M-CPBA-Mediated Intramolecular Aminohydroxylation of N-Sulfonyl Aminoalkenes to Synthesize β-Hydroxyl Cyclic Amines

Article abstract of DOI:10.1002/jhet.2169

A variety of structurally diverse N-sulfonyl-protected aminoalkenes readily reacted with m-CPBA to produce a series of β-hydroxyl cyclic amines in high yields through intramolecular aminohydroxylation. This metal-free and easy-to-handle synthetic methodol

Full text of DOI:10.1002/jhet.2169

Month 2014
m-CPBA-Mediated Intramolecular Aminohydroxylation of N-Sulfonyl
Aminoalkenes to Synthesize β-Hydroxyl Cyclic Amines
a
a
a
Yan Yin,a,b Hong Zhou, Guofeng Sun, and Xichen Liu
*
aSchool of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Hai Quan Rd., Shanghai,
201418, People’s Republic of China
bKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, 345 Ling Ling Rd., Shanghai, 200032, People’s Republic of China
*
E-mail: yinyan@sit.edu.cn
Received July 22, 2013
DOI 10.1002/jhet.2169
Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com).
A variety of structurally diverse N-sulfonyl-protected aminoalkenes readily reacted with m-CPBA to
produce a series of β-hydroxyl cyclic amines in high yields through intramolecular aminohydroxylation.
This metal-free and easy-to-handle synthetic methodology offered an environmentally friendly alternative
to vicinal difunctionalization of alkenes.
J. Heterocyclic Chem., 00, 00 (2014).
INTRODUCTION
succeed the m-CPBA-mediated intramolecular amino-
hydroxylation to cyclize pent-4-en-1-amines to prrolidin-2-
ylmethanols, substrates with substituted groups at double
bonds did not finish the cyclization in one step, and no cycli-
zation routes other than 5-exo were discovered [32].
The β-hydroxyl cyclic amine motif is found in a range of
bioactive naturally occurring molecules [1–6] and several
synthetic strategies to access this important structural unit
have been developed so far [7–15]. The employment of
either toxic or expensive metal salts and the high sensitivity
of the requested complexes to air and moisture have limited
the metal-catalyzed intramolecular aminohydroxylation to
build up β-hydroxyl cyclic amine moieties [16–19]. It was
a multi-step procedure to transfer alkenes to β-hydroxyl
cyclic amines through epoxidation reaction, followed by
epoxide ring opening by the attack of the nitrogen atom in
the presence of bases [20–23]. Iodine(III)/TFA system
was used to access β-hydroxyl five-eight membered cyclic
amines from aminoalkenes and the addition of excess
trifluoroacetic acid significantly accelerated this process
and improved its efficiency [24,25]. Tellitu’s group applied
the PIFA complex in the direct intramolecular amino-
hydroxylation of N-protected terminal olefins to form β-
hydroxyl cyclic amine scaffold [26–29]. In Togo’s method
Oxone was added as oxidant source and TsOH · H2O as
additive, and the addition of 10 mol% TsOH · H2O activated
the cyclization and at the same time increased the yield [30].
Several groups reported m-CPBA mediated conversion of
N-protected pent-4-en-1-amines to pyrrolidin-2-ylmethanol
derivatives through 5-exo cyclization route, which is a
metal-free and one-step procedure, but the detailed
information about this transformation including scope
and limitations were not well investigated [31–33]. Only
moderate yields and regioselectivities were achieved
while carbamates underwent m-CPBA-mediated intramo-
lecular alkene aminohydroxylation according to Petter’s
report [31]. In Mouline’s publication, few examples
Previously, we reported superacid-catalyzed intramolecu-
lar hydroamination of N-sulfonyl aminoalkenes to afford
nitrogen-containing heterocycles (Scheme 1, eq 1) [34–36].
During the continuous scientific research to synthesize N-
containing heterocycles through vicinal functionalization of
alkenes, Ts-protected 2-allylic-aniline 1a was successfully
transformed to 2-hydroxymethyl-indoline 2a at room
temperature with m-CPBA as oxidant source and CH2Cl2
as solvent (Scheme 1, eq 2). In this transformation, no trace
epoxytosylamide was separated after the reaction mixture
was purified with Et3N pre-treated silica gel although a
plausible epoxidized intermediate was observed through
TLC plate analysis. Actually, the conversion of 1a to 2a
was m-CPBA-mediated intramolecular aminohydroxylation
through 5-exo cyclization route. Comparing current work
with previous reports [31–33], current work expanded reac-
tion substrates from N-sulfonyl aliphatic amines to anilines.
Scheme 1. Functionalization of unsaturated sulfonamides.
© 2014 HeteroCorporation

Y. Yin, H. Zhou, G. Sun, and X. Liu
Vol 000
Furthermore, substrates that highly selectively underwent
intramolecular aminohydroxylation to form β-hydroxyl
cyclic amines through endo cyclization routes were found.
Herein, we report the successful development of this reaction
as an alternative to preparation of β-hydroxyl pyrrolidines,
piperidines, indolines, and tetrahedroquinolines from
amino alkenes.
were added, the higher oxidant loading would shorten the
transformation time (22 h for 1.5 equiv. vs 20 h for 1.8
equiv. entries 16 and 17). Lowering oxidant loading to 1
equivalent led to 58% separated yield after 24 h and
unconsumed starting material 1a was recovered (entry 18).
Analogs of 1a with different protective groups on the
nitrogen atom were easily prepared through coupling
reaction of 2-allylic-aniline with active chlorides in the
presence of dry pyridine, and submitted for the intramolec-
ular aminohydroxylation transformation to study the effects
of protective groups. The results were summarized in
Table 2. All sulfonamides underwent smoothly the tethered
aminohydroxylation reaction to give N-sulfonyl-protected
2-hydroxylmethyl-indolines in high yields (entries 1 and
2). However, the reaction of substrates containing acyl
groups (1c and 1d) only gave trace amount of expected 2-
hydroxylmethyl-indolines according to 1H-NMR spectrum
analysis even after 168 h, and only epoxides were separated
from the reaction mixtures with yields of 99% and 92%,
respectively (entries 3–4). While free amine 1e was used
as the reaction substrate, neither epoxides nor β-hydroxyl
cyclic amines were detected (entry 5). So sulfonyl groups
on the nitrogen atom were the key for the successful
conversions of these sulfonamides to 2-hydroxylmethyl-
indolines.
RESULTS AND DISCUSSION
For better investigation of this tethered aminohydroxy-
lation reaction, we first screened the reaction conditions
using 1a as the substrate of the template reaction includ-
ing oxidant, solvent, temperature, and oxidant loading
(Table 1). The survey of different reaction conditions
revealed that the transformation of 1a was best performed
at room temperature for 24 h with 1.2 equivalent m-CPBA
as oxidant source and CH2Cl2 as solvent (entry 1).
Markedly low to zero yields were observed when H2O2,
TBHP, NaClO2, or Oxone were utilized as the oxidants
(entries 2–5). Noncoordination solvents such as toluene,
benzene, and chloroform were proved to be suitable
solvents for the reaction, but the yields were a little bit
lower compared with CH2Cl2 as solvent (entries 6–8).
Reaction in coordination solvents such as CH3CN, H2O,
Et2O, or THF exhibited very low yields (entries 9–12).
Heating or cooling the reaction did not benefit the yields
(entries 13–15). Increasing the oxidant loading had no help
to improve the reaction yields, but had obvious influence on
the transformation rates (entries 16–18). Although reaction
yields were similar while 1.5 or 1.8 equivalents of m-CPBA
To gain insight on the electronic effect of the middle
phenyl ring on this intramolecular aminohydroxylation
transformation, a series of N-tosyl-2-allylic-anilines 1
bearing substituted groups para to nitrogen atom, includ-
ing CH3O, CH3, H, F, Cl, Br, and NO2, were readily syn-
thesized through a short sequence [34–37]. The synthetic
Table 1
Survey the reaction conditions.a
Entry
Oxidant
Oxidant loading, mole%
Solvent
Temp. (°C)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
m-CPBA
H2O2
TBHP
NaClO2
Oxone
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
150
180
100
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
toluene
benzene
CHCl3
H2O
CH3CN
Et2O
THF
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
À20
0
24
48
48
48
48
32
36
28
24
24
24
24
24
24
20
22
20
24
94
0c
Tracec
0c
0c
90
89
92
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
m-CPBA
9
trace
12c
Trace
5c
10
11
12
13
14
15
16
17
18
31c
69c
91
reflux
RT
RT
RT
92
94
58c
aReaction conditions: amine (0.5 mmol), m-CPBA (0.6 mmol), CH2Cl2 (10 mL), RT.
bIsolated yield after chromatograph.
cThe unconsumed starting material 1a was recovered.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
m-CPBA-Mediated Intramolecular Aminohydroxylation of N-Sulfonyl
Aminoalkenes to Synthesize β-Hydroxyl Cyclic Amines
Table 2
Table 3
Effect of the protected groups.a
Electronic effects of middle phenyl ring.a
Entry
PG
Substrate Time (h) Product Yield (%)b
Entry
R
Substrate
Time (h)
Yield (%)b
1
2
3
4
5
Ts
1a
1b
1c
1d
1e
24
48
168
168
168
2a
2b
3c
3d
NR
94
89
99
92
NR
1
2
3
4
5
6
7
CH3O
CH3
H
F
Cl
1f
18
20
24
36
36
36
48
90
84
94
84
87
82
85
p-Ns
PhCO
Cbz
H
1g
1a
1h
1i
1j
1k
Br
NO2
aReaction conditions: amine (0.5 mmol), m-CPBA (0.6 mmol), CH2Cl2
(10 mL), RT.
bIsolated yield after chromatograph.
aReaction conditions: amine (0.5 mmol), m-CPBA (0.6 mmol), CH2Cl2
(10 mL), RT.
bIsolated yield after chromatograph.
route was outlined in Scheme 2. An SN2 reaction of benzyl
amines with allylic bromide gave N-allylanilines 4. In the
presence of 1 equivalent of BF.3Et2O, 4 was transferred to
o-allylic anilines 5 through aza-Claisen rearrangement.9
Pyridine-promoted sulfonylation reactions underwent
smoothly by treating 5 with TsCl to produce targeted
molecules 1 in high yields.
substitution groups at unsaturated carbon–carbon double
bond in this transformation. Dozens of N-alkyltosylamides
and N-aryltosylamides (1l–1v) with different distances
(2, 3, 4, and 5 bonds) between C═C and N atom were
quickly prepared [40] and underwent the intramolecular
aminohydroxylation reaction. Most of them successfully
afforded β-hydroxyl cyclic amines as expected. At the same
time, the electronic and steric effects of the substitution
groups at the C═C bond exhibited remarkable influences
on the cyclization from the point of cyclization route,
reaction rate, regioselectivity, and stereoselectivity. The
results were shown in Table 4.
Treatment of allylic tosylamide 1l and homoallylic
tosylamides (1m and 1n) with 1.2 equiv. m-CPBA in
DCM afforded epoxidized products in excellent yields after
12h, and no trace amount of β-hydroxyl 3-membered, or
4-membered cyclic amines were detected even with
prolonged reaction time (entries 1–3) probably due to their
rigidity. Although the distances between double bond and
N atom were the same as 1m and 1n (three bonds), Π-Elec-
tron-rich polysubstituted β-amino alkenes 1o and 1p
underwent the 5-endo cyclization route to give β-hydroxyl
pyrrolidines with yields of 91% and 92% after 24 and 48h,
respectively (entries 4 and 5). After 24 h, substrates such as
terminal γ-amino olefins (1q and 1r) with one bond longer
than 1o and 1p underwent the same reaction smoothly
through 5-exo cyclization route to give pyrrolidine deriva-
tives (2o–2r) in high yields (89% and 88%, respectively,
entries 6 and 7). However, internal γ-amino olefins (1s and
1t) with phenyl group at the end of double bond were exclu-
sively transferred to 6-membered heterocycles (2s and 2t)
through 6-endo cyclization route and no 5-exo cyclization
products were observed even after 72 and 120h, respectively
(entries 8 and 9). Terminal δ-amino olefins (1u and 1v) were
cyclized to piperidin-2-ylmethanols through 6-exo cycliza-
tion route within 3 days (entries 10 and 11), and no
pyrrolidine analogs were observed. Alkyl-substituted acyclic
alkenes underwent the intramolecular aminohydroxylation.
1-[1-(Toluene-4-sulfonyl)-pyrrolidin-2-yl]- ethanol was sep-
arated in 86% yields while N-Hex-4-enyl-4-methyl-
benzenesulfonamide was treated with 120mol% m-CPBA.
Treated with the aforementioned optimized reaction
conditions, all para substituted N-tosyl-2-allylanilines 1
were transformed to 2-hydroxylmethyl-indolines in high
yields through a 5-exo cyclization route, favored by
Baldwin’s rules [38,39]. Cyclization results were outlined
in Table 3. Electron density in the middle phenyl ring
had little effects on the yields of the reaction, but substrates
with electron-withdrawing groups required longer reaction
time to finish the cyclization than substrates with electron-
donating groups (entries 1–7). It took the longest reaction
time to finish the transformation of the very electron
deficient alkene 1k (entry 7). We speculated this is because
the electron-withdrawing substitution groups lowered the
nucleophilicity of nitrogen atom, so as to decrease the rate
of epoxide ring opening by the attack of nitrogen atom.
After success to synthesize 2-hydroxylmethyl-indolines
from 2-allylanilines in which the distance between
unactive carbon–carbon double bond and nitrogen atom
was four bonds, we further anticipated to obtain β-hydroxyl
3-membered, 4-membered, and 6-membered cyclic amines
from Ts-protective amino alkenes to find out the effects of
Scheme 2. Synthetic route of 1.
Journal of Heterocyclic Chemistry
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Y. Yin, H. Zhou, G. Sun, and X. Liu
Vol 000
Table 4
Intramolecular aminohydroxylation of Ts-protected amino alkenes.a
Entry
1
Substrate
Product
Cyclization route
NR
Time (h)
12
Yield (%)b
96
2
NR
12
97
3
4
NR
12
24
94
91
5-endo
5
5-endo
48
92
6
7
5-exo
5-exo
24
24
89
88
8
9
6-endo
6-endo
72
91
120
78
(Continued)
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
m-CPBA-Mediated Intramolecular Aminohydroxylation of N-Sulfonyl
Aminoalkenes to Synthesize β-Hydroxyl Cyclic Amines
Table 4
(Continued)
Entry
10
Substrate
Product
Cyclization route
Time (h)
72
Yield (%)b
88
6-exo
11
6-exo
72
90
aReaction conditions: amine (0.5 mmol), m-CPBA (0.6 mmol), CH2Cl2 (10 mL), RT.
bIsolated yield after chromatography.
Scheme 3. Plausible transition state structures.
The nucleophilic addition of sulfonyl-protected nitrogen
atom to unsaturated double bond was highly regioselective.
The electron richer carbon would be exclusively attached
by nitrogen atom through either 5-endo or 6-endo cycliza-
tion routes (entries 4, 5, 8, and 9), and the 5-exo and 5-endo
cyclization routes were faster than 6-exo and 6-endo cycliza-
tion routes (entry 5 vs entry 8 and entry 6 vs entry 10). At the
same time, the cyclization rate would be drastically de-
creased, while nitrogen atom nucleophilic attack at the
phenyl-substituted amino alkenes because of the steric effect
(entry 5 vs entry 4 and entry 8 vs entry 6). And it took 5 days
to finish the cyclization of very bulky substrate 1t (entry 9).
The stereoisomerism of the intramolecular aminohydro-
xylation was further studied through 2D-NMR spectros-
copy analysis (Table 4, entries 4, 5 and 7–9). All internal
alkenes (1o, 1p, 1s, and 1t) were stereoselectively cyclized
to a single isomer (cis:trans > 99:1 for 1o, 1s, and 1t, and
trans:cis > 99:1 for 1p). And the plausible transition state
structures were shown in Scheme 3. Polysubstituted termi-
nal alkene (1r) was cyclized to a trans/cis mixture and the
thermodynamically stable trans isomer was the major
product (trans:cis = 3:2, entry 7).
Scheme 4. Base-promoted epoxide ring opening.
After the conversation of terminal α-amino and β-amino
alkenes to β-hydroxyl aziridines and azetidines under the
optimized conditions failed (Table 4, entries 1–3), we tried
a two-step procedure to synthesize the targeted products
[21]. Refluxing the mixture of epoxides in 5% NaOH for
5 min, both 3l and 3n were completely transformed to β-
hydroxyl cyclic amines in high yields (Scheme 4).
Scheme 5. Stable epoxytosylamides.
Although the epoxide intermediate was too labile to be
obtained while 1a was treated with m-CPBA (Scheme 1,
eq 2), epoxide intermediates such as 3p, 3u, and 3v were
successfully separated and characterized before substrates
additives such as TsOH · H2O would catalyze the intramo-
lecular amination of epoxides according to Moriyama’s
report [6]. In the present transformation, m-CPBA proba-
bly acted in a dual role by acting as an oxidant source to
epoxidize the unsaturated double bond and at the same time
by acting as the BrØnsted acid additive to catalyze the epoxide
1p, 1u, and 1v were completely converted to β-hydroxyl
cyclic amines (Scheme 5). Furthermore, 3p, 3u, and 3v
were stable in CDCl3 for more than 3 months without any
chemical changes.
For epoxide, intermediates were separated during the
intramolecular aminohydroxylation and BrØnsted acid
Journal of Heterocyclic Chemistry
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Y. Yin, H. Zhou, G. Sun, and X. Liu
Vol 000
Scheme 6. Proposed mechanism.
(m, 1H), 3.75–3.71 (m, 2H), 2.85–2.76 (dd, J = 9.3, 16.5 Hz,
1H), 2.66–2.59 (dd, J = 3.3, 16.5 Hz, 1H), 2.36 (s, 3H).
[1-(4-Nitro-benzenesulfonyl)-2, 3-dihydro-indol-2-yl]-methanol
(2b).
Yield: 148.8 mg (89%); white solid; mp 148–149°C; IR
(KBr, cmÀ1) 3574, 3105, 2926, 2871, 1530, 1479, 1351, 1171,
1
1089, 855, 735, 567. H-NMR (300 MHz, CDCl3) δ =8.24–8.21
(m, 2H), 7.86–7.67 (m, 3H), 7.28–7.07 (m, 3H), 4.358–4.30 (m,
1H), 3.76 (d, J = 5.7 Hz, 2H), 2.86-2.68 (m, 3H); MS (EI) (m/z)
334, 303, 186, 137, 117, 91, 77, 44; 13C-NMR (75MHz, CDCl3)
δ 150.5, 143.1, 140.4, 131.9, 128.4, 128.1, 125.8, 125.6, 124.2,
117.2, 65.3, 63.8, 31.2; HRMS Calcd for C15H14N2O5S: 357.0516
[M + Na+], Found: 357.0528; Anal. Calcd for C15H14N2O5S: C,
53.88; H, 4.22; N, 8.38. Found: C, 53.66; H, 4.37; N, 8.50.
ring opening attached by Ts-protected nitrogen atom. A plau-
sible mechanism of the tandem epoxidation/intramolecular
amination of epoxides reaction was described as shown in
Scheme 6: epoxidation of amino alkenes 1 with m-CPBA
produced complex A with hydrogen bond interactions, then
complex A was converted to the β-hydroxyl cyclic amines 2
through either exo-tet or endo-tet cyclization routes.
[5-Methoxy-1-(toluene-4-sulfonyl)-2, 3-dihydro-indol-2-yl]-
methanol (2f).
Yield: 150.0 mg (90%); colorless oil; IR
(KBr, cmÀ1) 3531, 2923, 2852, 1723, 1597, 1487, 1349, 1165,
1090, 1032, 814, 670, 547; 1H-NMR (300 MHz, CDCl3)
δ = 7.61–7.58 (m, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.17 (d,
J = 8.4Hz, 2H), 6.79–6.75 (m, 1H), 6.59–6.58 (m, 1H), 4.32–4.24
(m, 1H), 3.76 (s, 3H), 3.68 (d, J = 6 Hz, 2H), 2.73–2.64 (m, 1H),
2.55–2.42 (m, 1H), 2.36 (s, 3H); MS (EI) (m/z) 333, 302, 178,
156, 155, 149, 148, 139, 91, 65, 41; 13C-NMR (75 MHz, CDCl3)
δ 157.7, 144.1, 134.6, 134.3, 133.9, 129.6, 127.2, 118.8, 113.1,
110.8, 65.4, 63.9, 55.6, 31.4, 21.5; HRMS Calcd for
C17H19NO4S: 356.0927 [M+ Na+], Found: 356.0938; Anal. Calcd
for C17H19NO4S: C, 61.24; H, 5.74; N, 4.20. Found: C, 61.46; H,
5.92; N, 3.98.
CONCLUSIONS
We developed a metal-free and easy-to-handle intramolec-
ular aminohydroxylation to build up β-hydroxyl 5-membered
and 6-membered cyclic amines. Our studies indicated the pos-
sibility for high levels of reaction of regio- and stereocontrol,
making it a potentially attractive method in organic synthesis.
Future work will be directed at mechanism investigation to
explore the potential for asymmetric induction.
[5-Methyl-1-(toluene-4-sulfonyl)-2, 3-dihydro-indol-2-yl]-
methanol (2g).
Yield: 133.3 mg (84%); colorless oil; IR
(KBr, cmÀ1) 3542, 2921, 2864, 2253, 1598, 1488, 1349,
EXPERIMENTAL
1
1167, 1091, 908, 814, 736, 672; H-NMR (300 MHz, CDCl3)
1H-NMR and 13C-NMR spectra were recorded on a Bruker
DPX 300 MHz spectrometer (Billerica, MA; 300 and 75 MHz, re-
spectively) with TMS as an internal standard. Coupling constants
are reported in hertz (Hz). All 13C-NMR spectra were proton
decoupled. Mass spectral analyzed was measured on a HP-5989.
HRMS (EI) was measured on a Fimigan MA+ (Thermo Fisher
Scientific, Waltham, MA). IR was measured on Perkin-Elmer
983 (Waltham, MA). The melting points were measure on a Melting
point SGW X-4 (Shanghai Jingke, Shanghai, China). All the products
were purified by column chromatography on silica gel with ethyl
acetate-hexane in an appropriate ratio as the eluent. Spectroscopic
data and HRMS analyses are reported for all new compounds.
Preparation of 2a–2d, 2f–2k, 2o–2v, 3c, 3d, and 3l–3n.
To a mixture of aminoalkenes (1a–1v, 0.5 mmol) in CH2Cl2
(10 mL), m-CPBA (0.6 mmol) was added slowly, and the
resulting mixture was stirred at room temperature until the
started material completely disappeared monitored by TLC.
Then saturated Na2S2O3 (1 mL) and NaHCO3 (1 mL) were
added to quench the reaction, respectively. The reaction mixture
was extracted with CH2Cl2 (3 × 5 mL), and the combined
organic phases were washed with brine, dried over anhydrous
Na2SO4 and concentrated under reduced pressure to give a
residue. Finally, the crude product was purified through column
chromatography on silica gel (200–300 mesh) with hexane/
EtOAc as eluent to afford the targeted products 2a–2d, 2f–2k,
2o–2v, 3c, 3d, and 3l–3n in corresponding yields.
δ = 7.51–7.48 (m, 3H), 7.14–7.12 (m, 2H), 6.99–6.82 (m,
2H), 4.27–3.66 (m, 3H), 2.91–2.55 (m, 3H), 2.30 (s, 3H),
2.23 (s, 3H); MS (EI) (m/z) 317, 286, 155, 132, 117, 91, 77, 65;
13C-NMR (75MHz, CDCl3) δ 144.1, 138.9, 134.8, 134.4, 132.2,
129.6, 128.4, 127.2, 125.8, 117.3, 65.4, 63.7, 31.2, 21.5, 21.0;
HRMS Calcd for C17H19NO3S: 340.0978 [M+ Na+], Found:
340.0989; Anal. Calcd for C17H19NO3S: C, 64.33; H, 6.03; N,
4.41. Found: C, 64.47; H, 5.92; N, 4.28.
[5-Fluoro-1-(toluene-4-sulfonyl)-2, 3-dihydro-indol-2-yl]-
methanol (2h).
Yield: 135.0 mg (84%); colorless oil; IR
(KBr, cmÀ1) 3527, 2923, 2853, 1598, 1482, 1352, 1165,
1090, 815, 670; 1H-NMR (300 MHz, CDCl3) δ = 7.66–7.62
(m, 1H), 7.51 (d, J = 5.1 Hz, 2H), 7.20 (d, J = 5.1 Hz, 2H),
6.96–6.89 (m, 1H), 6.77–6.74 (m, 1H), 4.35–4.27 (m, 1H),
4.31 (d, J = 5.7 Hz, 2H), 2.79–2.58 (m, 3H), 2.37 (s, 3H); MS
(EI) (m/z) 321, 290, 166, 155, 136, 109, 91, 65; 13C-NMR
(75 MHz, CDCl3) δ 162.2, 158.9, 144.4, 137.4, 134.0, 129.8,
127.2, 118.9, 114.6, 112.3, 65.4, 64.0, 31.3, 21.6; HRMS
Calcd for C16H16FNO3S: 344.0727 [M + Na+], Found:
344.0740; Anal. Calcd for C16H16FNO3S: C, 59.80; H, 5.02;
N, 4.36. Found: C, 60.09; H, 5.00; N, 4.17.
[5-Chloro-1-(toluene-4-sulfonyl)-2, 3-dihydr-indol-2-yl]-
methanol (2i).
Yield: 146.0 mg (87%); colorless oil; IR
(KBr, cmÀ1) 3544, 2962, 1597, 1472, 1353, 1165, 1090, 1041,
814, 668, 591; 1H-NMR (300 MHz, CDCl3) δ = 7.56–7.45 (m,
3H), 7.15–6.95 (m, 4H), 4.25–4.21 (m, 1H), 3.67–3.66 (m, 2H),
2.76–2.56 (m, 3H), 2.30 (s, 3H); MS (EI) (m/z) 337, 308, 306,
155, 139, 117, 91, 65; 13C-NMR (75 MHz, CDCl3) δ 144.5,
140.2, 134.2, 133.9, 130.3, 129.8, 127.9, 127.1, 125.3, 118.4,
65.5, 63.8, 31.1, 21.5; HRMS Calcd for C16H16ClNO3S:
360.0432 [M+ Na+], Found: 360.0442; Anal. Calcd for
[1-(Toluene-4-sulfonyl)-2, 3-dihydro-indol-2-yl]-methanol
(2a). Yield: 109.1 mg (94%); white solid; mp 92–93°C; IR
(KBr, cmÀ1) 3536, 3067, 2923, 2867, 1597, 1479, 1461,
1
1351, 1167, 1091, 1041, 761, 669, 579. H-NMR (300 MHz,
CDCl3) δ = 7.72–7.52 (m, 3H), 7.23–7.04 (m, 5H), 4.33–4.25
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
m-CPBA-Mediated Intramolecular Aminohydroxylation of N-Sulfonyl
Aminoalkenes to Synthesize β-Hydroxyl Cyclic Amines
C16H16ClNO3S: C, 56.89; H, 4.77; N, 4.15. Found: C, 56.61; H,
5.00; N, 4.17.
1H), 2.60–2.50 (m, 1H), 2.47 (s, 3H), 2.31–2.22 (m, 1H),
1.95–1.84 (m, 1H).
[5-Bromo-1-(toluene-4-sulfonyl)-2, 3-dihydro-indol-2-yl]-
cis-2-Phenyl-1-(toluene-4-sulfonyl)-piperidin-3-ol (2s). Yield:
150.8 mg (91%); white solid; mp 76–77°C; IR (KBr, cmÀ1) 3498,
2925, 2867, 1453, 1336, 1157, 1091, 1044, 666, 588; 1H-NMR
(300 MHz, CDCl3) δ =7.80–7.77 (m, 2H), 7.43–7.29 (m, 7H), 4.65
(d, J= 8.4 Hz, 1H), 3.89 (s, 1H), 3.84–3.78 (m, 1H), 3.44–3.24 (m,
2H), 2.43 (s, 3H), 1.54–1.18 (m, 4H).
methanol (2j).
Yield: 156.7 mg (82%); colorless oil; IR
(KBr, cmÀ1) 3528, 2922, 2875, 1597, 1471, 1352, 1165, 1091,
815, 733, 666; 1H-NMR (300 MHz, CDCl3) δ = 7.56–7.51 (m,
3H), 7.33–7.16 (m, 4H), 4.32–4.24 (m, 1H), 3.72 (d, J = 6.3 Hz,
2H), 2.84–2.63 (m, 3H), 2.34 (s, 3H); MS (EI) (m/z) 383, 381,
352, 350, 155, 147, 117, 91, 65, 43; 13C-NMR (75 MHz, CDCl3)
δ 144.5, 140.8, 134.3, 134.2, 130.8, 129.8, 128.2, 127.1, 118.7,
117.8, 65.4, 63.7, 31.1, 21.6; HRMS Calcd for C16H16BrNO3S:
403.9926 [M+ Na+], Found: 403.9939; Anal. Calcd for
C16H16BrNO3S: C, 50.27; H, 4.22; N, 3.66. Found: C, 50.06; H,
4.49; N, 3.75.
cis-2-Phenyl-1-(toluene-4-sulfonyl)-1, 2, 3, 4-tetrahydro-quinolin-
3-ol (2t). Yield: 148.0 mg (78%); white solid; mp 129–130°
C; IR (KBr, cmÀ1) 3511, 2922, 2851, 2252, 1599, 1492,
1342, 1164, 1090, 814, 581. 1H-NMR (300 MHz, CDCl3)
δ = 7.81–7.78 (m, 1H), 7.54–7.51 (m, 2H), 7.30–6.99 (m,
10H), 5.14 (d, J = 6.3 Hz, 1H), 3.88–3.87 (m, 1H), 2.59–2.53
(m, 1H), 2.36 (s, 3H), 2.26 (s, 1H), 2.03–1.95 (m, 1H); MS
(ESI) (m/z) 380.0 [M + H+]; 13C-NMR (75 MHz, CDCl3) δ
143.8, 141.3, 136.3, 136.1, 129.5, 129.1, 128.9, 128.7,
127.6, 127.5, 127.4, 126.6, 125.6, 124.6, 72.9, 66.2, 34.2,
21.5; HRMS Calcd for C22H21NO3S: 402.1134 [M + Na+],
Found: 402.1134; Anal. Calcd for C22H21NO3S: C, 69.63;
H, 5.58; N, 3.69. Found: C, 69.61; H, 5.76; N, 3.84.
[1-(Toluene-4-sulfonyl)-piperidin-2-yl]-methanol (2u). Yield:
118.5 mg (88%); colorless oil; IR (KBr, cmÀ1) 3522, 2938,
[5-Nitro-1-(toluene-4-sulfonyl)-2, 3-dihydro-indol-2-yl]-methanol
(2k). Yield: 148.0 mg (85%); colorless oil; IR (KBr, cmÀ1) 3538,
2924, 2255,1724, 1598, 1525, 1364, 1171, 1092, 906, 814;
1H-NMR (300 MHz, CDCl3) δ = 8.01–7.99 (m, 1H), 7.83–7.52
(m, 4H), 7.17–7.14 (m, 2H), 4.38–4.34 (m, 1H), 3.80–3.74 (m,
2H), 3.00–2.91 (m, 3H), 2.28 (s, 3H); MS (EI) (m/z) 348, 317,
155, 139, 91, 65; 13C-NMR (75 MHz, CDCl3) δ 147.5, 145.2,
144.6, 134.3, 133.1, 130.1, 127.0, 124.4, 120.9, 115.5, 65.4, 64.4,
30.8, 21.5; HRMS Calcd for C16H16N2O5S: 349.0853 [M+ H+],
Found: 349.0863; Anal. Calcd for C16H16N2O5S: C, 55.16; H,
4.63; N, 8.04. Found: C, 55.06; H, 4.49; N, 8.30.
cis-1-(Toluene-4-sulfonyl)-octahydro-indol-3a-ol (2o). Yield:
134.4 mg (91%); colorless oil; IR (KBr, cmÀ1) 3510, 2938, 2862,
2254, 1698, 1598, 1453, 1344, 1156, 1097, 913, 814, 667;
1H-NMR (300 MHz, CDCl3) δ = 7.66 (d, J = 8.1 Hz, 2H),
7.21 (d, J = 8.1 Hz, 2H), 3.41–3.21 (m, 3H), 2.32–2.00 (m,
7H), 1.86–1.82 (m, 1H), 1.57–1.14 (m, 6H).
1
2869, 1738, 1597, 1327, 1158, 1093, 926, 816, 658; H-NMR
(300 MHz, CDCl3) δ = 7.75 (d, J = 8.1 Hz, 2H), 7.30 (d,
J = 8.1 Hz, 2H), 4.05-4.00 (m, 1H), 3.88-3.79 (m, 2H), 3.60-3.54
(m, 1H), 3.15-3.05 (m, 1H), 2.43 (s, 3H), 2.30 (s, 1H), 1.62-1.33
(m, 6H).
[1-(Toluene-4-sulfonyl)-1, 2, 3, 4-tetrahydro-quinolin-2-yl]-
methanol (2v). Yield: 142.8mg (90%); colorless oil; IR (KBr,
1
cmÀ1) 3527, 2923, 1722, 1346, 1164, 1091, 760, 662, 578; H-
cis-2-Phenyl-1-(toluene-4-sulfonyl)-pyrrolidin-3-ol (2p). Yield:
NMR (300MHz, CDCl3) δ = 7.72–7.69 (m, 1H), 7.36–7.13 (m,
6H), 6.98–6.96 (m, 1H), 4.29–4.25 (m, 1H), 3.66–3.56 (m, 2H),
2.44–2.39 (m, 4H), 2.28–2.23 (m, 1H), 2.05–1.92 (m, 1H),
1.48–1.24 (m, 2H); MS (EI) (m/z) 317, 286, 156, 155, 139,
111, 91, 65; 13C-NMR (75 MHz, CDCl3) δ 143.8, 135.7, 135.4,
135.2, 129.5, 128.4, 128.2, 127.5, 127.2, 126.4, 65.5, 58.4, 27.2,
25.2, 21.5; HRMS Calcd for C17H19NO3S: 340.0978 [M + Na+],
Found: 340.0988; Anal. Calcd for C17H19NO3S: C, 64.33; H,
6.03; N, 4.41. Found: C, 64.21; H, 5.89; N, 4.67.
N-(2-Oxiranylmethyl-phenyl)-benzamide (3c). Yield: 125.4 mg
(99%); white solid; mp 115–116°C; IR (KBr, cmÀ1) 3327, 3060,
2920, 1672, 1523, 1451, 1308, 1264, 1073, 932, 852, 709; 1H-NMR
(300 MHz, CDCl3) δ = 9.42 (S, 1H), 8.04–8.01 (m, 3H), 7.53–7.45
(m, 3H), 7.35–7.10 (m, 3H), 3.27–3.22 (m, 2H), 2.91–2.88 (m, 1H),
2.69–2.61 (m, 2H); MS (EI) (m/z) 253, 148, 105, 77; 13C-NMR
(75 MHz, CDCl3) δ 165.6, 137.3, 134.8, 131.7, 130.8, 128.8,
128.7, 127.9, 127.4, 125.2, 124.5, 53.8, 47.5, 35.5; HRMS Calcd
for C16H15NO2: 254.1176 [M + H+], Found: 254.1184; Anal.
Calcd for C16H15NO2: C, 75.87; H, 5.97; N, 5.53. Found: C,
75.69; H, 5.89; N, 5.67.
(2-Oxiranylmethyl-phenyl)-carbamic acid benzyl ester
(3d). Yield: 130.3 mg (92%); white solid; mp 88–89°C; IR
(KBr, cmÀ1) 3270, 2922, 2844, 1736, 1454, 1218, 1043, 747;
1H-NMR (300 MHz, CDCl3) δ = 7.85 (s, 1H), 7.44–7.30 (m,
6H), 5.21 (s, 2H), 3.22–3.16 (m, 2H), 2.86–2.84 (m, 1H),
2.68–2.63 (m, 1H), 2.60–2.58 (m, 1H); MS (ESI) (m/z) 284.2
[M + H+]; 13C-NMR (75 MHz, CDCl3) δ 154.2, 145.9, 130.6,
128.5, 128.2, 128.1, 128.0, 124.3, 119.6, 119.1, 111.3, 66.8,
63.2, 47.2, 35.3; HRMS Calcd for C17H17NO3 306.1101,
Found: 306.1120; Anal. Calcd for C17H17NO3: C, 72.07; H,
6.05; N, 4.94. Found: C, 72.21; H, 5.89; N, 4.67.
146.0 mg (92%); white solid; mp 155–156 °C; IR (KBr, cmÀ1) 3512,
1
2924, 2844, 1334, 1157, 1095, 666, 550; H-NMR (300 MHz,
CDCl3) δ = 7.75–7.72 (m, 2H), 7.34–7.26 (m, 7H), 4.67–4.66
(m, 1H), 4.15–4.14 (m, 1H), 3.75–3.69 (m, 1H), 3.56–3.47
(m, 1H), 2.22 (s, 3H), 2.08–1.70 (m, 3H); MS (ESI) (m/z)
318.2 [M + H+]; 13C-NMR (75 MHz, CDCl3) δ 143.5, 139.8,
134.5, 129.6, 128.5, 127.7, 127.5, 126.2, 78.8, 71.9, 46.7,
31.2, 21.6; HRMS Calcd for C17H19NO3S: 319.1086, Found:
317.1077; Anal. Calcd for C17H19NO3S: C, 64.33; H, 6.03;
N, 4.41. Found: C, 64.61; H, 6.00; N, 4.17.
[1-(Toluene-4-sulfonyl)-pyrrolidin-2-yl]-methanol (2q). Yield:
113.6 mg (89%); colorless oil; IR (KBr, cmÀ1) 3515, 2951, 1597,
1339, 1158, 1092, 665, 588, 551; 1H-NMR (300 MHz, CDCl3)
δ =7.75 (d, J=8.7Hz, 2H), 7.34 (d, J=8.7Hz, 2H), 3.73–3.64 (m,
3H), 3.50–3.43 (m, 1H), 3.31–3.22 (m, 1H), 2.44 (s, 3H),
1.84–1.68 (m, 3H), 1.51–1.24 (m, 2H).
trans-[4-Phenyl-1-(toluene-4-sulfonyl)-pyrrolidin-2-yl]-methanol
(2r). Yield: 87.5 mg (53%); colorless oil; IR (KBr, cmÀ1) 3525,
2924, 2254, 1598, 1496, 1340, 1161, 1026, 909, 816, 666, 550;
1H-NMR (300 MHz, CDCl3) δ = 7.75 (d, J = 8.1 Hz, 2H), 7.34
(d, J = 8.1 Hz, 2H), 7.26–7.17 (m, 3H), 7.02–7.00 (m, 2H),
3.95–3.89 (m, 1H), 3.84–3.78 (m, 3H), 3.59–3.47 (m, 1H),
3.05–2.98 (m, 1H), 2.81 (s, 1H), 2.45 (s, 3H), 2.19–2.13 (m,
1H), 1.82–1.71 (m, 1H).
cis-[4-Phenyl-1-(toluene-4-sulfonyl)-pyrrolidin-2-yl]-methanol
(2rr). Yield: 58.3 mg (35%); colorless oil; IR (KBr, cmÀ1
)
3503, 2923, 1723, 1496, 1341, 1158, 1090, 1029, 700, 664,
549; 1H-NMR (300 MHz, CDCl3) δ = 7.80 (d, J = 8.1 Hz,
2H), 7.38 (d, J = 8.1 Hz, 2H), 7.30–7.24 (m, 3H), 7.09–7.06
(m, 2H), 3.94–3.72 (m, 4H), 3.41–3.33 (m, 1H), 3.01 (s,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Y. Yin, H. Zhou, G. Sun, and X. Liu
Vol 000
4-Methyl-N-oxiranylmethyl-benzenesulfonamide (3l). Yield:
109.1 mg (96%); white solid; mp 66–67°C; IR(KBr, cmÀ1
125.3, 51.6, 47.7, 32.6, 26.9, 21.5; HRMS Calcd for
C17H19NO3S: 340.0978 [M+ Na+], Found: 340.0987; Anal. Calcd
for C17H19NO3S: C, 64.33; H, 6.03; N, 4.41. Found: C, 64.08; H,
)
3304, 2925, 2868, 1598, 1441, 1339, 1168, 1094, 914, 851,
664; 1H-NMR (300 MHz, CDCl3) δ = 7.68 (d, J = 8.1 Hz,
2H), 7.23 (d, J = 8.1 Hz, 2H), 5.59 (t, J = 6 Hz, 1H), 3.24–3.16
(m, 1H), 3.02–2.93 (m, 2H), 2.68–2.65 (m, 1H), 2.55–2.53 (m,
1H), 2.34 (s, 3H).
6.29; N, 4.62.
Procedure for the conversation of 3l and 3n to 2l and 2n. The
mixture of epoxides (3l or 3n, 0.75 mmol) in 5% NaOH (10 mL)
was stirred under refluxing temperature. After the starting material
was completely converted monitored by TLC, the reaction
mixture was cooled to room temperature and extracted with ethyl
ether (3× 20mL). The combined organic phases were washed
with brine, dried over anhydrous Na2SO4, concentrated under
reduced pressure, and purified through column chromatography
with hexane/EtOAc as eluent to give targeted product as a
white solid.
4-Methyl-N-(2-oxiranyl-ethyl)-benzenesulfonamide (3m). Yield:
117.0 mg (97%); white solid; mp 86–87°C; IR (KBr, cmÀ1
)
3227, 2925, 2874, 1597, 1491, 1441, 1328, 1157, 1094, 900,
733, 550; 1H-NMR (300 MHz, CDCl3) δ = 7.72 (d, J = 7.8 Hz,
2H), 7.27 (d, J = 7.8 Hz, 2H), 5.27 (s, 1H), 3.06–3.04 (m, 2H),
2.90–2.69 (m, 2H), 2.42–2.39 (m, 4H), 1.89–1.52 (m, 2H).
4-Methyl-N-(1-oxiranylmethyl-cyclohexyl)-benzenesulfonamide
[1-(Toluene-4-sulfonyl)-aziridin-2-yl]-methanol (2l).
Yield:
(3n).
Yield: 145.4 mg (94%); white solid; mp 146–147°C; IR
161.9 mg (95%); white solid; mp 220–221°C; IR (KBr, cmÀ1
)
(KBr, cmÀ1) 3283, 2935, 2862, 1451, 1332, 1152, 1094, 998, 815,
667; 1H-NMR (300 MHz, CDCl3) δ =7.78 (d, J=8.1Hz, 2H), 7.25
(d, J= 8.1 Hz, 2H), 5.13 (s, 1H), 3.03-3.00 (m, 1H), 2.70–2.67 (m,
1H), 2.42–2.39 (m, 4H), 2.22–2.16 (m, 1H), 1.83–1.74 (m, 2H),
1.55–1.23 (9H).
1
3502, 2924, 1738, 1338, 1158, 1089, 547; H-NMR (300 MHz,
CDCl3) δ = 7.70 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 8.1 Hz, 2H),
4.29–4.21 (m, 1H), 3.51–3.59 (m, 5H), 2.46 (s, 3H).
[1-(Toluene-4-sulfonyl)-1-aza-spiro [3.5] non-2-yl]-methanol
(2n).
Yield: 218.1 mg (94%); white solid; mp 101–102°C
Preparation of 3p, 3u, and 3v.
To a mixture of
(Lit.4b mp 102°C); IR (KBr, cmÀ1) 3506, 2926, 2858, 2252,
aminoalkenes (1p, 1u, and 1v, 0.5 mmol) in CH2Cl2 (10 mL),
m-CPBA (0.6 mmol) was added slowly. The reaction was stirred
at room for 4 h. Then saturated Na2S2O3 (1 mL) and NaHCO3
(1 mL) were added to quench the reaction, respectively. The
resulting mixture was extracted with CH2Cl2 (3 × 5 mL). And
the combined organic phases were washed with brine, dried
over anhydrous Na2SO4, and concentrated under reduced
pressure to give a residue. Finally, the crude product was
purified through column chromatography on silica gel (200–300
mesh) with hexane/EtOAc as eluent to afford 3p, 3u, and 3v in
corresponding yields.
4-Methyl-N-[2-(3-phenyl-oxiranyl)-ethyl]-benzenesulfonamide
(3p). Yield: 30.2mg (19%); white solid; mp 78–79°C; IR (KBr,
cmÀ1) 3284, 2978, 2926, 1453, 1323, 1160, 1093, 702, 663, 551;
1H-NMR (300 MHz, CDCl3) δ = 7.71–7.68 (m, 2H), 7.34–7.21
(m, 7H), 4.97–4.93 (m, 1H), 4.06–4.05 (m, 1H), 3.25–3.19 (m,
1H), 3.13–3.95 (m, 2H), 2.41 (s, 3H), 1.57–1.35 (m, 2H); MS
(ESI) (m/z) 318.2 [M+ H+]; 13C-NMR (75MHz, CDCl3) δ 143.4,
136.7, 134.8, 129.8, 128.2, 127.8, 127.1, 126.4, 57.2, 57.0, 40.7,
26.9, 21.6; HRMS Calcd for C17H19NO3S: 317.1086. Found:
317.1086; Anal. Calcd for C17H19NO3S: C, 64.33; H, 6.03; N,
4.41. Found: C, 64.64; H, 5.89; N, 4.38.
1
1598, 1495, 1449, 1152, 816, 729; H-NMR (300 MHz, CDCl3)
δ = 7.75 (d, J = 7.8 Hz, 2H), 7.31 (d, J = 7.8 Hz, 2H), 4.16–4.08
(m, 1H), 3.74 (d, J = 4.2 Hz, 2H), 3.21 (s, 1H), 2.44 (s, 3H),
1.96–1.10 (m, 12H).
Acknowledgments. The work was partially supported by Science
and Technology Commission of Shanghai Municipality (grant no.
12ZR1431100) and Shanghai Institute of Technology (grant no.
YJ2011-73). Support from Professor Fanhong Wu was also
greatly appreciated.
REFERENCES AND NOTES
[1] Schwartz, C. E. Bioorg Med Chem Lett 1999, 9, 1541.
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[4] Yokoshima, S.; Ueda, T.; Kobayashi, S.; Sato, A.;
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[5] Draper, J. A.; Britton, R. Org Lett 2010, 12, 4034.
[6] Pradilla, R. F.; Lwoff, N.; Viso, A. Tetrahedron Lett 2007, 48,
8141.
4-Methyl-N-(4-oxiranyl-butyl)-benzenesulfonamide (3u). Yield:
20.2 mg (15%); white solid; mp 77–78°C; IR (KBr, cmÀ1) 3285, 2932,
1
2864, 1598, 1457, 1322, 1160, 1093, 915, 816, 661, 551; H-NMR
[7] Donohoe, T. J.; Callens, C. K. A.; Flores, A.; Lacy, A. R.;
Rathi, A. H. Chem Eur J 2011, 17, 58.
[8] Haro, T.; Nevado, C. Angew Chem Int Ed 2011, 50, 906.
[9] Akiyama, T.; Ishida, T.; Kagoshima, H. Tetrahedron Lett
1999, 40, 4219.
[10] Kokotos, C. G.; Aggarwal, V. K. Chem Commun 2006,
2156.
[11] Amat, M.; Pérez, M.; Proto, S.; Gatti, T.; Bosch, J. Chem Eur J
2010, 16, 9438.
[12] Farid, U.; Wirth, T. Angew Chem Int Ed 2012, 51, 3462.
[13] Mancheno, D. E.; Thornton, A. R.; Stoll, A. H.; Kong, A. D.;
Blakey, S. B. Org Lett 2010, 12, 4110.
[14] Cochran, B. M.; Michael, F. E. Org Lett 2008, 10, 5039.
[15] Alexanian, E. J.; Lee, C.; Sorensen, E. J. J. Am Chem Soc
2005, 127, 7690.
(300 MHz, CDCl3) δ =7.71 (d, J= 8.1 Hz, 2H), 7.26 (d, J=8.1Hz,
2H), 5.21 (s, 1H), 2.88–2.80 (m, 3H), 2.68–2.65 (m, 1H), 2.38–2.37
(m, 4H), 1.47–1.41 (m, 6H); MS (ESI) (m/z) 252.2 [M-H2O+H+];
13C-NMR (75 MHz, CDCl3) δ 143.3, 137.0, 129.7, 127.0, 52.1, 47.0,
43.0, 31.8, 29.2, 23.0, 21.5; HRMS Calcd for C13H19NO3S:
251.0980 [M-H2O], Found: 251.0980; Anal. Calcd for C13H19NO3S:
C, 57.97; H, 7.11; N, 5.20. Found: C, 57.77; H, 7.03; N, 5.38.
4-Methyl-N-[2-(2-oxiranyl-ethyl)-phenyl]-benzenesulfonamide
(3v). Yield: 23.8 mg (15%); colorless oil; IR (KBr, cmÀ1) 3274,
3063, 2990, 2923, 1598, 1494, 1332, 1160, 1092, 917, 664, 567;
1H-NMR (300 MHz, CDCl3) δ = 7.63–7.61 (m, 2H), 7.26–7.10
(m, 6H), 2.85–2.82 (m, 1H), 2.75–2.72 (m,1H), 2.54–2.43 (m,
3H), 2.37 (s, 3H), 1.78–1.47 (m, 2H); MS (EI) (m/z) 317, 286,
156, 155, 139, 130, 111, 91, 43; 13C-NMR (75 MHz, CDCl3) δ
143.7, 136.9, 135.4, 134.2, 129.9, 129.6, 127.2, 127.1, 126.5,
[16] See: Donohoe, T. J.; Callens, C. K. A.; Lacy, A. R.; Winter, C.
Eur J Org Chem 2012, 655–663 and references therein.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
m-CPBA-Mediated Intramolecular Aminohydroxylation of N-Sulfonyl
Aminoalkenes to Synthesize β-Hydroxyl Cyclic Amines
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet