoxide (10 mg, 0.1 mmol) in THF (0.6
mL) at 0 °C. After 0.5 h of stirring at this temperature, benzyl chloroformate (34 mg, 0.2 mmol) was
added to the mixture. After 5 min of stirring at the same temperature, the reaction was quenched by
crushed ice, and the whole mixture was extracted with EtOAc (20 mL). The organic layer was washed
with water (5 mL) and brine (2 × 5 mL), and dried over Na2SO4. Filtration and evaporation in vacuo
followed by column chromatography (silica gel, 20:1 toluene/EtOAc) provided benzyl
tetrahydro-3(3aH)-cyclopent-1,2,3-oxathiazole-3-carboxylate (10.3 mg, 70%) as a colorless oil; Rf = 0.60
(1:1 hexane/EtOAc); [α]D +6.51° (c 0.85, CHCl3); IR (neat) ν 1740, 1380, 1335,1305,1196 cm-1; 1H
23
NMR (400 MHz, CDCl3) δ 1.83-1.90 (m, 2H), 1.96-2.06 (m, 3H), 2.21 (m, 1H), 4.60 (dt J = 2.7, 5.4 Hz,
1H, C6a-H), 5.21 (t, J = 5.4 Hz, 1H, C3a-H), 5.30 (d, J = 12.4 Hz, 1H, PhCH), 5.34 (d, J = 12.4 Hz,
PhCH), 7.32-7.41 (m, 5H, ArH); 13C NMR (100 MHz, CDCl3) δ 22.69 (CH2), 32.31 (CH2), 32.63 (CH2),
61.52 (CH), 69.26 (CH2), 84.13 (CH), 127.83 (CH), 128.51 (CH), 128.59 (CH), 134.40 (C), 150.05
(C=O); HRMS (EI) calcd for C13H15NO5S (M+) 297.0671, found 297.0681. The enantiomeric excess was
determined to be 27% by HPLC [Daicel Chiralpak AD column (9:1 hexane/i-PrOH, 1.0 mL/min): tR
(major)= 17.9 min; tR (minor) = 21.0 min].

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Tetrahydro-4-phenyl-1,2,3-oxathiazine 2,2-dioxide (6c).3b According to the general procedure for C–H
amidation, 6c was prepared from 5c (43.1 mg, 0.20 mmol), PhI(OAc)2 (70.9 mg, 0.22 mmol), MgO (18.5
mg, 0.46 mmol), and Rh2(S-PTTL)4·2EtOAc (5.69 mg, 0.004 mmol, 2 mol %). The crude product (70 mg)
was purified by column chromatography (silica gel, 6:1 hexane/EtOAc) to provide 6c (28.4 mg, 67%) as a
white solid; Rf = 0.44 (2:1 hexane/EtOAc); mp 120–120.5 °C; [α]D23 +1.09° (c 0.99, THF) for 21% ee; IR
1
(KBr) ν 3212, 1355, 1180 cm-1; H NMR (400 MHz, CDCl3) δ 2.00 (dq J = 14.7, 1.8 Hz, 1H, C5eq-H),
2.25 (ddt, J = 4.9, 14.7, 12.8 Hz, 1H, C5ax-H), 4.50 (br-d, J = 9.1 Hz, 1H, NH), 4.64 (ddd, J = 1.8, 4.9,
11.8 Hz, 1H, C6eq-H), 4.81-4.88 (m, 2H, C4-H and C6ax-H), 7.33-7.41 (m, 5H, ArH); 13C NMR (100 MHz,
CDCl3) δ 30.13 (CH2), 58.94 (CH), 71.91 (CH2), 126.17 (CH), 128.76 (CH), 129.02 (CH), 137.84 (C);
HRMS (EI) calcd for C9H11NO3S (M+) 213.0459, found 213.0462. The enantiomeric excess of 6c was
determined to be 21% by HPLC with a Chiralcel OD column (3:1 hexane/i-PrOH, 0.5 mL/min): tR
(major)= 26.4 min; tR (minor) = 30.1 min. The absolute stereochemistry of 6c was not determined.
3a,4,5,6-Tetrahydro-3H-naphth[1,8-de]-1,2,3-oxathiazine 2,2-dioxide (6d).3e According to the general
procedure for C–H amidation, 6d was prepared from 5d (45.5 mg, 0.20 mmol), PhI(OAc)2 (70.9 mg, 0.22
mmol), MgO (18.5 mg, 0.46 mmol), and Rh2(S-TFPTTL)4·2EtOAc (6.8 mg, 0.004 mmol, 2 mol %). The
crude product (102 mg) was purified by column chromatography (silica gel, 3:1 hexane/EtOAc) to
provide 6d (22.2 mg, 49%) as an orange solid, along with recovered 5d (17.6 mg, 39%). 6d: Rf = 0.47
24
(2:1 hexane/EtOAc); mp 123-124 °C; [α]D +5.28° (c 0.90, MeOH) for 14% ee; IR (KBr) ν 3259, 1370,
1
1174 cm-1; H NMR (400 MHz, CDCl3) δ 1.62 (dq, J = 3.6, 12.4 Hz, 1H, C4-H), 1.87 (m, 1H, C5-H),
2.11 (m, 1H, C5-H), 2.34 (m, 1H, C4-H), 2.82 (ddd, J = 6.2, 11.3, 17.5 Hz, 1H, C6-H), 2.91 (ddd, J = 2.4,
7.0, 17.5 Hz, 1H, C6-H), 4.52 (br-s, 1H, NH), 4.71 (dt, J = 5.1, 11.5, 1H, C3a-H), 6.78 (d, J = 7.9 Hz, 1H,
ArH), 6.95 (d, J = 7.9 Hz, 1H, ArH), 7.20 (t, J = 7.9 Hz, 1H, ArH); 13C NMR (100 MHz, CDCl3) δ 21.29
(CH2), 27.97 (CH2), 28.06 (CH2), 53.39 (CH), 114.86 (CH), 119.87 (C), 125.04 (CH), 128.97 (CH),
137.51 (C), 151.80 (C); HRMS (EI) calcd for C10H11NO3S (M+) 225.0460, found 225.0461. The
enantiomeric excess of 6d was determined to be 14% by HPLC with a Chiralpak IA column (3:1
hexane/i-PrOH, 1.0 mL/min): tR (major)= 17.2 min; tR (minor) = 19.0 min. The absolute stereochemistry
of 6d was not determined.
ACKNOWLEDGEMENTS
This research was supported, in part, by a Grant-in-Aid for Scientific Research on Priority Areas
"Advanced Molecular Transformations of Carbon Resources" from the Ministry of Education, Culture,
Sports, Science and Technology, Japan. We thank S. Oka, M. Kiuchi, A. Maeda, H. Matsumoto and T.

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HETEROCYCLES, Vol. 69, 2006
Hirose of the Center for Instrumental Analysis at Hokkaido University for mass measurements and
elemental analysis.
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