Copper-mediated cross-coupling reaction of N-protected sulfonimidamides and aryl halides

Article abstract of DOI:10.1055/s-2008-1032139

Copper-mediated cross-coupling reactions of N-protected sulfonimidamides with aryl iodides and aryl bromides provide N-protected N′-aryl sulfonimidamides in moderate to good yields. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1032139

PAPER
739
Copper-Mediated Cross-Coupling Reaction of N-Protected Sulfonimidamides
and Aryl Halides
N-Arylation of
S
h
rides istin Worch, Carsten Bolm*
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany
Fax +49(241)8092391; E-mail: Carsten.Bolm@oc.RWTH-Aachen.de
Received 21 November 2007
Table 1 Reaction Conditions Tested for the Copper-Mediated N-
Arylation of Sulfonimidamides 1a and 1b with Phenyl Iodide (2a)a
Abstract: Copper-mediated cross-coupling reactions of N-protect-
ed sulfonimidamides with aryl iodides and aryl bromides provide
N-protected N¢-aryl sulfonimidamides in moderate to good yields.
O
N
PG
I
copper salt,
base
S
Key words: N-arylation, aryl halides, copper, cross-coupling, sul-
fonimidamide
O
N
PG
4-Tol
NH
+
S
DMSO,
100 °C, 20 h
4-Tol
NH2
Sulfonimidamides are the aza-analogues of sulfonamides.
They are potent reagents in nitrene transfer chemistry1 as
exemplified by diastereoselective C–H aminations.2 Prep-
aration of various chiral sulfonimidoylguanidines have
recently been carried out by the reaction of sulfonimid-
amides with uronium reagents.3 Since both sulfonimid-
amides and guanidine moities occur in several
biologically active molecules, we became interested in the
preparation of compounds that contain both of these inter-
esting functional groups. From a more fundamental point
of view, we wanted to design new compounds, which con-
tained the sulfonimidamide moiety as a basic module to
be incorporated into chiral ligands for asymmetric cataly-
sis.
1a: PG = Ts
1b: PG = Bz
3aa: PG = Ts
3ba: PG = Bz
2a
Entry
Substrate
Copper salt
Base
Yield (%)b
1
2
3
4
5
1a
1a
1a
1b
1b
CuI
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
K2CO3
32
22
35
54
65
CuBr
CuCl
CuCl
CuCl
a Reaction conditions: sulfonimidamide (1.0 equiv), phenyl iodide
(2.0 equiv), base (2.5 equiv), and copper salt (1.0 equiv) in DMSO
(0.4 M with respect to the sulfonimidamide) at 100 °C.
b Determined after column chromatography.
Metal-catalyzed C–N cross-coupling reactions are power-
ful tools in organic synthesis and offer the possibility of
versatile structural modifications of a nitrogen containing
substrate. The use of palladium-based catalysts in C–N
cross-coupling has extensively been studied by Buchwald
and Hartwig, who also developed robust and sustainable
procedures for efficient couplings of several substrates.4
Copper-mediated reactions provide a low cost alternative
to palladium-catalyzed cross-coupling protocols and ex-
hibit improved functional group tolerance in some cases.
Cross-coupling reactions using stoichiometric and cata-
lytic amounts of copper have extensively been examined
during the last decade,5 which resulted in improvements
with respect to the choice of copper salt, base, ligand, and
additive.
of N-protected N¢-aryl sulfonimidamides by copper-
promoted cross-coupling reactions. The protocol is easy
to perform and all starting materials, except for the sulfon-
imidamides, are commercially available. The products
were obtained in moderate to good yields, and several de-
rivatives became accessible.
As test reactions, the cross-couplings between sulfonimid-
amides 1 and phenyl iodide (2a) were chosen. To identify
the best reaction conditions, the effects of different sol-
vents, copper salts, and bases were studied. The results of
the initial screening are summarized in Table 1.
A solvent screening showed that performing the cross-
coupling in dimethyl sulfoxide gave the product in higher
yield than in 1,4-dioxane. Unsatisfactory results were ob-
tained with toluene, N,N-dimethylformamide, and N-
methyl-2-pyrrolidone. To our delight, several copper salts
promoted the N-arylation yielding N-phenyl sulfonimid-
amides 3, and the best results were obtained with copper(I)
halides, especially copper(I) chloride (Table 1, entries 3–
5). Changing the N-protecting group of the sulfonimid-
amide from N-tosyl to N-benzoyl led to a significant in-
crease in yield (entries 3 and 4). Moreover, potassium
Stimulated by our findings on the ligand-free copper-pro-
moted N-arylation of sulfoximines, which gave the de-
sired products in high yields starting from S-alkyl-S-
arylsulfoximines and aryl iodides or aryl bromides,6,7 we
wondered, if similar N-arylation conditions would also be
applicable in sulfonimidamide cross-couplings. Herein,
we confirm this hypothesis and report on the preparation
SYNTHESIS 2008, No. 5, pp 0739–0742
x
x
.
x
x
.2
0
0
8
Advanced online publication: 31.01.2008
DOI: 10.1055/s-2008-1032139; Art ID: Z27207SS
© Georg Thieme Verlag Stuttgart · New York

740
C. Worch, C. Bolm
PAPER
equivalents of the sulfonimidamide (with respect to the
aryl iodide 2g) were used.
Table 2 Copper-Mediated Cross-Coupling of Sulfonimidamide 1b
with Aryl Halides 2b–ka
In conclusion, we have developed a copper-mediated
cross-coupling method for the synthesis of various N-ary-
lated sulfonimidamides. This synthetic pathway is highly
flexible, allowing the coupling of several aryl iodides and
bromides with sulfonimidamides.
O
N
Bz
X
S
O
N
Bz
4-Tol
NH
CuCl, K3CO3
+
S
DMSO,
100 °C, 20 h
4-Tol
NH2
R
R
1b
2
3
All reactions were carried out under argon using standard Schlenk
techniques. The sulfonimidamides 1 were prepared according to lit-
erature protocols.1 All other starting materials were obtained from
commercial suppliers and used without further purification. NMR
spectra were recorded in CDCl3 containing TMS as an internal stan-
dard on a Varian Mercury 300 spectrometer (300 and 75 MHz for
1H and 13C NMR spectra, respectively) or a Varian Inova 400 spec-
trometer (400 and 100 MHz for 1H and 13C NMR spectra, respec-
tively). IR spectra were measured on a Perkin-Elmer PE-1760 FT
instrument as KBr pellets and MS spectra were recorded on a Vari-
an MAT 212 using EI as an ionization technique. TLC was carried
out on silica gel 60 F254 aluminum sheets (Merck) with spot detec-
tion under UV light.
Entry
ArX
2b
2c
2d
2e
2f
X
I
Aryl
Product
Yield (%)b
1
2
4-MeOC6H4
4-FC6H4
3bb
3bc
3bd
3be
3bf
3bg
3bh
3bi
70
59
67
62
68
66
55
55
75
50
I
3
I
4-ClC6H4
3-ClC6H4
2-ClC6H4
4-IC6H4
4
I
5
I
6
2g
2h
2i
I
7
I
4-MeC6H4
3-MeC6H4
2-naphthyl
N-Benzoyl N¢-Aryl Sulfonimidamides; General Procedure
8
I
A
dry, sealable vial was charged with sulfonimidamide 1
(1.0 equiv), aryl halide 2 (2.0 equiv), CuCl (1.0 equiv), K2CO3
(2.5 equiv), and degassed DMSO (1 mL per 0.4 mmol of the sulfon-
imidamide). After heating to 100 °C for 20 h, the heterogeneous
mixture was cooled to r.t., taken up in CH2Cl2, and the CH2Cl2 layer
was washed with 25% aq ammonia, aq sat. NaHCO3, and brine. The
organic layer was dried (MgSO4), filtered, and concentrated under
reduced pressure. The products were purified by column chroma-
tography on silica gel affording the N-protected N¢-aryl
sulfonimidamides 3.
9
2j
I
3bj
10
2k
Br 4-MeOC6H4
3bb
a Reaction conditions: sulfonimidamide (1.0 equiv), aryl halide (2.0
equiv), K2CO3 (2.5 equiv), and CuCl (1.0 equiv) in DMSO (0.4 M
with respect to the sulfonimidamide) at 100 °C.
b Determined after column chromatography.
N-(4-Toluenesulfonyl)-4-toluenesulfonimid-N¢-phenylamide
(3aa)
Solid; mp 149–150 °C; Rf = 0.13 (pentane–EtOAc, 5:2).
IR (KBr): 3182, 1490, 1306, 1265, 1148, 1068, 756, 540 cm–1.
carbonate proved to be superior to cesium carbonate as
base (entry 5).
1H NMR (400 MHz, CDCl3): d = 2.36 (s, 3 H, CH3), 2.40 (s, 3 H,
CH3), 7.01–7.11 (m, 3 Harom), 7.15–7.27 (m, 6 Harom), 7.76–7.80 (m,
2 Harom), 7.86–7.90 (m, 2 Harom), 8.39 (s, 1 H, NH).
13C NMR (100 MHz, CDCl3): d = 21.5 (CH3), 21.6 (CH3), 122.5
(2 CH), 125.8 (CH), 126.7 (2 CH), 127.8 (2 CH), 129.1 (2 CH),
129.1 (2 CH), 129.6 (2 CH), 134.5 (C), 135.1 (C), 139.9 (C), 142.8
(C), 144.7 (C).
Next, the substrate scope using various aryl iodides and
bromides was investigated. The results are summarized in
Table 2.
The optimized conditions for the cross-coupling of 1a and
1b with phenyl iodide (2a) proved to be effective for all
other substrates as well, and the corresponding arylated
sulfonimidamides 3 were isolated in moderate to good
yields. The electronic properties of the substituents of the
aryl iodide 2 appeared to have no significant influence on
the yield regardless of whether the substituents were elec-
tron-donating or -withdrawing. Substituents in ortho or
meta position did not hamper the coupling (Table 2, en-
MS (EI, 70 eV): m/z (%) = 400 (52, [M+]), 308 (57), 247 (16), 183
(19), 155 (100), 139 (22), 91 (51).
Anal. Calcd for C20H20N2O3S2: C, 59.98; H, 5.03; N, 6.99. Found:
C, 59.75; H, 4.98; N, 6.98.
N-Benzoyl-4-toluenesulfonimid-N¢-phenylamide (3ba)
tries 3–5, 7, and 8). Both aryl iodide 2b and aryl bromide Solid; mp 140–141 °C; Rf = 0.19 (pentane–EtOAc, 3:1).
2k were suitable aryl sources as the direct comparison
showed, but in the case of the aryl bromide the isolated
yield was somewhat lower (entries 1 and 10). Further-
more, the reaction seemed to proceed more rapidly for
aryl iodides. When 1-bromo-4-iodobenzene was used as
aryl source a mixture of N-(4-bromo) and N-(4-iodophe-
nyl) sulfonimidamide was isolated, and to our surprise no
chemoselectivity was observed. In the case of 1,4-diiodo- (CH), 127.0 (2 CH), 127.9 (2 CH), 129.3 (2 CH), 129.4 (2 CH),
benzene (2g) only the monoarylated product 3bg was iso-
lated (entry 6). No diarylation was observed even when 2
IR (KBr): 3107, 1634, 1490, 1329, 1288, 1223, 1160, 840, 705, 635,
526 cm–1.
1H NMR (400 MHz, CDCl3): d = 2.37 (s, 3 H, CH3), 7.10–7.18 (m,
3 Harom), 7.24 (d, J = 8.0 Hz, 4 Harom), 7.40–7.44 (m, 2 Harom), 7.50–
7.56 (m, 1 Harom), 7.79–7.83 (m, 2 Harom), 8.18–8.22 (m, 2 Harom),
10.41 (br s, 1 H, NH).
13C NMR (100 MHz, CDCl3): d = 21.5 (CH3), 122.0 (2 CH), 125.3
129.7 (2 CH), 132.4 (CH), 135.1 (C), 135.6 (C), 135.9 (C), 144.3
(C), 172.6 (C).
Synthesis 2008, No. 5, 739–742 © Thieme Stuttgart · New York

PAPER
N-Arylation of Sulfonimidamides
741
MS (EI, 70 eV): m/z (%) = 350 (45, [M+]), 258 (71), 155 (27), 105
(100), 77 (19).
N-Benzoyl-4-toluenesulfonimid-N¢-(3-chlorophenyl)amide
(3be)
Solid; mp 167–168 °C; Rf = 0.25 (pentane–EtOAc, 4:1).
Anal. Calcd for C20H18N2O2S: C, 68.55; H, 5.18; N, 7.99. Found: C,
68.22; H, 5.18; N, 7.88.
IR (KBr): 3116, 2834, 1598, 1472, 1323, 1277, 1152, 1091, 959,
860, 809, 782, 711, 681, 643, 520 cm–1.
N-Benzoyl-4-toluenesulfonimid-N¢-(4-methoxyphenyl)amide
(3bb)
Low-melting, glassy product; Rf = 0.24 (pentane–EtOAc, 3:1).
1H NMR (300 MHz, CDCl3): d = 2.38 (s, 3 H, CH3), 7.01–7.09 (m,
2 Harom), 7.15 (d, J = 7.9 Hz, 1 Harom), 7.17–7.20 (m, 1 Harom), 7.24–
7.29 (m, 2 Harom), 7.38–7.45 (m, 2 Harom), 7.50–7.56 (m, 1 Harom),
7.79–7.84 (m, 2 Harom), 8.15–8.29 (m, 2 Harom), the NH signal was
not resolved.
IR (KBr): 3166, 1607, 1573, 1509, 1448, 1320, 1284, 1250, 1217,
1174, 1145, 1029, 954, 861, 830, 715, 528 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.37 (s, 3 H, CH3), 3.74 (s, 3 H,
CH3), 6.72–6.79 (m, 2 Harom), 7.03–7.09 (m, 2 Harom), 7.20–7.25 (m,
2 Harom), 7.38–7.45 (m, 2 Harom), 7.49–7.55 (m, 1 Harom), 7.73–7.78
(m, 2 Harom), 8.17–8.22 (m, 2 Harom), 9.90 (s, 1 H, NH).
13C NMR (75 MHz, CDCl3): d = 21.6 (CH3), 119.6 (CH), 121.7
(CH), 125.4 (CH), 127.1 (2 CH), 128.1 (2 CH), 129.6 (2 CH), 130.0
(2 CH), 130.4 (CH), 132.7 (CH), 135.0 (C), 135.1 (C), 135.9 (C),
144.9 (C), 172.9 (C).
13C NMR (75 MHz, CDCl3): d = 21.8 (CH3), 55.4 (CH3), 114.6
(2 CH), 125.9 (2 CH), 127.3 (2 CH), 127.7 (C), 128.1 (2 CH), 129,6
(2 CH), 129.8 (2 CH), 132.5 (CH), 135.4 (C), 136.0 (C), 144.4 (C),
158.0 (C), 173.1 (C).
MS (EI, 70 eV): m/z (%) = 384 (26, [M+]), 258 (81), 155 (33), 105
(100), 77 (24).
Anal. Calcd for C20H17ClN2O2S: C, 62.41; H, 4.45; N, 7.28. Found:
C, 62.71; H, 4.39; N, 7.27.
MS (EI, 70 eV): m/z (%) = 380 (88, [M+]), 258 (7), 227 (17), 155
(4), 122 (100), 105 (35), 77 (12).
N-Benzoyl-4-toluenesulfonimid-N¢-(2-chlorophenyl)amide
(3bf)
Solid; mp 62–65 °C; Rf = 0.36 (pentane–EtOAc, 5:1).
Anal. Calcd for C21H20N2O3S: C, 66.29; H, 5.30; N, 7.36. Found: C,
65.89; H, 5.58; N, 7.23.
IR (KBr): 3147, 3064, 1605, 1573, 1490, 1320, 1292, 1145, 1093,
951, 813, 713, 649, 559, 535, 503 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.35 (s, 3 H, CH3), 6.98–7.05 (m,
1 Harom), 7.12–7.18 (m, 1 Harom), 7.20–7.25 (m, 2 Harom), 7.31–7.35
(m, 1 Harom), 7.38–7.45 (m, 2 Harom), 7.49–7.58 (m, 2 Harom), 7.80–
7.85 (m, 2 Harom), 8.19–8.24 (m, 2 Harom), 11.00 (s, 1 H, NH).
13C NMR (75 MHz, CDCl3): d = 21.6 (CH3), 122.2 (CH), 125.1 (C),
125.8 (CH), 127.0 (2 CH), 127.7 (CH), 128.1 (2 CH), 129.7 (2 CH),
129.9 (2 CH), 132.6 (CH), 133.6 (C), 135.1 (C), 136.2 (C), 144.7
(C), 172.5 (C).
N-Benzoyl-4-toluenesulfonimid-N¢-(4-fluorophenyl)amide
(3bc)
Solid; mp 129–130 °C; Rf = 0.25 (pentane–EtOAc, 4:1).
IR (KBr): 3121, 3062, 2921, 2844, 1603, 1572, 1509, 1467, 1330,
1284, 1258, 1212, 1176, 1156, 1092, 957, 817, 711, 642, 584, 531,
503 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.38 (s, 3 H, CH3), 6.89–6.97 (m,
2 Harom), 7.08–7.15 (m, 2 Harom), 7.22–7.27 (m, 2 Harom), 7.39–7.45
(m, 2 Harom), 7.50–7.56 (m, 1 Harom), 7.74–7.79 (m, 2 Harom), 8.16–
8.21 (m, 2 Harom), 10.26 (s, 1 H, NH).
13C NMR (75 MHz, CDCl3): d = 21.6 (CH3), 116.3 (d, J = 23 Hz,
2 CH), 125.2 (d, J = 8 Hz, 2 CH), 127.2 (2 CH), 128.1 (2 CH),
129.6 (2 CH), 129.9 (2 CH), 131.4 (C), 132.6 (CH), 135.2 (C),
135.8 (C), 144.7 (C), 160.7 (d, J = 247 Hz, C), 173.0 (C).
MS (EI, 70 eV): m/z (%) = 384 (21, [M+]), 258 (81), 155 (32), 105
(100), 77 (28).
Anal. Calcd for C20H17ClN2O2S: C, 62.41; H, 4.45; N, 7.28. Found:
C, 62.43; H, 4.33; N, 7.24.
19F NMR (400 MHz, CDCl3): d = 115.5.
MS (EI, 70 eV): m/z (%) = 368 (45, [M+]), 269 (46), 155 (27), 105
N-Benzoyl-4-toluenesulfonimid-N¢-(4-iodophenyl)amide (3bg)
Low-melting, glassy product; Rf = 0.27 (pentane–EtOAc, 4:1).
IR (KBr): 1606, 1485, 1319, 1292, 1147, 951, 814, 713, 540 cm–1.
(100), 77 (29).
Anal. Calcd for C20H17FN2O2S: C, 65.20; H, 4.65; N, 7.60. Found:
C, 65.26; H, 4.81; N, 7.54.
1H NMR (400 MHz, CDCl3): d = 2.38 (s, 3 H, CH3), 6.89–6.93 (m,
2 Harom), 7.23–7.27 (m, 2 Harom), 7.39–7.45 (m, 2 Harom), 7.50–7.56
(m, 3 Harom), 7.77–7.81 (m, 2 Harom), 8.15–8.19 (m, 2 Harom); the NH
signal was not resolved.
13C NMR (100 MHz, CDCl3): d = 21.7 (CH3), 89.4 (C), 123.6
(2 CH), 127.1 (2 CH), 128.0 (2 CH), 129.5 (2 CH), 129.9 (2 CH),
132.6 (CH), 135.0 (C), 135.7 (C), 135.8 (C), 138.3 (2 CH), 144.7
(C), 172.7 (C).
N-Benzoyl-4-toluenesulfonimid-N¢-(4-chlorophenyl)amide
(3bd)
Solid; mp 143–144 °C; Rf = 0.25 (pentane–EtOAc, 4:1).
IR (KBr): 1618, 1483, 1396, 1317, 1289, 1253, 1155, 911, 769, 708,
669, 646, 535 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.38 (s, 3 H, CH3), 7.06–7.11 (m,
2 Harom), 7.17–7.22 (m, 2 Harom), 7.22–7.28 (m, 2 Harom), 7.38–7.45
(m, 2 Harom), 7.50–7.56 (m, 1 Harom), 7.76–7.81 (m, 2 Harom), 8.15–
8.21 (m, 2 Harom), 10.40 (s, 1 H, NH).
13C NMR (75 MHz, CDCl3): d = 21.6 (CH3), 123.5 (2 CH), 127.1
(2 CH), 128.1 (2 CH), 129.5 (2 CH), 129.6 (2 CH), 130.0 (2 CH),
131.1 (C), 132.7 (CH), 134.4 (C), 135.1 (C), 135.8 (C), 144.8 (C),
172.9 (C).
MS (EI, 70 eV): m/z (%) = 476 (28, [M+]), 258 (32), 155 (23), 105
(100), 77 (35).
HRMS (EI): m/z calcd for C20H17IN2O2S: 476.0055; found:
476.0057.
N-Benzoyl-4-toluenesulfonimid-N¢-4-tolylamide (3bh)
Solid; mp 151 °C; Rf = 0.24 (pentane–EtOAc, 4:1).
IR (KBr): 3057, 1600, 1569, 1512, 1385, 1326, 1251, 1148, 957,
863, 817, 712, 584, 506 cm–1.
MS (EI, 70 eV): m/z (%) = 384 (41, [M+]), 258 (54), 155 (35), 126
(5), 105 (100), 77 (26).
1H NMR (75 MHz, CDCl3): d = 2.26 (s, 3 H, CH3), 2.36 (s, 3 H,
CH3), 7.03 (s, 4 Harom), 7.19–7.25 (m, 2 Harom), 7.38–7.45 (m,
1 Harom), 7.49–7.55 (m, 1 Harom), 7.76–7.82 (m, 2 Harom), 8.16–8.21
(m, 2 Harom), 10.19 (s, 1 H, NH).
Anal. Calcd for C20H17ClN2O2S: C, 62.41; H, 4.45; N, 7.28. Found:
C, 62.19; H, 4.51; N, 7.19.
Synthesis 2008, No. 5, 739–742 © Thieme Stuttgart · New York

742
C. Worch, C. Bolm
PAPER
13C NMR (300 MHz, CDCl3): d = 20.8 (CH3), 21.6 (CH3), 122.7
(CH), 127.2 (2 CH), 128.1 (2 CH), 129.6 (2 CH), 129.8 (2 CH),
130.0 (2 CH), 132.5 (CH), 132.8 (C), 135.4 (C), 135.6 (C), 136.1
(C), 144.4 (C), 172.9 (C).
MS (EI, 70 eV): m/z (%) = 364 (67, [M+]), 258 (51), 211 (20), 155
(23), 105 (100), 77 (28).
(C), 132.5 (CH), 134.1 (C), 135.3 (C), 136.1 (C), 144.4 (C), 173.1
(C).
MS (EI, 70 eV): m/z (%) = 400 (69, [M+]), 258 (5), 247 (13), 155
(15), 115 (28), 105 (100), 77 (18).
Anal. Calcd for C24H20N2O2S: C, 71.98; H, 5.03; N, 6.99. Found: C,
72.15; H, 5.18; N, 6.69.
Anal. Calcd for C21H20N2O2S: C, 69.20; H, 5.52; N, 7.69. Found: C,
69.15; H, 5.61; N, 7.66.
Acknowledgment
N-Benzoyl-4-toluenesulfonimid-N¢-3-tolylamide (3bi)
Solid; mp 151–152 °C; Rf = 0.27 (pentane–EtOAc, 4:1).
This work was supported by the Fonds der Chemischen Industrie.
IR (KBr): 3121, 1600, 1569, 1475, 1324, 1280, 1246, 1144, 1093,
1018, 960, 827, 724, 644, 531 cm–1.
References
1H NMR (300 MHz, CDCl3): d = 2.27 (s, 3 H, CH3), 2.36 (s, 3 H,
CH3), 6.88–7.00 (m, 3 Harom), 7.07–7.14 (m, 1 Harom), 7.21–7.25 (m,
2 Harom), 7.38–7.45 (m, 1 Harom), 7.49–7.55 (m, 1 Harom), 7.78–7.84
(m, 2 Harom), 8.16–8.21 (m, 2 Harom), 10.37 (s, 1 H, NH).
13C NMR (75 MHz, CDCl3): d = 21.3 (CH3), 21.6 (CH3), 118.9
(CH), 122.7 (CH), 126.3 (CH), 127.2 (2 CH), 128.1 (2 CH), 129.1
(CH), 129.6 (2 CH), 129.8 (2 CH), 132.5 (CH), 135.3 (C), 135.7
(C), 136.2 (C), 139.5 (C), 144.4 (C), 172.8 (C).
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H.; Dauban, P. Angew. Chem. Int. Ed. 2006, 45, 4641;
Angew. Chem. 2006, 118, 4757.
MS (EI, 70 eV): m/z (%) = 364 (47, [M+]), 258 (76), 211 (14), 155
(30), 105 (100), 77 (35).
(3) Worch, C.; Bolm, C. Synthesis 2007, 1355.
(4) Muci, A. R.; Buchwald, S. L. Top. Curr. Chem. 2002, 219,
131; and references cited therein.
HRMS (EI): m/z calcd for C21H20N2O2S: 364.1246; found:
(5) (a) Kunz, K.; Scholz, U.; Ganzer, D. Synlett 2003, 2428.
(b) Ley, S. V.; Thomas, A. T. Angew. Chem. Int. Ed. 2003,
42, 5400, Angew. Chem. 2003, 115, 5558; and references
cited therein.
364.1246.
N-Benzoyl-4-toluenesulfonimid-N¢-naphthalen-1-amide (3bj)
Solid; mp 146–147 °C; Rf = 0.23 (pentane–EtOAc, 6:1).
(6) Cho, G. Y.; Rémy, P.; Jansson, J.; Moessner, C.; Bolm, C.
Org. Lett. 2004, 6, 3293.
IR (KBr): 3293, 3056, 1602, 1570, 1401, 1292, 1259, 1145, 1089,
942, 802, 713, 644, 538, 499 cm–1.
(7) For related metal-catalyzed cross-couplings involving
sulfoximines, see: (a) Bolm, C.; Hildebrand, J. P.
Tetrahedron Lett. 1998, 39, 5731. (b) Bolm, C.; Hildebrand,
J. P. J. Org. Chem. 2000, 65, 169. (c)Bolm, C.;Hildebrand,
J. P.; Rudolph, J. Synthesis 2000, 911. (d) Sedelmeier, J.;
Bolm, C. J. Org. Chem. 2005, 70, 6904. (e) Moessner, C.;
Bolm, C. Org. Lett. 2005, 7, 2667. (f) Correa, A.; Bolm, C.
Adv. Synth. Catal. 2007, 349, 2673. (g) Correa, A.; Bolm,
C. Adv. Synth. Catal. accepted for publication.
1H NMR (300 MHz, CDCl3): d = 2.29 (s, 3 H, CH3), 7.11–7.15 (m,
2 Harom), 7.29–7.35 (m, 1 Harom), 7.42–7.60 (m, 6 Harom), 7.63–7.66
(m, 1 Harom), 7.75–7.79 (m, 2 Harom), 7.79–7.83 (m, 1 Harom), 8.18–
8.22 (m, 1 Harom), 8.25–8.29 (m, 2 Harom), 11.41 (s, 1 H, NH).
13C NMR (75 MHz, CDCl3): d = 21.6 (CH3), 120.2 (CH), 121.5
(CH), 125.3 (CH), 126.2 (CH), 126.3 (CH), 126.9 (CH), 127.0
(2 CH), 127.4 (C), 128.1 (2 CH), 128.4 (CH), 129.6 (4 CH), 131.3
Synthesis 2008, No. 5, 739–742 © Thieme Stuttgart · New York