Intramolecular asymmetric amidations of sulfonamides and sulfamates catalyzed by chiral dirhodium(II) complexes

Article abstract of DOI:10.1002/hlca.200490148

Enantioselective intramolecular amidation of aliphatic sulfonamides was achieved for the first time by means of chiral carboxylatodirhodium(II) catalysts in conjunction with PhI(OAc)₂ and MgO in high yields and with enantioselectivities of up to 66% (Scheme 3, Table 1). The best results were obtained with [Rh₂{(S)-nttI)₄] and [Rh ₂{(R)-ntv)₄] as catalysts ((S)-nttl = (αS)-α- (tert-butyl)-1,3-dioxo-2H-benz[de]isoquinoline-2-acetato, (R)-nto = (αR)-α-isopropyl-1,3-dioxo-2H-benz[de] isoquinoline-2-acetato). In addition, these carboxylatodirhodium(II) catalysts were also efficient in intramolecular amidations of aliphatic sulfamates esters, although the enantioselectivity of these latter reactions was significantly lower (Scheme 4, Table 3).

Full text of DOI:10.1002/hlca.200490148

Helvetica Chimica Acta Vol. 87 (2004)
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Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates
Catalyzed by Chiral Dirhodium(II) Complexes
by Corinne Fruit* and Paul M¸ller
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211 Geneva 4
Dedicated to Dr. G¸nther Ohloff on the occasion of his 80th birthday
Enantioselective intramolecular amidation of aliphatic sulfonamides was achieved for the first time by
means of chiral carboxylatodirhodium(II) catalysts in conjunction with PhI(OAc)2 and MgO in high yields and
with enantioselectivities of up to 66% (Scheme 3, Table 1). The best results were obtained with [Rh2{(S)-nttl)4]
and [Rh2{(R)-ntv)4] as catalysts ((S)-nttl ˆ (aS)-a-(tert-butyl)-1,3-dioxo-2H-benz[de]isoquinoline-2-acetato,
(R)-nto ˆ (aR)-a-isopropyl-1,3-dioxo-2H-benz[de] isoquinoline-2-acetato). In addition, these carboxylatodi-
rhodium(II) catalysts were also efficient in intramolecular amidations of aliphatic sulfamates esters, although
the enantioselectivity of these latter reactions was significantly lower (Scheme 4, Table 3).
Introduction. Amidation of saturated CÀH bonds and aziridination of olefins
catalyzed by metal complexes based on Fe, Mn, Ru, Cu, or Rh are established
methodologies for CÀN bond-formation [1] and, consequently, for the synthesis of
amine derivatives. Some years ago, the RhII-catalyzed aziridination [2] and sulfona-
midation [3] with phenyliodinanes derived from aromatic sulfonamides has been
investigated in our group. The reactions exhibited features analogous to the
corresponding metal-catalyzed carbene-transfer reactions [4]. The aziridination was
found to be stereospecific, except in the case of stilbene, and the amidation proceeded
with retention of configuration at the reacting C-atom, indicating intervention of a
metal-complexed nitrene, in analogy to the corresponding intermediate metallocar-
benes resulting from decomposition of diazo compounds with RhII catalysts. Some
preliminary experiments showed that the system was suitable for asymmetric nitrene
transfer. However, it suffered several shortcomings. Owing to the requirement of
aromatic sulfonamides as precursors for the phenyliodinanes [5], the possibilities of
carrying out intramolecular aziridinations and/or amidations [6] appeared very limited.
In addition, a large excess of substrate was necessary in the case of intermolecular
reactions to achieve satisfactory yields, while reactions carried out with an excess of
reagent over the substrate produced unsatisfactory results. Finally, some reactions, in
particular intermolecular amidations, proceeded very sluggishly and resulted in
decomposition of the phenyliodinanes to afford sulfonamides without generation of
the expected products of nitrene insertion.
The transition-metal-catalyzed nitrene transfer has been further developed by other
groups. Dodd, Dauban, and co-workers reported that, contrary to the traditional
opinion [7], phenyliodinanes derived from aliphatic sulfonamides are isolable and may
be used for nitrene-transfer reactions [8]. In addition, they found conditions allowing

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Helvetica Chimica Acta Vol. 87 (2004)
generation of phenyliodinanes from sulfamates and PhIˆO, followed by Cu-catalyzed
decomposition in situ to afford aziridines. At the same time, an analogous system for in
situ generation of phenyliodinanes with PhI(OAc)2 from sulfamates and carbamates,
and their subsequent RhII-catalyzed nitrene transfer was designed by Du Bois and co-
workers [9]. RhII-Catalyzed intramolecular asymmetric aziridinations with ee values of
up to 76% have been reported [10]; however, so far, the highest inductions in catalytic
intramolecular amidations have been achieved with porphyrinatoruthenium complexes
[11]. In view of these recent developments, we carried out a series of RhII-catalyzed
intramolecular amidations with in situ generated phenyliodinanes derived from
sulfonamides and sulfamates (Scheme 1).
Scheme 1
Results and Discussion. Synthesis of Sulfonamides and Sulfamates. The aliphatic
sulfonamides 1a d (R(CH2)4SO2NH2) were prepared according to the literature from
the corresponding bromo derivatives in a three-step procedure with overall yields of
44 63% [12]. Aromatic sulfonamides, in turn, were obtained in a three-step procedure
starting from commercially available benzenesulfonyl chloride. Ethyl and benzyl
groups were introduced in ortho position via metallation-alkylation [13] and Negishi
cross-coupling [14], respectively, starting from N-(tert-butyl)benzenesulfonamide (2)
[15] ( ! 3a and 3b, resp.; Scheme 2). Subsequent acid cleavage with CF3COOH
afforded sulfonamides 4a and 4b [12]. The synthesis of the aliphatic sulfamates 5a c
was achieved starting from the corresponding alcohols and in situ generated sulfamoyl
chloride [16] with good yields (Scheme 2).
Intramolecular Amidations with Sulfonamides. The amidations with 1 were carried
out under in situ conditions with PhI(OAc)2 in the presence of MgO with 2 5% of
catalyst (see Fig.), generally at 408, and afforded cyclization products in quite variable
yield (Scheme 3, Table 1). Formation of six-membered sultams (see 6) was preferred
over the five-membered ones (see 7). This trend is opposite to the one found in
carbenoid insertion where cyclopentanones or g-lactones usually are formed prefer-
entially over cyclohexanones or d-lactones, respectively. No insertion products could be
isolated upon decomposition of butanesulfonamide (1a). In this case, formation of the
five-membered sultam 7a is disfavored; however, the six-membered isomer 6a is not
formed either, presumably owing to the low tendency of the Me group to undergo
nitrene insertion [3b]. No five-membered sultam 7d was observed in any reaction of 1d,
where the presence of the CˆC bond activates the allylic position and contributes
further to the selective formation of the six-membered-ring compound 6d. As
previously reported [3b], the carboxamidatodirhodium(II) catalysts were insufficiently
effective and gave only poor yields of insertion products. Among the carboxylatodi-

Helvetica Chimica Acta Vol. 87 (2004)
1609
Scheme 2
TFA ˆ CF3COOH, NMP ˆ 1-methylpyrrolidin-2-one
Scheme 3
rhodium(II)-catalysts, [Rh2{(S)-nttl}4] ((S)-nttl ˆ (aS)-a-(tert-butyl)-1,3-dioxo-2H-
benz[de]isoquinoline-2-acetato; see Fig.) was most selective and gave 57% ee at 408
and 66% ee at À 208, respectively, followed by [Rh2{(R)-ntv}4] ((R)-ntv ˆ (aR)-a-
isopropyl-1,3-dioxo-2H-benz[de]isoquinoline-2-acetato; see Fig.). The selectivity of
the other catalysts was disappointing, however.
The enantioselectivity of the aromatic sulfonamides 4a,b was investigated with the
same catalysts. These reactions proceeded with respectable yields to five-membered
sultams 8a,b. However the enantioselectivity never exeeded 20% (Table 2).

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Helvetica Chimica Acta Vol. 87 (2004)
Figure. RhII Catalysts used in the intramolecular amidation
Table 1. Intramolecular Amidation of Aliphatic Sulfonamides 1a d (R(CH2)4SO2NH2)a)
b
c
6/7d)
ee [%]
*
R(CH2)4SO2NH2
)
[Rh2L4 ] )
mol-%
T [8]
t [h]
Yield [%]
1a
1b
1c
1d
1b
1d
1b
1b
1c
1d
1b
1c
1b
1d
1d
1d
1d
1d
1b
1d
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2(OAc)4]
2.0
5.0
5.0
2.0
3.5
5.0
3.5
3.5
3.5
2.0
2.0
3.5
2.5
5.0
5.0
2.0
2.5
5.0
2.0
4.0
40
40
40
40
40
4.5
4
2
3
4
4
4
6.5
2
3
3
2
4
3
48
51
72
4
32
24
0
70
77
51
100
31
83
94
98
23
90
90
6
93 : 7
77: 23
99 : 1
95 : 5
99 : 1
98 : 2
99 : 1
98 : 2
99 : 1
97: 3
97: 3
n.d.e)
99 : 1
99 : 1
99 : 1
92 : 8
99.1
[Rh2{(S)-ptpa}4]
[Rh2{(S)-ptpa}4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-nttl}4]
[Rh2{(R)-ntv}4]
[Rh2{(R)-ntv}4]
[Rh2{(5S)-mepy}4]
[Rh2{(5S)-mepy}4]
[Rh2{(5S)-mepy}4]
[Rh2{(4S)-meox}4]
[Rh2{(S)-bsp}4]
[Rh2{(S)-bsp}4]
[Rh2{(S)-bnp}4]
[Rh2{(S)-bnp}4]
15
10
57
66
13
8
À 20
40
À 20
40
40
40
40
54
22
n.d.e)
8
40
40
23
6
22
54
50
À 20
n.d.e)
6
6
40
40
À 20
7
40
20
a) Conditions: all reactions were performed in CH2Cl2 at 408 or À 208 with a 1/PhI(OAc)2/MgO molar ratio of
1 : 1.5 : 2.5. b) a, R ˆ H; b, R ˆ Me; c, R ˆ Et; d, R ˆ CH2ˆCH. c) For the catalysts, see Figure. d) Ratio
determined by GC. e) n.d. ˆ not determined.

Helvetica Chimica Acta Vol. 87 (2004)
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Table 2. Intramolecular Amidation of Aromatic Sulfonamides 4a,ba)
b
*
[Rh2L4 ] )
mol-%
t [h]
Yield [%]
ee [%]
4a
4b
4a
4b
4a
4b
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-ptpa}4]
[Rh2{(R)-ntv}4]
5
5
3.5
3.5
3.5
3.5
2.5
2.5
2.5
2.5
2.5
5.5
65
45
31
44
)
33
20
n.d.c)
d
n.d.c)
a) Conditions: all reactions were performed at 408 in CH2Cl2 for 2.5 or 5.5 h with a 4/PhI(OAc)2/MgO molar
ratio of 1 : 1.5 : 2.5. b) For the catalysts, see Figure. c) n.d. ˆ not determined. d) Degradation of 4a.
Intramolecular Amidation with Sulfamate Esters. The decomposition of phenyl-
iodonium ylides derived from sulfamates in the presence of dirhodium catalysts results
in cyclic sulfamidates that are versatile reagents for organic synthesis [17]. This
class of compounds is of interest for the synthesis of various products possessing
heteroatomic functional groups. For example, they are useful precursors for the
preparation of amino acid derivatives [18], amino alcohols [19], piperazines or
thiomorpholines [20], oligosaccharides [21], glycopeptides [22], or indolizidine
derivatives [23].
Following the pioneering work of Du Bois and co-workers, we explored the in situ
generation and chiral RhII-catalyzed decomposition of phenyliodonium ylides derived
from aliphatic sulfamate esters 5a c (Scheme 4, Table 3). The reaction conditions were
optimized with [Rh2(OAc)4], and PhI(OAc) in conjunction with MgO was superior to
PhIˆO for the generation of the phenyliodinane. CH2Cl2 was the most suitable solvent
for this reaction. Screening of chiral RhII catalysts showed that [Rh2{(S)-nttl}4] [24] and
[Rh2{(R)-ntv}4] [25] gave the highest ee values, although the enantioselectivity was
significantly below that obtained in the intramolecular amidation of sulfonamides. This
contrasts with the intramolecular amidation of aromatic sulfamates, where ee values of
up to 52% have been reported with these catalysts [26].
Scheme 4

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Helvetica Chimica Acta Vol. 87 (2004)
Table 3. Intramolecular Amidation of Sulfamates 5a ca)
b
*
[Rh2L4 ] )
mol-%
Solvent
T [8]
t [h]
Yield [%]
ee [%]
5a
5b
5b
5b
5b
5c
5c
5a
5b
5c
5a
5a
5b
5c
5a
5b
5c
5a
5b
5c
5a
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2(OAc)4]
[Rh2{(S)-ptpa}4]
[Rh2{(S)-ptpa}4]
[Rh2{(S)-ptpa}4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-nttl}4]
[Rh2{(S)-nttl}4]
[Rh2{(R)-ntv}4]
[Rh2{(R)-ntv}4]
[Rh2{(R)-ntv}4]
[Rh2{(4S)meox}4]
[Rh2{(4S)-meox}4]
[Rh2{(4S)-meox}4]
[Rh2{(S)-bsp}4]
5
5
5
CH2Cl2
CH2Cl2
MeCN
CH2Cl2
MeCN
CH2Cl2
PhMe
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
40
40
40
40
40
40
80
40
40
40
40
À 20
40
40
40
40
40
40
40
40
40
10
10
24
10
32
3.5
3.5
6
10
3.5
4
10
10
3.5
4
87
67
31
29
20
55
43
97
82
71
97
97
60
62
80
91
52
42
16
34
42
5c)
5c)
5
5
2.5
3.5
3.5
3.5
3.5
3.5
3.5
2.0
3.5
3.5
2.0
2.0
3.5
2.0
9
< 5
18
19
21
< 5
22
17
< 5
30
< 5
< 5
< 5
< 5
10
3.5
29
22
3.5
17
a) Standard conditions: see Exper. Part. b) For the catalysts, see Figure. c) Iodosylbenzene was used instead of
PhI(OAc)2.
Conclusions. In summary, we reported the first enantioselective intramolecular
amidation reactions by using aliphatic sulfonamides and chiral dirhodium catalysts. We
demonstrated that [Rh2{(S)-nttl}4], developed in our group, is the most effective
catalyst for enantioselective amidation of CÀH bonds (ee up to 66%). Intramolecular
nitrene insertion into CÀH bonds was also achieved by using aliphatic sulfamate esters
and chiral dirhodium complexes. These amidations proceed with up to 30% ee in the
presence of [Rh2{(R)-ntv}4].
This work was supported by the Swiss National Science Foundation (Projects No. 20-52581.97 and 2027-
048156) and by the European Commission for Science, Research and Development (COST Action D12). The
authors are indebted to A. Pinto and J.-P. Saulnier for the NMR spectra and D. Klink for the mass spectra.
Experimental Part
1. General. All reactions were carried out under Ar. CH2Cl2, MeCN, and toluene were dried (CaH2) and
distilled. The other solvents were purchased from Fluka or Acros and used without purification. Flash
chromatography (FC): silica gel 32-63 60 ä (Merck 9385). CC ˆ column chromatography. TLC: Macherey-
Nagel Polygram Sil/UV254; detection by UV light or with KMnO4. The enantiomeric excess (ee) of the products
was determined by GC (b-Dex column) or by HPLC (Chiracel OD H); retention times tR in min. IR Spectra:
Mattson-Instruments Polaris FT-IR instrument; NaCl cells; in cmÀ1. NMR Spectra: Bruker AV-300, Bruker
DRX-500; chemical shifts d in ppm with respect to SiMe4 (ˆ0 ppm), coupling constants J in Hz. MS: Varian-
CH4 or -SM1 spectrometer with electron impact or electrospray; in m/z (rel. %). High-resolution (HR) MS:
anal. VG-7070 spectrometer (data system 11 250, resolution 7000).
2. Aliphatic Sulfonamides: General Procedure. A soln. of bromoalkane or bromoalkene and sodium sulfite
(1.2 equiv.) in H2O (5 ml) was refluxed overnight. After cooling to r.t., the aq. soln. was washed with Et2O and

Helvetica Chimica Acta Vol. 87 (2004)
1613
evaporated. The resulting white solid was dried under vacuum at 1308 and then treated with POCl3 (10 equiv.)
for 4 h at 1308. After evaporation, the residue was taken up in MeCN, and a soln. of aq. ammonia in MeCN was
slowly added at 08. The mixture was stirred at 08 for 1 h, then diluted with CH2Cl2, and washed with H2O. The
org. phase was dried (Na2SO4) and evaporated: white solid.
Butane-1-sulfonamide (1a): Yield 44%. M.p. 578.
Pentane-1-sulfonamide (1b): Yield 63%. M.p. 768.
Hexane-1-sulfonamide (1c): Yield 55%. M.p. 1148.
Hex-5-ene-1-sulfonamide (1d) [12]: Yield 50%. M.p. 528.
2-Benzyl-N-(tert-butyl)benzenesulfonamide (3a). A mixture of N-(tert-butyl)benzenesulfonamide (2) [15]
(1.066 g, 5 mmol) and THF (10 ml) was purged with Ar and cooled at À 788. Then 1.6m BuLi in hexane (6.6 ml,
10.5 mmol) was added dropwise. The mixture was stirred for 30 min at 08 and then cooled to À 788. ZnCl2
(1.70 g, 12.5 mmol) in THF (5 ml) was added, and the mixture was stirred for another 15 min and allowed to
reach 08. Then benzyl bromide (0.71 ml, 6 mmol) and [Pd(PPh3)4] (0.310 g, 5 mol-%) were added. The mixture
was warmed to 508, stirred for 21 h, then poured into 2n HCl (20 ml), and extracted with CH2Cl2. The org. phase
was dried (MgSO4) and evaporated and the residue purified by FC (silica gel, pentane/AcOEt 5 :1): 3a (1.02 g,
67%). White solid. TLC: Rf 0.58. M.p. 1268. IR (neat): 3288, 2973, 1494, 1474, 1419, 1390, 1305, 1145, 1122, 1065,
997, 765. 1H-NMR (CDCl3, 300 MHz): 1.06 (s, Me3C); 4.34 (br., NH); 4.51 (s, CH2); 7.25 (m, 4 CH); 7.37
(m, 3 CH); 7.49 (m, 1 CH); 8.12 (d, J ˆ 7.9, 1 CH). 13C-NMR (CDCl3, 75 MHz): 29.9 (Me3C); 38.4 (CH2); 54.7
(C); 126.7 (CH); 128.9 (CH); 129.2 (CH); 129.5 (CH); 132.3 (CH); 132.7 (CH); 138.9 (C); 139.7 (C); 141.4 (C).
‡
HR-MS: 303.12924 (C17H21NO2S ; calc. 303.12930).
N-(tert-Butyl)-2-ethylbenzenesulfonamide (3b). A soln. of 2 [15] (2.133 g, 10 mmol) in THF (25 ml),
precooled to 08 under Ar, was treated dropwise with 1.6m BuLi in hexane (13 ml, 20.1 mmol). The resulting
bright yellow soln. was stirred at 08 for 30 min, prior to quenching with iodoethane (0.96 ml, 12 mmol) in THF
(5 ml). After stirring for 1 h, the mixture (white suspension) was quenched with sat. NH4Cl soln. (50 ml), and
the mixture was extracted with CH2Cl2 (3 Â 50 ml). The org. phase was dried (MgSO4) and evaporated and the
residue purified by FC (silica gel, pentane/AcOEt 7 :1): 3b (2.28 g, 73%). White solid. TLC: Rf 0.50. IR (neat):
3277, 2981, 1446, 1426, 1392, 1309, 1142, 1097, 1009, 995, 865, 754. 1H-NMR (CDCl3, 300 MHz): 1.24 (s, Me3C);
1.34 (t, J ˆ 7.4, MeCH2); 3.10 (q, J ˆ 7.4, MeCH2); 5.21 (br., NH); 7.29 (m, 1 CH); 7.38 (d, J ˆ 7.4, 1 CH); 7.49
(m, 1 CH); 8.04 (d, J ˆ 8.1, 1 CH). 13C-NMR (CDCl3, 75 MHz): 15.0 (Me); 25.5 (CH2); 30.1 (Me3C); 54.9 (C);
125.8 (CH); 129.1 (CH); 130.3 (CH); 132.4 (CH); 140.8 (C); 142.9 (C).
2-Benzylbenzenesulfonamide (4a). A soln. of 3a (0.910 g, 3.0 mmol) in anisole (ˆ methoxybenzene; 9.7 ml,
3 equiv.) and neat CF3COOH (33 ml) was stirred for 24 h at 08. After dilution with AcOEt (40 ml), the soln. was
neutralized at 08 with aq. Na2CO3 soln. The org. phase was dried (Na2SO4) and evaporated: 4a (0.679 g, 91%).
White solid. M.p. 1428. IR (neat): 3327, 1662, 1453, 1300, 1221, 1132, 910. 1H-NMR ((D6)DMSO, 300 MHz): 4.38
(s, CH2); 7.09 (d, J ˆ 7.0, 1 CH ) ; 7.20 7.45 ( m, 7 H); 7.52 (br., NH2); 7.90 (d, J ˆ 7.9, 1 H ) . 13C-NMR
((D6)DMSO, 75 MHz): 37.6 (CH2); 126.6 (CH); 126.7 (CH); 127.6 (CH); 128.8 (CH); 129.8 (CH); 132.0
‡
(CH); 132.2 (CH); 139.6 (C); 140.7 (C); 142.5 (C). HR-MS: 230.03985 (C13H11O2S ; calc. 230.04015).
2-Ethylbenzenesulfonamide (4b). As described for 4a, with 3b (0.600 g, 2.48 mmol), anisole (8 ml,
3 equiv.), CF3COOH (27 ml), and AcOEt (30 ml): 4b (0.450 g, 98%). Creamy solid. M.p. 1248. IR (neat): 3342,
3240, 1309, 1295, 1137. 1H-NMR ((D6)DMSO, 300 MHz): 1.21 (t, J ˆ 7.4, MeCH2); 2.99 (q, J ˆ 7.4, MeCH2);
7.31 7.39 (m, 2 CH); 7.41 (br., NH2); 7.49 (m, 1 CH); 7.83 (d, J ˆ 6.8, 1 CH). 13C-NMR ((D6)DMSO, 75 MHz):
15.9 (Me); 25.7 (CH2); 126.3 (CH); 127.5 (CH); 131.0 (CH); 132.4 (CH); 142.4 (C); 142.9 (C). HR-MS
‡
185.05029 (C8H11NO2S ; calc. 185.05105).
3. Sulfamates: General Procedure. To chlorosulfonyl isocyanate (ˆsulfuryl chloride isocyanate; 3.5 ml,
40 mmol, 2.0 equiv.) at 08 under Ar, anh. formic acid (1.5 ml, 40 mmol, 2.0 equiv.) was added dropwise with
rapid stirring. The mixture was stirred at r.t. until gas evolution ceased (from 1 to 4 h). To the resulting sulfamoyl
chloride, a soln. of alcohol (20 mmol) in 1-methylpyrrolidin-2-one (30 ml) was added dropwise with ice-cooling
over 30 60 min. The mixture was stirred at r.t. for 3 h (yellow-orange soln.) and was then poured into cold brine
(100 ml) and washed twice with AcOEt (150 ml). The combined org. extract was dried (MgSO4) and
evaporated. Purification of the residue by FC (silica gel, pentane/AcOEt) afforded the desired sulfamate ester.
Butyl Sulfamate (5a): From butan-1-ol (1.8 ml), after FC (pentane/AcOEt 3 :2): colorless oil (2.87 g, 94%).
1
TLC: Rf 0.63. IR (neat): 3374, 3282, 2963, 1558, 1467, 1351, 1172, 920, 792. H-NMR (CDCl3, 300 MHz): 0.93
(t, J ˆ 7.4, Me); 1.42 (m, 1 CH2); 1.71 (m, 1 CH2); 4.19 (t, J ˆ 6.6, 1 CH2); 5.36 (br., NH2). 13C-NMR (CDCl3,
‡
75 MHz): 13.4 (Me); 18.6 (CH2); 30.6 (CH2); 71.3 (CH2O). HR-MS: 125.01121 (C2H7NO3S ; calc. 125.01185).
Pentyl Sulfamate (5b): From pentan-1-ol (2.2 ml), after FC (pentane/AcOEt 3 :2): white solid (3.13 g,
94%). M.p. 598. TLC: Rf 0.63. IR (neat): 3385, 3277, 2959, 2927, 2868, 1770, 1556, 1467, 1354, 1178, 965. 1H-NMR

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Helvetica Chimica Acta Vol. 87 (2004)
(CDCl3, 300 MHz): 0.93 (t, J ˆ 7.0, Me); 1.39 (m, 2 CH2); 1.76 (m, 1 CH2); 4.21 (t, J ˆ 6.6, 1 CH2); 5.22
(br., NH2). 13C-NMR (CDCl3, 75 MHz): 13.9 (Me); 22.1 (CH2); 27.5 (CH2); 28.4 (CH2); 71.6 (CH2O). HR-MS:
‡
138.02367 (C3H8NO3S ; calc138.02249).
Indan-2-yl Sulfamate (ˆ1,3-Dihydro-2H-inden-2-yl Sulfamate; 5c) [9a][11]: From indan-2-ol (2.68 g), after
FC (pentane/AcOEt 1:1): white solid (2.52 g, 59%). M.p. 898. TLC: Rf 0.56. IR (neat): 3347, 2938, 1750, 1731,
1349, 1207, 892. 1H-NMR (CDCl3, 300 MHz): 3.35 (m, 2 CH2); 4.95 (br., NH2); 5.46 (m, 1 CH); 7.22 7.30
(m, 4 H). 13C-NMR (CDCl3, 75 MHz): 39.8 (CH2); 83.6 (CH); 124.7 (CH); 127.2 (CH); 139.3 (C).
4. Cyclic Sulfonamides or Oxathiazinanes by Dirhodium(II) Complex Catalysis: General Procedure.
CH2Cl2 (3 5 ml) was added by syringe to the sulfonamide or sulfamate (0.3 0.5 mmol), PhI(OAc)2
(1.5 equiv.), MgO (2.5 equiv.), activated 4-ä molecular sieves, and the rhodium catalyst (0.5 5 mol-%) under
Ar at r.t. The resulting suspension was stirred vigorously under reflux until complete consumption of starting
material was indicated by TLC. The mixture was diluted with CH2Cl2 (5 ml) and filtered through a pad of Celite.
The filter cake was washed with CH2Cl2, the filtrate evaporated, and the residue purified by CC (silica gel,
pentane/AcOEt): cyclic sulfonamide, or oxathiazinane or oxathiazole product.
3-Methyl-1,2-thiazinane 1,1-Dioxide (ˆ Tetrahydro-3-methyl-2H-1,2-thiazine 1,1-Dioxide; 6b): From 1b
(0.076 g, 0.50 mmol) and [Rh2(OAc)4] (5 mol-%), after FC (pentane/AcOEt 1 :1): white solid (0.052 g, 70%).
M.p. 1138. TLC (KMnO4): Rf 0.30. GC (b-Dex-120, 1458, 2 min, then 0.258/min): tR 18.9, 19.9. IR (neat): 3271,
2930, 1726, 1287, 1132. 1H-NMR (CDCl3, 500 MHz): 1.21 (d, J ˆ 8.4, Me); 1.29 (m, 1 CH); 1.76 (m, 1 CH); 2.18
(m, 1 CH2); 2.86 (m, 1 CH); 3.16 (m, 1 CH); 3.56 (m, 1 CH); 4.31 (br., NH). 13C-NMR (CDCl3, 125 MHz): 21.4
‡
(Me); 23.1 (CH2); 31.9 (CH2); 48.8 (CH2); 52.6 (CH). HR-MS: 149.05042 (C4H9NO2S ; calc. 149.05105).
3-Ethyl-1,2-thiazinane 1,1-Dioxide (ˆ 3-Ethyl-tetrahydro-2H-1,2-thiazine 1,1-Dioxide; 6c): From 1c
(0.082 g, 0.50 mmol) and [Rh2(OAc)4] (5 mol-%), after FC (pentane/AcOEt 1 :1): colorless oil (0.063 g,
77%). TLC (KMnO4) Rf 0.37. GC (b-Dex-120, 1358): tR 48.5, 50.6. IR (neat): 3213, 2961, 2929, 1739, 1706, 1667,
1587, 1378, 1339, 1239, 1130, 779. 1H-NMR (CDCl3, 500 MHz): 0.95 (t, J ˆ 7.5, Me); 1.51 (m, 1 CH2); 1.77
(m, 1 CH); 2.17 (m, 1 CH2); 2.87 (m, 1 CH); 3.16 (m, 1 CH2); 3.36 (m, 1 CH); 4.32 (d, J ˆ 9.2, NH). 13C-NMR
(CDCl3, 125 MHz): 10.1 (Me); 23.0 (CH2); 28.6 (CH2); 29.7 (CH2); 49.2 (CH2); 58.3 (CH). HR-MS: 163.06755
‡
(C6H13NO2S ; calc. 163.06670).
3-Ethenyl-1,2-thiazinane 1,1-Dioxide (ˆ 3-Ethenyl-tetrahydro-2H-thiazine 1,1-Dioxide; 6d) [12]: From 1d
(0.076 g, 0.50 mmol) and [Rh2(OAc)4] (5 mol-%), after FC (pentane/AcOEt 1 :1): white solid (0.052 g, 70%).
TLC (KMnO4): Rf 0.30. GC (Betadex-120, 1508, 10 min, then 5.08/min): tR 18.8, 19.7. 1H-NMR (CDCl3,
500 MHz): 1.42 (m, 1 H, CH2); 1.91 (qd, J ˆ 3.1, 14, 1 H, CH2); 2.22 2.30 (m, 1 CH2); 2.89 2.99 (m, 1 CH2);
3.22 (dt, J ˆ 3.6, 13.4, 1 CH2); 4.08 (m, 1 CH); 4.36 (d, J ˆ 8.4, NH); 5.21 (d, J ˆ 10, 1 H, CH2); 5.28 (d, J ˆ 18,
1 H, CH2); 5.82 (ddd, J ˆ 5, 10, 18, 1 CH). 13C-NMR (CDCl3, 125 MHz): 22.9 (CH2); 29.7 (CH2); 49.1 (CH2);
‡
57.9 (CH); 116.4 (CH2); 136.4 (CH). HR-MS: 161.05184 (C6H11NO2S ; calc. 161.05105).
2,3-Dihydro-3-methyl-1,2-benzisothiazole 1,1-Dioxide (8a): From 4a (0.092 g, 0.50 mmol) and [Rh2(OAc)4]
(5 mol-%), after FC (pentane/AcOEt 1:2): brown oil (0.059 g, 65%). TLC: Rf 0.30. GC (b-Dex-120, 1608,
2 min, then 0.258/min): tR 57.0, 59.3. IR (neat): 3247, 2979, 1736, 1373, 1278, 1155, 1128, 756. 1H-NMR (CDCl3,
300 MHz): 1.62 (d, J ˆ 6.8, Me); 4.81 (m, 1 CH); 5.16 (br., NH); 7.40 (d, J ˆ 7.7, 1 CH); 7.53 (m, 1 CH); 7.64
(m, 1 CH); 7.77 (d, J ˆ 7.7, 1 CH ) . 13C-NMR (CDCl3, 75 MHz): 21.4 (Me); 53.4 (CH); 121.1 (CH); 124.0 (CH);
‡
129.2 (CH); 133.2 (CH); 135.5 (C); 141.8 (C). HR-MS: 183.03358 (C8H9NO2S ; calc. 183.03540).
2,3-Dihydro-3-phenyl-1,2-benzisothiazole 1,1-Dioxide (8b): From 4b (0.076 g, 0.50 mmol) and [Rh2(OAc)4]
(5 mol-%), after FC (pentane/AcOEt 1:2): white solid (0.038 g, 45%). M.p. 1308. TLC: Rf 0.30. IR (neat): 3460,
3018, 2948, 1738, 1366, 1217. 1H-NMR (CDCl3, 500 MHz): 5.30 (br., NH); 5.73 (d, J ˆ 3.6, 1 CH); 7.15
(m, 1 CH); 7.39 (m, 2 CH); 7.58 (m, 2 CH); 7.70 7.78 (m, 4 H). 13C-NMR (CDCl3, 125 MHz): 61.4 (CH); 121.1
(CH); 123.1 (CH); 125.3 (CH); 126.6 (CH); 127.5 (CH); 130.4 (CH); 133.3 (C); 133.6 (C); 141.0 (C). HR-MS:
‡
245.05366 (C13H11NO2S ; calc. 245.05105).
4-Methyl-1,2,3-oxathiazinane 2,2-Dioxide (ˆ Tetrahydro-4-methyl-1,2,3-oxathiazine 1,1-Dioxide; 9a): From
5a (0.080 g, 0.52 mmol) and [Rh2(OAc)4] (5 mol-%), after FC (pentane/AcOEt 3.5 :1): orange oil (0.070 g,
87%). TLC (KMnO4): Rf 0.20. GC (b-Dex-120, 1308): tR 39.64, 41.47. IR (neat): 3234, 1419, 1341, 1304, 1169,
1134, 1078, 1011, 960, 933, 868, 777, 715. 1H-NMR (CDCl3, 300 MHz): 1.30 (d, J ˆ 6.6, Me); 1.75 (m, 1 CH2); 3.83
(m, CH); 4.27 (br., NH); 4.55 (m, 1 CH2); 4.73 (m, 1 CH2). 13C-NMR (CDCl3, 300 MHz): 20.9 (Me); 31.3
(CH2); 52.0 (CH); 72.1 (CH2O). EI-MS: 151 (10), 136 (62), 124 (100), 106 (9), 56 (19).
4-Ethyl-1,2,3-oxathiazinane 2,2-Dioxide (ˆ4-Ethyl-tetrahydro-1,2,3-oxathiazine 1,1-Dioxide; 9b): From 5b
(0.080 g, 0.52 mmol) and [Rh2(OAc)4] (5 mol-%), after FC (pentane/AcOEt 2 :1): colorless oil (0.055 g, 67%).
TLC (KMnO4): Rf 0.30. GC (b-Dex-120, 1358): tR 46.83, 47.99. IR (neat): 3262, 1419, 1349, 1179, 1014, 997, 861,
1
774. H-NMR (CDCl3, 300 MHz): 1.02 (t, J ˆ 7.5, Me); 1.61 (m, 1 CH2); 1.77 (m, 1 CH2); 3.65 (m, 1 CH); 4.20

Helvetica Chimica Acta Vol. 87 (2004)
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(br., NH); 4.57 (m, 1 H, CH2); 4.74 (m, 1 H, CH2). 13C-NMR (CDCl3, 75 MHz): 9.8 (Me); 28.3 (CH2); 29.6
‡
(CH2); 57.6 (CH); 72.1 (CH2O). HR-MS: 165.04506 (C5H11NO3S ; calc. 165.04597).
3,3a,8,8a-Tetrahydroindeno[1,2-d]-1,2,3-oxathiazole 2,2-Dioxide (9c) [9a][11]: From 5c (0.085 g,
0.40 mmol) and [Rh2(OAc)4] (5 mol-%), after FC (CH2Cl2): white solid (0.046 g, 55%). M.p. 1748. TLC: Rf
0.34. HPLC (OD-H, 238, hexane/iPrOH 90 :10, 0.5 ml/min): tR 52.3, 59.3. IR (neat): 3008, 2970, 1739, 1438, 1366,
1
1217. H-NMR (CDCl3, 300 MHz): 3.50 (m, 1 CH2); 4.64 (br., NH); 5.33 (t, 1 CH); 5.55 (m, 1 CH); 7.30 7.42
(m, 4 CH). 13C-NMR (CDCl3, 75 MHz): 37.6 (CH2); 64.4 (CH); 84.8 (CH); 125.4 (CH); 125.6 (CH); 128.4
‡
(CH); 130.3 (CH); 137.4(C); 139.6 (C). HR-MS: 211.03161 (C9H9NO3S ; calc. 211.03032).
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Received January 23, 2004