Copper-catalyzed Regioselective Hydroaminations of Allylic Sulfones With Aromatic Amines

Article abstract of DOI:10.1002/bkcs.12264

The highly regioselective copper-catalyzed hydroaminations of terminal or γ-substituted allylic sulfones with aromatic amines is described. The combination of an N-heterocyclic carbene-copper complex and KOt-Bu plays an important role in promoting selective amination under mild reaction conditions. This catalytic reaction tolerates a wide range of functional groups and enables the efficient syntheses of new and versatile functionalized β-amino sulfones in high yields (up to 98%) with >98% regioselectivity.

Full text of DOI:10.1002/bkcs.12264

Article
DOI: 10.1002/bkcs.12264
BULLETIN OF THE
K. Kim et al.
KOREAN CHEMICAL SOCIETY
Copper-catalyzed Regioselective Hydroaminations of Allylic Sulfones
With Aromatic Amines
*
Kundo Kim, Soohong Cho, Subin Park, and Yunmi Lee
Department of Chemistry, Kwangwoon University, Seoul 01897, Republic of Korea.
*E-mail: ymlee@kw.ac.kr
Received December 30, 2020, Accepted February 25, 2021, Published online March 11, 2021
The highly regioselective copper-catalyzed hydroaminations of terminal or γ-substituted allylic sulfones
with aromatic amines is described. The combination of an N-heterocyclic carbene-copper complex and
KOt-Bu plays an important role in promoting selective amination under mild reaction conditions. This cat-
alytic reaction tolerates a wide range of functional groups and enables the efficient syntheses of new and
versatile functionalized β-amino sulfones in high yields (up to 98%) with >98% regioselectivity.
Keywords: Allyl sulfones, Aromatic amines, Copper catalyst, Hydroamination, Regioselectivity
Introduction
coworkers reported that a copper catalyst promoted the
regioselective intermolecular hydroaminations of terminal
vinylarenes with arylamines in the presence of visible
light.8 Despite recent advances related to highly efficient
and selective Cu-catalyzed additions of aromatic amines to
alkenes, most reactions are limited in substrate scope to ter-
minal alkenes.
The direct addition of a nitrogen–hydrogen bond across a
carbon–carbon double bond is one of the most powerful
carbon–nitrogen bond forming processes due to its simplic-
ity and atom economy.1 Nitrogen-containing compounds
play significant roles in medicinal and organic chemistry as
valuable building blocks and synthetically useful intermedi-
ates.2 Therefore, a number of catalytic systems for the mild
and efficient syntheses of various amines through
hydroamination or aza-Michael addition have been inten-
sively studied. In particular, the direct intermolecular addi-
tion of an aromatic amine to an alkene is a useful and
attractive way of synthesizing a functionalized N-alkyl aro-
matic amine from readily accessible alkene substrates but is
challenging in that regioselectivity should be controlled and
aromatic amines are less nucleophilic.3 Among various cat-
alysts that promote direct intermolecular addition reactions
of arylamines to alkenes, copper, which is readily available,
relatively inexpensive, and easy-to-handle, is a promising
candidate for efficient and practical amination reactions. In
the past decade, copper-based catalysts have been used to
improve reactivity and regio-, chemo-, and stereo-control
under mild reaction conditions.4 For example, the Cu-cata-
lyzed intermolecular additions of anilines to highly acti-
vated α,β-unsaturated carbonyl compounds with copper(II)
triflate as the Lewis acid catalyst have been reported by
Yamazaki and coworkers.5 Copper(II) triflate has also been
used to intermolecularly hydroaminate arylalkenes with sul-
fonamides, but this amination reaction is thought to be cata-
lyzed by Brønsted acids accidently produced under the
reaction conditions, rather than a copper catalyst.6 Gunnoe
and coworkers reported that a copper(I) amido complex
coordinated to an N-heterocyclic carbene (NHC) ligand cat-
alyzes the additions of anilines to terminal alkenes with
high regioselectivities.7 In a recent study, Zhang and
We recently reported that copper catalysts using phos-
phine- or NHC-based CuCl and KOt-Bu enhance reactivity
to promote the intermolecular additions of anilines or hetero-
cycles to 1,2-disubstituted alkenes, including α,β-unsaturated
carbonyls, α,β-unsaturated sulfones, 1-sulfonyl-1,3-dienes,
and arylalkenes, while also controlling regio- and
stereoselectivities, to afford versatile functionalized amines in
a highly efficient manner.9 To further develop copper cata-
lysts that widely promote the aminations of a broad range of
alkenes, we devised the copper-catalyzed hydroaminations of
aromatic amines with readily accessible β,γ-unsaturated sul-
fones as alternatives to β-substituted β-amino sulfones.
Hence, herein we report that NHC-CuCl and KOt-Bu cata-
lyze the additions of aromatic amines selectively at the
β-positions of β,γ-unsaturated sulfones. This catalytic process
facilitates access to new and versatile β-amino sulfones that
can be functionalized using a variety of synthetic transforma-
tions and used in the syntheses of biologically active
molecules.10
Results and Discussion
We initially evaluated the ability of an NHC-based copper
catalyst to promote the amination of allyl phenyl sulfone
(1) with p-anisidine (2a), the results of which are presented
in Table 1. When 1 was treated with 2a in the presence of
5.5 mol % IPrCuCl and 5 mol % KOt-Bu at ambient tem-
perature, the reaction proceeded regioselectively to afford
the desired aminated product 3a in 75% yield (entry 1).
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Table 1. Optimizing the reaction conditions.a
entry
NHC-CuCl
KOt-Bu
Temp (ꢀC)
Time (h)
Conv (%)b
3a:4a:4b (%)b
1
2
3
4
5
6
7
8
IPrCuCl
SIPrCuCl
IMesCuCl
SIMesCuCl
TripPy-IPr-CuCl
IPrCuCl
IPrCuCl
No
5
5
5
5
5
5
5
no
0
5
22
22
22
22
22
40
40
40
40
40
40
15
15
15
15
15
15
5
15
15
15
15
75
87
>98
>98
89
>98
71
<2
75:<2:<2
70:16:<2
86:14:<2
86:14:<2
47:<2:37
>98:<2:<2
68:<2:3
<2
9
10
11
IPrCuCl
No
CuCl
<2
>98
<2
<2
<2:30:<2
<2
5
a Reaction conditions: allyl phenyl sulfone (1, 0.30 mmol), p-anisidine (2a, 0.36 mmol), NHCCuCl (5.5 mol %), KOt-Bu (5 mol %), toluene
(1.0 M) under N2.
b Determined by 1H NMR spectroscopy against 1,3,5-trimethoxybenzene as the internal standard.
While various NHC–CuCl complexes, such as SIPrCuCl,
IMesCuCl, and SIMesCuCl, also catalyzed amination,
non-negligible amounts of the dimerized side product 4a
was obtained (14–16%, entries 2–4). The reaction of 1 with
2a catalyzed by sterically demanding TripPy-IPr-CuCl
was less efficient, providing the desired product 3a in 47%
yield along with vinyl sulfone 4b (entry 5). After optimiz-
ing the reaction temperature and time, 3a was obtained in
>98% yield with >98% regioselectivity using the IPrCuCl
catalyst under the reaction conditions described in entry
6. The results summarized in entries 8–11 show that the
NHC ligand plays an important role in promoting the addi-
tion of anisidine 2a to allyl sulfone 1, with KOt-Bu also
essential for amination. In the absence of the NHC-CuCl
catalyst, the reaction of 1 with 2a proceeded to completion
in the presence of 5 mol % KOt-Bu, but the desired product
was not obtained (<2% of 3a); instead, 1 was observed to
decompose and also form 30% of the dimerized product 4a
(entry 10). The dimerized product 4a is possibly formed by
the conjugate addition of allyl sulfone 1 to vinyl sulfone
4b, which was formed by the base-promoted isomerization
of allyl sulfone 1 with KOt-Bu or arylamide.11 When allyl
sulfone 1 was treated with 5.5 mol % IPrCuCl and 5 mol
% KOt-Bu at room temperature in the absence of anisidine
Scheme 1. Plausible mechanism for the Cu-catalyzed amination
reaction.
2a, 1 predominantly dimerized to give 4a in 80% yield
(90% conv., 10% 4b). This result reveals that the NHC-
CuOt-Bu complex also promotes the isomerization of allyl
sulfone 1 to vinyl sulfone 4b, resulting in dimerization.
Therefore, 4a is formed during tedious catalytic aminations
(entries 2–4).
Based on our studies and reports by the Gunnoe
group,7b,9d,12 we assume that NHC-Cu-NHAr complex II
derived from ligand exchange between in situ generated
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Cu-catalyzed Hydroaminations of Allylic Sulfones With Aromatic Amines
KOREAN CHEMICAL SOCIETY
Table 2. Cu-catalyzed hydroaminations of allyl sulfone 1 with
various aromatic amines.a
Scheme 2. Cu-catalyzed hydroaminations of γ-substituted allyl
sulfone 5a with anisidine 2a.
Table 3. Cu-catalyzed hydroamination reactions of γ-substituted
allylic sulfones with arylamines.a
a Reaction conditions: allyl phenyl sulfone (1, 0.30 mmol), aniline 2
(0.36 mmol), IPrCuCl (5.5 mol %), KOt-Bu (5 mol %), toluene
(1.0 M) under N2. Yields of isolated products.
bSIMesCuCl was used.
NHC-CuOt-Bu I and anisidine acts as the main catalytic
species (Scheme 1). After NHC-Cu-NHAr II coordinates to
the vinyl sulfone intermediate 4b, obtained from isomeriza-
tion of allyl sulfone 1 promoted by I or II, copper complex
II activated by the electron-donating NHC ligand inserts
into vinyl sulfone 4b. As a result, intermediate IVb, which
has a C─N bond at the β-position and a Cu─C bond at the
α-position with respect to the sulfonyl group, or intermedi-
ate IVa bearing a Cu─O bond, is generated. The reaction
of IVa or IVb with aniline releases protonated product
3 and regenerates copper-amino complex II.
a Reaction conditions: allylic sulfone (5, 0.30 mmol), aniline 2
(0.36 mmol), SIMesCuCl (7.5 mol %), KOt-Bu (7 mol %), toluene
(1.0 M) under N2. Yields of isolated products.
b7.5 mol % Xantphos (4,5-bis(diphenylphosphino)-9,9-
dimethylxanthene) and CuCl were used.
With the optimized reaction conditions in hand, we next
explored the scope of the substituent on the aromatic
amine. A variety of arylamines effectively and selectively
added to the β-position of allyl sulfone 1 in the presence of
5.5 mol % of the NHC-Cu catalyst and 5 mol % KOt-Bu,
as summarized in Table 2. These Cu-catalyzed aminations
successfully provided a broad range of β-substituted
β-amino sulfones in high yields and excellent reg-
ioselectivities. The reaction of 1 with aniline 2b gave the
desired product 3b in 86% yield, and arylamines, including
those substituted with methoxy, tert-butyl, fluoro, chloro,
or bromo substituents at their para, meta, and ortho posi-
tions, were well tolerated, to afford the corresponding
β-amino sulfones 3a–3m in yields of 86–98%. Notably, the
reaction temperature needed to be raised to 60 ꢀC or 80 ꢀC
to more efficiently add several anilines (i.e., 62% of 3d at
40 ꢀC vs. 98% at 60 ꢀC). In addition, the yield of the
desired product was improved when 1 was aminated with
o- or m-bromoaniline using the less sterically demanding
SIMesCuCl catalyst (i.e., 70% of 3m with IPrCuCl
vs. 90% with SIMesCuCl). The catalytic reaction involv-
ing N-methylaniline (2n) was sluggish under the optimized
conditions, affording the desired product 3n in 46% yield
along with 40% of the dimerized side product 4a.
Dihydroindole 2o also participated well in this amination
reaction to give the corresponding amine in excellent yield;
this amine serves as a valuable building block for the syn-
theses of biologically active molecules.13
We subsequently turned our attention to γ-substituted
allyl sulfones bearing a variety of functional groups. As
shown in Scheme 2, SIMesCuCl more effectively catalyzes
the amination of the more sterically demanding
γ-substituted allyl sulfone 5a with anisidine 2a, to afford
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Cu-catalyzed Hydroaminations of Allylic Sulfones With Aromatic Amines
KOREAN CHEMICAL SOCIETY
the desired product 6aa in 80% yield (60% yield with
IPrCuCl). We noted that the yield of the aminated product
6aa could be improved to 90% by adding 1 equiv. of
MeOH. We believe that MeOH promotes the regeneration
of the Cu-amido complex II through the efficient reaction
with copper intermediate IV.9b,14
(HRMS) was performed at the Korea Basic Science Insti-
tute using an electrospray ionization (ESI) time-of-flight
mass spectrometer.
Unless otherwise noted, all reactions were carried out
with distilled solvents under an atmosphere of dry N2 in
oven-dried (130 ꢀC) glassware. Toluene was purified by
distillation from sodium benzophenone ketyl immediately
prior to use unless otherwise specified. Potassium tert-
butoxide was purchased from the Sigma-Aldrich corpora-
tion and used as received. All work-up and purification pro-
cedures were carried out using reagent grade solvents in
air. A variety of NHC–CuCl complexes15 and allyl sul-
fones16 were prepared according to reported experimental
procedures.
Various disubstituted allyl sulfones and arylamines were
catalytically aminated, as summarized in Table 3. Sub-
strates 5b–5e containing n-butyl, n-heptyl, isopentyl, and
phenylpropyl groups at the γ-position of allyl sulfone were
highly efficient and provided the corresponding amines
6ba–6ea in high yields (80–90%) and excellent reg-
ioselectivities under the established reaction conditions.
This catalytic copper amination tolerates synthetically valu-
able functional groups, such as alkenes, nitriles, silyl ethers,
and benzyl ethers; new functionalized β-amino sulfones
6fa–6ja were obtained in yields of 73–83%. Arylamines
substituted with fluoro, chloro, and bromo groups at their
meta or para positions were also smoothly aminated with
γ-substituted allyl sulfone 5a, to give aminated products
6ae–6ak in yields of 63–85%. We noted that the phos-
phine-based copper catalyst formed using a combination of
7.5 mol % Xantphos and CuCl was more effective in reac-
tions involving 5a with meta-substituted anilines 2i–k (i.e.,
85% yield vs. 68% yield with SIMesCuCl).
Representative Experimental Procedure for the Cu-Cat-
alyzed Hydroamination of an β,γ-Unsaturated Sulfone
With an Aromatic Amine
4-Methoxy-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3a).
IPr-CuCl (8.1 mg, 17 × 10−3 mmol), KOt-Bu (1.7 mg,
15 × 10−3 mmol) and 4-methoxyaniline (44 mg,
0.36 mmol) were added to a 4-mL vial charged with a mag-
netic bar in glove box. The vial was sealed with a cap and
was removed from the glove box. The vial was purged with
N2 gas for 5 min, after which toluene (0.2 mL) was added.
The solution was allowed to premix for 30 min and a solu-
tion of (allylsulfonyl)benzene (1, 55 mg, 0.30 mmol) in tol-
uene (0.1 mL) was added to the mixture, which was
allowed to stir at 40 ꢀC for 15 h. The organic layers were
combined, dried over MgSO4, filtered, and concentrated in
vacuo. The crude product was purified by silica gel column
chromatography (EtOAc:hexanes = 1:3) to afford the
desired 3a (86 mg, 0.28 mmol, 94%) as a brown solid. mp.
69–70 ꢀC; 1H NMR (CDCl3, 400 MHz): δ 7.90 (d,
J = 7.3 Hz, 2H), 7.66 (tt, J = 7.3, 1.4 Hz, 1H), 7.55 (t,
J = 7.8 Hz, 2H), 6.72 (dt, J = 9.2, 3.0 Hz, 2H), 6.44 (dt,
J = 9.2, 3.0 Hz, 2H), 3.95–3.87 (m, 1H), 3.74 (s, 3H), 3.43
(br s, 1H), 3.41 (dd, J = 14.2, 4.1 Hz, 1H), 3.05 (dd,
J = 14.2, 7.8 Hz, 1H), 1.43 (d, J = 6.4 Hz, 3H); 13C NMR
(CDCl3, 100 MHz): δ 152.7. 139.7, 139.4, 133.7, 129.3,
127.8, 115.1, 114.9, 60.7, 55.6, 45.5, 21.2; IR (neat): 3387
(w), 2955 (w), 1512 (s), 1443 (m), 1288 (s), 1234 (s), 1134
(s), 1034 (m), 810 (m), 748 (s) cm−1; HRMS (ESI) m/z:
[M + H]+ Calcd for C16H20NO3S 306.1164, Found
306.1164.
Conclusion
A broad range of new and versatile functionalized β-amino
sulfones was synthesized by the Cu-catalyzed hydro-
aminations of easily accessible β,γ-unsaturated sulfones
with aromatic amines. Reactions catalyzed by an N-hetero-
cyclic carbene-copper complex and KOt-Bu proceeded suc-
cessfully with excellent regioselectivities under mild
reaction conditions. This catalytic transformation features
good functional group tolerance, good substrate scope, and
the use of readily available allylic sulfones and catalysts.
The syntheses of valuable amines through the Cu-catalyzed
hydroaminations of other nucleophiles are currently in
progress.
Experimental Section
General Information. Infrared (IR) spectra were recorded
on the wavenumber (cm−1) scale on a ABB MB3000 FT-
IR spectrophotometer. Bands are characterized as strong
(s), medium (m), and weak (w). 1H NMR spectra were
recorded on a JEOL JNM-AL400 (400 MHz) spectrometer.
Chemical shifts are reported in ppm relative to the solvent
resonance of tetramethylsilane as the internal standard
(CDCl3: δ 7.27 ppm. Data are reported as follows: chemical
shift, multiplicity (s = singlet, d = doublet, t = triplet,
q = quartet, sext = sextet, m = multiplet), coupling constant
(Hz), and integration. 13C NMR spectra were recorded on
the abovementioned spectrometer with complete proton
decoupling. Chemical shifts are reported in ppm (relative to
TMS) and were referenced against CDCl3 (δ 77.00) as the
internal standard. High-resolution mass spectrometry
(E)-(2-Methylpent-3-ene-1,3-diyldisulfonyl)dibenzene (4a).
1H NMR (CDCl3, 400 MHz): δ 7.86 (dd, J = 7.3, 0.9 Hz,
2H), 7.76 (d, J = 7.3 Hz, 2H), 7.71–7.67 (m, 1H), 7.63–
7.56 (m, 3H), 7.51 (t, J = 7.6 Hz, 2H), 6.96 (q, J = 7.3 Hz,
1H), 3.48–3.42 (m, 1H), 3.37 (d, J = 7.3 Hz, 2H), 1.94 (d,
J = 7.3 Hz, 3H), 1.23 (d, J = 6.9 Hz, 3H); 13C NMR
(CDCl3, 100 MHz): δ 143.8, 140.1, 139.5, 139.1, 133.8,
133.2, 129.3, 129.1, 127.8, 127.7, 60.1, 27.7, 18.6, 14.5;
IR (neat): 3063 (w), 2986 (w), 2939 (w), 2361 (s), 1450
(w), 1296 (s), 1149 (s), 1088 (m), 733 (s), 697 (s) cm−1
;
HRMS (ESI) m/z: [M + H]+ Calcd for C18H21O4S2
365.0881, Found 365.0881.
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Cu-catalyzed Hydroaminations of Allylic Sulfones With Aromatic Amines
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(E)-(Prop-1-en-1-ylsulfonyl)benzene (4b). 1H NMR
(CDCl3, 400 MHz)17: δ 7.89 (d, J = 7.3 Hz, 2H), 7.63 (t,
J = 7.6 Hz, 1H), 7.55 (t, J = 7.6 Hz, 2H), 7.05–6.96 (m,
1H), 6.36 (dq, J = 14.9, 1.6 Hz, 1H), 1.94 (dd, J = 7.3,
1.8 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 142.6, 140.4,
133.2, 131.6, 129.1, 127.4, 17.3.
0.27 mmol) as a light yellow solid. The crude product was
purified using silica gel column chromatography (EtOAc:
hexanes = 1:5). mp 113–114 ꢀC; 1H NMR (CDCl3,
400 MHz): δ 7.89 (dd, J = 8.0, 1.1 Hz, 2H), 7.67 (t,
J = 7.8 Hz, 1H), 7.56 (t, J = 7.6 Hz, 2H), 7.06 (d,
J = 8.7 Hz, 2H), 6.36 (d, J = 8.7 Hz, 2H), 3.98–3.90 (m,
1H), 3.76 (br s, 1H), 3.36 (dd, J = 14.2, 4.6 Hz, 1H), 3.09
(dd, J = 14.2, 7.3 Hz, 1H), 1.44 (d, J = 6.4 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 144.1, 139.5, 133.9, 129.3,
129.2, 127.9, 122.7, 114.3, 60.6, 44.6, 21.2; IR (neat):
3387 (m), 2962 (w), 2932 (w), 1597 (s), 1497 (s), 1450
(w), 1396 (w), 1296 (s), 1134 (s), 1080 (m), 887 (m),
810 (s), 741 (s), 679 (s) cm−1; HRMS (ESI) m/z: [M + H]+
Calcd for C15H17ClNO2S 310.0669, Found 310.0669.
N-(1-(Phenylsulfonyl)propan-2-yl)aniline (3b). Compound
3b was synthesized in 86% yield (71 mg, 0.26 mmol) as a
light orange solid. The crude product was purified using sil-
ica gel column chromatography (EtOAc:hexanes = 1:4).
1
mp 79–80 ꢀC; H NMR (CDCl3, 400 MHz): δ 7.92 (dd,
J = 8.2, 1.1 Hz, 2H), 7.67 (t, J = 7.8 Hz, 1H), 7.56 (t,
J = 7.8 Hz, 2H), 7.13 (t, J = 8.2 Hz, 2H), 6.73 (t,
J = 7.3 Hz, 1H), 6.44 (d, J = 8.2 Hz, 2H), 4.03–3.99 (m,
1H), 3.69 (brs, 1H), 3.43 (dd, J = 14.2, 4.1 Hz, 1H), 3.08
(dd, J = 14.2, 7.3 Hz, 1H), 1.47 (d, J = 6.4 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 145.4, 139.7, 133.8, 129.4,
129.3, 127.9, 118.1, 113.2, 60.7, 44.4, 21.3; IR (neat):
2978 (w), 2885 (w), 2854 (w), 2381 (m), 2330 (m), 1605
(s), 1504 (s), 1304 (s), 1149 (s), 748 (s) cm−1; HRMS
(ESI) m/z: [M + H]+ Calcd for C15H18NO2S 276.1058,
Found 276.1058 Supporting Information.
4-Bromo-N-(1-(phenylsulfonyl)propan-2-yl)aniline
(3f).
Compound 3f was synthesized in 97% yield (103 mg,
0.29 mmol) as a white solid. The crude product was puri-
fied using silica gel column chromatography (EtOAc:hex-
anes
=
1:5). mp 114–115 ꢀC; 1H NMR (CDCl3,
400 MHz): δ 7.89 (dd, J = 8.0, 1.1 Hz, 2H), 7.68 (t,
J = 7.8 Hz, 1H), 7.56 (t, J = 7.6 Hz, 2H), 7.16 (d,
J = 8.7 Hz, 2H), 6.30 (d, J = 8.7 Hz, 2H), 3.98–3.90 (m,
1H), 3.79 (br s, 1H), 3.36 (dd, J = 14.2, 4.6 Hz, 1H), 3.08
(dd, J = 14.2, 7.3 Hz, 1H), 1.44 (d, J = 6.4 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 144.5, 139.4, 133.9, 132.1,
129.4, 127.8, 114.6, 109.7, 60.5, 44.4, 21.2; IR (neat):
3433 (w), 2978 (w), 2924 (w), 1589 (m), 1497 (s), 1396
(w), 1296 (s), 1257 (m), 1142 (s), 1080 (s), 995 (w),
802 (s), 748 (s) cm−1; HRMS (ESI) m/z: [M + H]+ Calcd
for C15H17BrNO2S 354.0163, Found 354.0161.
4-(tert-Butyl)-N-(1-(phenylsulfonyl)propan-2-yl)aniline
(3c). Compound 3c was synthesized in 96% yield (95 mg,
0.29 mmol) as a light yellow oil. The crude product was
purified using silica gel column chromatography (EtOAc:
1
hexanes = 1:5). H NMR (CDCl3, 400 MHz): δ 7.93 (dd,
J = 7.2, 1.4 Hz, 2H), 7.68 (t, J = 6.9 Hz, 1H), 7.57 (t,
J = 7.8 Hz, 2H), 7.17 (dd, J = 8.7, 1.4 Hz, 2H), 6.41 (dd,
J = 8.7, 1.4 Hz, 2H), 4.04–3.96 (m, 1H), 3.61 (br s, 1H),
3.46 (dd, J = 14.2, 4.1 Hz, 1H), 3.06 (ddd, J = 14.1, 7.9,
1.4 Hz, 1H), 1.47 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 1.4 Hz,
9H); 13C NMR (CDCl3, 100 MHz): δ 143.0, 140.9, 139.7,
133.8, 129.3, 127.9, 126.2, 112.9, 60.8, 44.5, 33.8, 31.4,
21.4; IR (neat): 3371 (w), 2970 (m), 2870 (m), 2361 (s),
1612 (m), 1520 (s), 1450 (w), 1304 (s), 1257 (w), 1142 (s),
1088 (w), 825 (s), 748 (s) cm−1; HRMS (ESI) m/z: [M
+ H]+ Calcd for C19H26NO2S 332.1684, Found 332.1685.
4-Fluoro-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3d).
Compound 3d was synthesized in 98% yield (86 mg,
0.29 mmol) as a light yellow solid. The crude product was
purified using silica gel column chromatography (EtOAc:
3-Methoxy-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3g).
Compound 3g was synthesized in 98% yield (90 mg,
0.29 mmol) as a white solid. The crude product was puri-
fied using silica gel column chromatography (EtOAc:hex-
1
anes = 1:3). mp 55–56 ꢀC; H NMR (CDCl3, 400 MHz): δ
7.91 (d, J = 7.7 Hz, 2H), 7.67 (tt, J = 7.0, 1.3 Hz, 1H),
7.56 (t, J = 7.8 Hz, 2H), 7.04 (t, J = 8.2 Hz, 1H), 6.32 (dd,
J = 8.3 Hz, 1H), 6.12–6.07 (m, 2H), 4.21 (br s, 1H), 4.05–
3.98 (m, 1H), 3.76 (s, 3H), 3.46 (dd, J = 14.2, 4.1 Hz, 1H),
3.10 (dd, J = 14.2, 7.8 Hz, 1H), 1.47 (d, J = 6.4 Hz, 3H);
13C NMR (CDCl3, 100 MHz): δ 160.8, 146.9, 139.6,
133.7, 130.1, 129.3, 127.8, 105.9, 103.5, 99.0, 60.7, 55.0,
44.3, 21.2; IR (neat): 3387 (m), 2970 (w), 1597 (s), 1288
(m), 1211 (m), 1072 (w), 748 (s), 679 (s) cm−1; HRMS
(ESI) m/z: [M + H]+ Calcd for C16H20NO3S 306.1164,
Found 306.1164.
hexanes
=
1:5). mp 96–97 ꢀC; 1H NMR (CDCl3,
400 MHz): δ 7.89 (d, J = 6.9 Hz, 2H), 7.66 (tt, J = 7.4,
1.4 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 6.83 (t, J = 8.7 Hz,
2H), 6.41–6.36 (m, 2H), 3.95–3.88 (m, 1H), 3.53 (br s,
1H), 3.37 (dd, J = 14.2, 4.1 Hz, 1H), 3.08 (dd, J = 14.2,
7.3 Hz, 1H), 1.42 (d, J = 1.4 Hz, 3H); 13C NMR (CDCl3,
100 MHz): δ 156.0 (d, J = 118 Hz), 141.9, 139.6, 133.8,
129.3, 127.8, 115.8 (d, J = 11.1 Hz), 114.2 (d, J = 3.9 Hz),
60.6, 45.1, 21.2; IR (neat): 3425 (m), 2924 (w), 1612 (w),
1512 (s), 1296 (s), 1211 (s), 1142 (s), 1080 (m), 818 (s),
748 (s), 687 (s) cm−1; HRMS (ESI) m/z: [M + H]+ Calcd
for C15H17FNO2S 294.0964, Found 294.0964.
3-Fluoro-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3h).
Compound 3h was synthesized in 95% yield (84 mg,
0.29 mmol) as a white solid. The crude product was puri-
fied using silica gel column chromatography (EtOAc:hex-
1
anes = 1:4). mp 50–51 ꢀC; H NMR (CDCl3, 400 MHz): δ
7.90 (dd, J = 8.2, 1.4 Hz, 2H), 7.67 (t, J = 7.3 Hz, 1H),
7.56 (t, J = 7.3 Hz, 2H), 7.05 (td, J = 8.2, 6.4 Hz, 1H),
6.38 (td, J = 8.3, 2.5 Hz, 1H), 6.20 (dd, J = 8.0, 2.5 Hz,
1H), 6.06 (dt, J = 11.6, 2.5 Hz, 1H), 3.92 (br s, 2H), 3.39
(dd, J = 14.2, 2.7 Hz, 1H), 3.11 (dd, J = 14.2, 6.9 Hz, 1H),
4-Chloro-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3e).
Compound 3e was synthesized in 90% yield (83 mg,
Bull. Korean Chem. Soc. 2021, Vol. 42, 699–708
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703

BULLETIN OF THE
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Cu-catalyzed Hydroaminations of Allylic Sulfones With Aromatic Amines
KOREAN CHEMICAL SOCIETY
1.44 (d, J = 5.5 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ
163.9 (d, J = 243.8 Hz), 147.3 (d, J = 10.6 Hz), 139.3,
133.9, 130.5 (d, J = 9.6 Hz), 129.4, 127.8, 108.8 (d,
J = 1.9 Hz), 104.4 (d, J = 21.2 Hz), 99.7 (d, J = 25.0 Hz),
60.6, 44.4, 21.1; IR (neat): 2998 (w), 2885 (w), 2854 (w),
2368 (m), 2330 (m), 1620 (s), 1520 (m), 1497 (m), 1296
(s), 1149 (s), 1080 (m), 849 (m), 756 (m) cm−1; HRMS
(ESI) m/z: [M + H]+ Calcd for C15H17FNO2S 294.0964,
Found 294.0963.
cm−1; HRMS (ESI) m/z: [M + H]+ Calcd for C16H20NO3S
306.1164, Found 306.1164.
2-Fluoro-N-(1-(phenylsulfonyl)propan-2-yl)aniline
(3l).
Compound 3l was synthesized in 88% yield (77 mg,
0.26 mmol) as white solid. The crude product was purified
using silica gel column chromatography (EtOAc:hex-
1
anes = 1:4). mp 62–63 ꢀC; H NMR (CDCl3, 400 MHz): δ
7.91 (dd, J = 8.5, 1.1 Hz, 2H), 7.67 (t, J = 7.3 Hz, 1H),
7.55 (t, J = 7.3 Hz, 2H), 6.97–6.91 (m, 2H), 6.64 (tdd,
J = 7.7, 4.9, 1.6 Hz, 1H), 6.49 (td, J = 8.5, 1.4 Hz, 1H),
4.07–4.03 (m, 1H), 3.88 (d, J = 6.4 Hz, 1H), 3.42 (dd,
J = 14.2, 3.7 Hz, 1H), 3.11 (dd, J = 14.2, 7.8 Hz, 1H), 1.49
(d, J = 6.4 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 151.4
(d, J = 151.4, Hz), 139.6, 134.0, 133.8, 129.3, 127.8, 124.7
(d, J = 3.8 Hz), 117.4 (d, J = 6.7 Hz), 114.7 (d,
J = 18.3 Hz), 112.1 (d, J = 2.9 Hz), 60.8, 44.0, 21.3; IR
(neat): 3394 (w), 2986 (w), 2361 (s), 1620 (m), 1520 (s),
1450 (m), 1304 (s), 1142 (s), 748 (s) cm−1; HRMS (ESI)
m/z: [M + H]+ Calcd for C15H17FNO2S 294.0964, Found
294.0964.
2-Bromo-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3m).
Compound 3m was synthesized in 90% yield (95 mg,
0.27 mmol) as a brown oil. The crude product was purified
using silica gel column chromatography (EtOAc:hex-
anes = 1:4). 1H NMR (CDCl3, 400 MHz): δ 7.89 (dd,
J = 7.8 Hz, 2H), 7.65 (t, J = 7.8 Hz, 1H), 7.54 (t,
J = 7.8 Hz, 2H), 7.38 (dd, J = 7.8, 1.4 Hz, 1H), 7.10 (td,
J = 7.8, 0.9 Hz, 1H), 6.57 (t, J = 7.8 Hz, 1H), 6.43 (d,
J = 7.8 Hz, 1H), 4.24 (br s, 1H), 4.10–4.06 (m, 1H), 3.39
(dd, J = 14.2, 3.7 Hz, 1H), 3.10 (dd, J = 14.2, 7.8 Hz, 1H),
1.50 (d, J = 6.4 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ
142.2, 139.5, 133.8, 132.7, 129.3, 128.6, 127.8, 118.4,
111.3, 109.9, 60.8, 44.1, 21.3; IR (neat): 2978 (w), 2854
(w), 2381 (m), 2322 (m), 1597 (m), 1512 (s), 1450 (m),
1304 (s), 1142 (s), 748 (s) cm−1; HRMS (ESI) m/z: [M
+ H]+ Calcd for C15H17BrNO2S 354.0163, Found
354.0163.
3-Chloro-N-(1-(phenylsulfonyl)propan-2-yl)aniline
(3i).
Compound 3i was synthesized in 88% yield (82 mg,
0.26 mmol) as a light pink solid. The crude product was
purified using silica gel column chromatography (EtOAc:
hexanes
=
1:4). mp 76–77 ꢀC; 1H NMR (CDCl3,
400 MHz): δ 7.89 (d, J = 7.3 Hz, 2H), 7.67 (t, J = 7.8 Hz,
1H), 7.56 (t, J = 7.8 Hz, 2H), 7.02 (t, J = 8.0 Hz, 1H), 6.66
(dd, J = 7.8, 1.8 Hz, 1H), 6.32 (t, J = 8.2 Hz, 2H), 3.93–
3.88 (m, 2H), 3.38 (dd, J = 14.4, 3.9 Hz, 1H), 3.10 (dd,
J = 14.2, 6.0 Hz, 1H), 1.43 (d, J = 6.0 Hz, 3H); 13C NMR
(CDCl3, 100 MHz): δ 146.7, 139.3, 134.9, 133.9, 130.3,
129.4, 127.8, 117.8, 112.6, 111.2, 60.5, 44.3, 21.0; IR
(neat): 3394 (w), 2854 (w), 2361 (s), 2330 (s), 1597 (m),
1497 (m), 1296 (m), 1142 (s), 1080 (w), 741 (m) cm−1
;
HRMS (ESI) m/z: [M + H]+ Calcd for C15H17ClNO2S
310.0669, Found 310.0670.
3-Bromo-N-(1-(phenylsulfonyl)propan-2-yl)aniline
(3j).
Compound 3j was synthesized in 96% yield (102 mg,
0.29 mmol) as a yellow oil. The crude product was purified
using silica gel column chromatography (EtOAc:hex-
anes = 1:4). 1H NMR (CDCl3, 400 MHz): δ 7.89 (d,
J = 8.2 Hz, 2H), 7.67 (t, J = 7.3 Hz, 1H), 7.56 (t,
J = 7.8 Hz, 2H), 6.96 (t, J = 8.2 Hz, 1H), 6.81 (d,
J = 7.8 Hz, 1H), 6.53 (s, 1H), 6.35 (dd, J = 8.2, 2.3 Hz,
1H), 3.90 (m, 2H), 3.38 (dd, J = 14.4, 4.3 Hz, 1H), 3.11
(dd, J = 14.2, 6.9 Hz, 1H), 1.43 (d, J = 5.9 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 146.8, 139.3, 133.9, 130.7,
129.4, 127.8, 123.2, 120.7, 115.6, 111.6, 60.5, 44.3, 21.0;
IR (neat): 3387 (m), 2978 (m), 2870 (w), 2368 (w), 2330
(w), 1597 (s), 1504 (m), 1481 (m), 1296 (s), 1142 (s), 1080
(m), 748 (s) cm−1; HRMS (ESI) m/z: [M + H]+ Calcd for
C15H17BrNO2S 354.0163, Found 354.0164.
N-Methyl-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3n).
Compound 3n was synthesized in 46% yield (40 mg,
0.14 mmol) as a brown oil. The crude product was purified
using silica gel column chromatography (EtOAc:hex-
anes = 1:4). 1H NMR (CDCl3, 400 MHz): δ 7.81 (d,
J = 7.3 Hz, 2H), 7.60 (t, J = 7.8 Hz, 1H), 7.54 (t,
J = 7.3 Hz, 2H), 7.21 (dd, J = 8.9, 7.1 Hz, 2H), 6.77 (t,
J = 7.1 Hz, 1H), 6.70 (d, J = 8.2 Hz, 2H), 4.57 (sext,
J = 6.8 Hz, 1H), 3.46 (dd, J = 14.6, 6.9 Hz, 1H), 3.20 (dd,
J = 14.4, 6.6 Hz, 1H), 2.37 (s, 3H), 1.30 (d, J = 6.4 Hz,
3H); 13C NMR (CDCl3, 100 MHz): δ 148.7, 139.6, 133.5,
129.2, 129.0, 127.9, 118.0, 114.0, 59.2, 49.8, 30.0, 17.3;
IR (neat): 3063 (w), 2978 (m), 2924 (m), 2870 (m), 1597
(s), 1504 (s), 1450 (m), 1389 (m), 1304 (s), 1142 (s), 748
2-Methoxy-N-(1-(phenylsulfonyl)propan-2-yl)aniline (3k).
Compound 3k was synthesized in 93% yield (85 mg,
0.28 mmol) as a white solid. The crude product was puri-
fied using silica gel column chromatography (EtOAc:hex-
1
anes = 1:3). mp 53–54 ꢀC; H NMR (CDCl3, 400 MHz): δ
7.93 (d, J = 6.9 Hz, 2H), 7.67 (tt, J = 7.3 Hz, 1.6 Hz, 1H),
7.56 (t, J = 7.7 Hz, 2H), 6.81–6.68 (m, 3H), 6.38 (d,
J = 7.8 Hz, 1H), 4.45 (br s, 1H), 4.07–4.00 (m, 1H), 3.80
(s, 3H), 3.49 (dd, J = 14.2, 3.7 Hz, 1H), 3.07 (dd, J = 14.2,
8.2 Hz, 1H), 1.52 (d, J = 6.4 Hz, 3H); 13C NMR (CDCl3,
100 MHz): δ 146.8, 139.7, 135.2, 133.7, 129.2, 127.9,
121.2, 117.2, 109.9, 109.6, 60.8, 55.2, 43.7, 21.4; IR
(neat): 3425 (w), 2978 (w), 2353 (w), 1520 (m), 1458 (m),
1304 (m), 1250 (m), 1227 (m), 1142 (m), 1028 (m), 741 (s)
;
(s) cm−1 HRMS (ESI) m/z: [M + Na]+ Calcd for
C16H19NNaO2S 312.1034, Found 312.1034.
1-(1-(Phenylsulfonyl)propan-2-yl)indoline
(3o).
Compound 3o was synthesized in 96% yield (87 mg,
0.29 mmol) as a brown oil. The crude product was purified
Bull. Korean Chem. Soc. 2021, Vol. 42, 699–708
© 2021 Korean Chemical Society, Seoul & Wiley-VCH GmbH
www.bkcs.wiley-vch.de
704

BULLETIN OF THE
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Cu-catalyzed Hydroaminations of Allylic Sulfones With Aromatic Amines
KOREAN CHEMICAL SOCIETY
using silica gel column chromatography (EtOAc:hex-
anes = 1:4 with 1% Et3N). H NMR (CDCl3, 400 MHz): δ
J = 14.2, 4.1 Hz, 1H), 3.14 (dd, J = 14.2, 6.9 Hz, 1H),
1.94–1.86 (m, 1H), 1.60–1.53 (m, 1H), 1.43–1.26 (m,
12H), 0.89 (t, J = 6.6 Hz, 3H); 13C NMR (CDCl3,
100 MHz): δ 152.3, 140.0, 139.9, 133.6, 129.1, 127.8,
114.9, 114.6, 59.4, 55.6, 49.8, 35.1, 31.7, 29.3, 29.2, 29.1,
25.7, 22.5, 14.0; IR (neat): 3364 (w), 2916 (w), 2847 (w),
1512 (s), 1458 (m), 1304 (s), 1242 (s), 1142 (s), 1088 (m),
1041 (m), 825 (s), 741 (s) cm−1; HRMS (ESI) m/z: [M
+ H]+ Calcd for C23H34NO3S 404.2259, Found 404.2256.
4-Methoxy-N-(6-methyl-1-(phenylsulfonyl)heptan-2-yl)
aniline (6da). Compound 6da was synthesized in 80%
yield (90 mg, 0.24 mmol) as an ivory solid. The crude
product was purified using silica gel column chromatogra-
phy (EtOAc:hexanes = 1:1). mp 83–84 ꢀC; 1H NMR
(CDCl3, 400 MHz): δ 7.88 (d, J = 7.3 Hz, 2H), 7.65 (t,
J = 7.3 Hz, 1H), 7.53 (t, J = 7.8 Hz, 2H), 6.73 (d,
J = 8.7 Hz, 2H), 6.43 (d, J = 8.7 Hz, 2H), 3.82–3.76 (m,
1H), 3.74 (s, 3H), 3.36 (br s, 1H), 3.34 (d, J = 14.3,
4.3 Hz, 1H), 3.14 (dd, J = 14.2, 6.9 Hz, 1H), 1.94–1.86 (m,
1H), 1.61–1.43 (m, 3H), 1.41–1.30 (m, 1H), 1.20–1.13 (m,
2H), 0.86 (d, J = 6.4 Hz, 3H), 0.85(d, J = 6.4 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ.152.4, 140.0, 139.9, 133.6,
129.2, 127.8, 114.9, 114.7, 59.4, 55.7, 50.0, 38.5, 35.4,
27.8, 23.6, 22.5, 22.4; IR (neat): 2955 (w), 2908 (w), 2870
(w), 2253 (w), 1512 (m), 1304 (m), 1242 (m), 1149 (m),
910 (s), 733 (s) cm−1; HRMS (ESI) m/z: [M + H]+ Calcd
for C21H30NO3S 376.1946, Found 376.1948.
1
7.88 (d, J = 7.3Hz, 2H), 7.63 (t, J = 7.3 Hz, 1H), 7.50 (t,
J = 7.8 Hz, 2H), 7.03–6.99 (m, 2H), 6.64 (t, J = 7.3 Hz,
1H), 6.28 (d, J = 7.8 Hz, 1H), 4.27 (sext, J = 6.7 Hz, 1H),
3.41–3.29 (m, 2H), 3.16 (dd, J = 14.2, 7.3 Hz, 1H), 2.95–
2.79 (m, 2H), 2.63 (ddd, J = 15.6, 9.1, 6.9 Hz, 1H), 1.39
(d, J = 6.9 Hz, 3 H); 13C NMR (CDCl3, 100 MHz): δ
149.4, 139.9, 133.5, 129.8, 129.1, 127.9, 127.4, 124.5,
118.0, 107.1, 58.5, 46.3, 46.0, 27.9, 17.0; IR (neat): 3055
(w), 2978 (m), 2932 (m), 2854 (m), 1605 (s), 1489 (s),
1450 (m), 1396 (m), 1304 (s), 1257 (s), 1142 (s), 1080 (s),
741 (s) cm−1; HRMS (ESI) m/z: [M + Na]+ Calcd for
C17H19NNaO2S 324.1034, Found 324.1033.
4-Methoxy-N-(1-(phenylsulfonyl)pentan-2-yl)aniline
(6aa). Compound 6aa was synthesized in 90% yield
(90 mg, 0.27 mmol) as an ivory solid. The crude product
was purified using silica gel column chromatography
(EtOAc:hexanes = 1:5). mp 106–107 ꢀC; 1H NMR
(CDCl3, 400 MHz): δ 7.88 (d, J = 7.3 Hz, 2H), 7.64 (t,
J = 7.3 Hz, 1H), 7.55–7.51 (m, 2H), 6.72 (d, J = 8.9 Hz,
2H), 6.43 (d, J = 8.9 Hz, 2H), 3.84–3.80 (m, 1H), 3.74 (s,
3H), 3.40 (br s, 1H), 3.34 (dd, J = 14.2, 4.6 Hz, 1H), 3.14
(dd, J = 14.2, 6.9 Hz, 1H), 1.94–1.86 (m, 1H), 1.62–1.53
(m, 1H), 1.50–1.34 (m, 2H), 0.92 (t, J = 7.3 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 152.4, 140.0, 139.9, 133.6,
129.2, 127.6, 114.9, 114.7, 59.4, 55.7, 49.6, 37.2, 19.0,
13.7; IR (neat): 3394 (w), 3009 (w), 2947 (w), 1520 (s),
1450 (m), 1296 (s), 1234 (s), 1142 (s), 1080 (m), 1034 (m),
810 (m), 748 (s) cm−1; HRMS (ESI) m/z: [M + Na]+ Calcd
for C18H23NNaO3S 356.1296, Found 356.1298.
4-Methoxy-N-(6-phenyl-1-(phenylsulfonyl)hexan-2-yl)ani-
line (6ea). Compound 6ea was synthesized in 85% yield
(108 mg, 0.26 mmol) as an ivory solid. The crude product
was purified using silica gel column chromatography
1
4-Methoxy-N-(1-(phenylsulfonyl)heptan-2-yl)aniline
(6ba). Compound 6ba was synthesized in 90% yield
(98 mg, 0.27 mmol) as an ivory solid. The crude product
was purified using silica gel column chromatography
(EtOAc:hexanes = 1:5). mp 76–77 ꢀC; H NMR (CDCl3,
400 MHz): δ 7.89 (d, J = 7.3 Hz, 2H), 7.65 (t, J = 7.3 Hz,
1H), 7.54 (t, J = 7.8 Hz, 2H), 7.31 (t, J = 7.3 Hz, 2H),
7.23–7.18 (m, 3H), 6.75 (d, J = 8.7 Hz, 2H), 6.45 (d,
J = 8.7 Hz, 2H), 3.85–3.79 (m, 1H), 3.76 (s, 3H), 3.45 (br
s, 1H), 3.35 (dd, J = 14.2, 4.1 Hz, 1H), 3.15 (dd, J = 14.2,
6.9 Hz, 1H), 2.62 (t, J = 7.5 Hz, 2H), 2.04–1.95 (m, 1H),
1.70–1.59 (m, 3H), 1.57–1.39 (m, 2H); 13C NMR (CDCl3,
100 MHz): δ 152.4, 142.1. 139.9, 139.8, 133.6, 129.2,
128.3, 128.2, 127.7, 125.6, 114.9, 114.7, 59.3, 55.6, 49.8,
35.5, 34.8, 30.9, 25.3; IR (neat): 3109 (w), 2970 (w), 1589
(w), 1497 (w), 1450 (w), 1304 (s), 1142 (s), 1088 (m),
972 (s), 895 (m), 741 (s), 687 (s) cm−1; HRMS (ESI) m/z:
[M + H]+ Calcd for C25H30NO3S 424.1946, Found
424.1945.
(Z)-4-Methoxy-N-(1-(phenylsulfonyl)trideca-2,12-dien-2-
yl)aniline (6fa). Compound 6fa was synthesized in 83%
yield (110 mg, 0.25 mmol) as an ivory solid. The crude
product was purified using silica gel column chromatogra-
phy (EtOAc:hexanes = 1:1). mp 76–77 ꢀC; 1H NMR
(CDCl3, 400 MHz): δ 7.88 (d, J = 6.9 Hz, 2H), 7.65 (t,
J = 7.8 Hz, 1H), 7.54 (t, J = 7.8 Hz, 2H), 6.73 (d,
J = 9.1 Hz, 2H), 6.44 (d, J = 8.7 Hz, 2H), 5.82 (ddt,
J = 17.0, 10.3, 6.7 Hz, 1H), 5.00 (dq, J = 17.0, 1.8 Hz,
1H), 4.94 (dt, J = 10.2, 1.1 Hz, 1H), 3.82–3.77 (m, 1H),
1
(EtOAc:hexanes = 1:5). mp 57–58 ꢀC; H NMR (CDCl3,
400 MHz): δ 7.88 (d, J = 7.8 Hz, 2H), 7.65 (t, J = 7.3 Hz,
1H), 7.56–7.52 (m, 2H), 6.73 (d, J = 8.7 Hz, 2H), 6.44 (d,
J = 8.7 Hz, 2H), 3.78 (br s, 1H), 3.74 (s, 3H), 3.51 (br s,
1H), 3.34 (dd, J = 14.3, 4.3 Hz, 1H), 3.15 (dd, J = 14.3,
6.4 Hz, 1H), 1.97–1.88 (m, 1H), 1.63–1.54 (m, 1H), 1.45–
1.35 (m, 2H), 1.35–1.25 (m, 4H), 0.88 (t, J = 6.6 Hz, 3H);
13C NMR (CDCl3, 100 MHz): δ152.5, 139.9, 139.9, 133.7,
129.2, 127.9, 115.0, 114.9, 59.4, 55.7, 50.0, 35.1, 31.5,
25.5, 22.5, 14.0; IR (neat): 3402 (m), 3032 (w), 2932 (m),
1520 (s), 1450 (m), 1296 (s), 1250 (s), 1134 (s), 1080 (m),
1034 (m), 810 (s), 748 (s) cm−1; HRMS (ESI) m/z: [M
+ H]+ Calcd for C20H28NO3S 362.1790, Found 362.1787.
4-Methoxy-N-(1-(phenylsulfonyl)decan-2-yl)aniline (6ca).
Compound 6ca was synthesized in 87% yield (105 mg,
0.26 mmol) as an ivory solid. The crude product was puri-
fied using silica gel column chromatography (EtOAc:hex-
1
anes = 1:5). mp 54–55 ꢀC; H NMR (CDCl3, 400 MHz): δ
7.87 (d, J = 7.8 Hz, 2H), 7.64 (t, J = 7.3 Hz, 1H), 7.54–
7.51 (m, 2H), 6.72 (d, J = 8.5 Hz, 2H), 6.42 (d, J = 8.5 Hz,
2H), 3.78 (s, 1H), 3.73 (s, 3H), 3.43 (br s, 1H), 3.33 (dd,
Bull. Korean Chem. Soc. 2021, Vol. 42, 699–708
© 2021 Korean Chemical Society, Seoul & Wiley-VCH GmbH
www.bkcs.wiley-vch.de
705

BULLETIN OF THE
Article
Cu-catalyzed Hydroaminations of Allylic Sulfones With Aromatic Amines
KOREAN CHEMICAL SOCIETY
3.74 (s, 3H), 3.48 (br s, 1H), 3.34 (dd, J = 14.2, 4.6 Hz,
1H), 3.15 (dd, J = 14.2, 6.9 Hz, 1H), 2.07–2.02 (m, 2H),
1.92 (ddt, J = 14.2, 9.7, 5.2 Hz, 1H), 1.63–1.53 (m, 1H),
1.44–1.34 (m, 4H), 1.26 (s, 10H); 13C NMR (CDCl3,
100 MHz): δ 152.5, 139.9, 139.9, 139.2, 133.6, 129.2,
127.9, 114.9, 114.8, 114.1, 99.9, 59.4, 55.7, 50.0, 35.1,
33.7, 29.4, 29.4, 29.3, 29.1, 28.9, 25.8; IR (neat): 3387
(w), 2924 (s), 2854 (m), 1512 (s), 1450 (m), 1304 (s), 1242
(s), 1142 (s), 1041 (m), 910 (s), 825 (m), 733 (s); HRMS
(ESI) m/z: [M + H]+ Calcd for C26H38NO3S 444.2572,
Found 444.2571.
(dd, J = 14.2, 6.9 Hz, 1H), 2.04–1.97 (m, 1H), 1.73–1.58
(m, 3H), 0.90 (s, 9H), 0.05 (s, 6H); 13C NMR (CDCl3,
100 MHz): δ 140.0, 137.4, 137.1, 133.7, 133.5, 129.3,
127.9, 115.0, 62.6, 55.7, 44.2, 29.0, 25.9, 20.9, 18.3, 17.8,
−5.3; IR (neat): 3379 (w), 2932 (m), 2862 (m), 2361 (s),
1512 (s), 1450 (w), 1304 (m), 1250 (s), 1149 (s), 1119 (s),
1041 (w), 833 (s), 779 (m) cm−1; HRMS (ESI) m/z: [M
+ H]+ Calcd for C24H38NO4SSi 464.2291, Found
464.2289.
N-(7-(Benzyloxy)-1-(phenylsulfonyl)heptan-2-yl)-4-meth-
oxyaniline (6ja). Compound 6ja was synthesized in 80%
yield (112 mg, 0.24 mmol) as a brown oil. The crude prod-
uct was purified using silica gel column chromatography
(Z)-4-Methoxy-N-(1-(phenylsulfonyl)non-6-en-2-yl)aniline
(6ga). Compound 6ga was synthesized in 73% yield
(85 mg, 0.22 mmol) as an orange solid. The crude product
was purified using silica gel column chromatography
1
(EtOAc:hexanes = 1:3). H NMR (CDCl3, 400 MHz): δ
7.88 (dd, J = 8.5, 1.1 Hz, 2H), 7.65 (t, J = 7.3 Hz, 1H),
7.53 (t, J = 7.8 Hz, 2H), 7.36–7.34 (m, 4H), 7.31-7.28 (m,
1H), 6.73 (d, J = 8.7 Hz, 2H), 6.42 (d, J = 9.1 Hz, 2H),
4.51 (s, 2H), 3.82-3.76 (m, 1H), 3.75 (s, 3H), 3.46 (t, J
= 6.4 Hz, 2H), 3.39 (s, 1H), 3.33 (dd, J = 14.2, 4.1 Hz,
1H), 3.12 (dd, J = 14.2, 6.9 Hz, 1H), 2.00-1.92 (m, 1H),
1.65–1.53 (m, 3H), 1.51–1.37 (m, 4H); 13C NMR (CDCl3,
100 MHz): 152.3, 139.9, 139.7, 138.5, 133.7, 129.2, 128.3,
127.8, 127.5, 127.4, 114.8, 114.6, 72.8, 70.1, 49.2, 55.6,
49.7, 35.1, 29.5, 25.9, 25.6; IR (neat): 3387 (w), 2978 (m),
2932 (m), 2862 (m), 2361 (s), 1512 (s), 1450 (m), 1381
(w), 1304 (s), 1242 (s), 1142 (s), 1034 (m), 825 (m), 748
1
(EtOAc:hexanes = 1:3). mp 55–56 ꢀC; H NMR (CDCl3,
400 MHz): δ 7.88 (d, J = 7.3 Hz, 2H), 7.65 (t, J = 7.6 Hz,
1H), 7.54 (t, J = 7.8 Hz, 2H), 6.73 (d, J = 8.7 Hz, 2H),
6.43 (d, J = 8.7 Hz, 2H), 5.42–5.35 (m, 1H), 5.31–5.25 (m,
1H), 3.83–3.77 (m, 1H), 3.75 (s, 3H), 3.36 (br s, 1H), 3.34
(dd, J = 14.2, 4.6 Hz, 1H), 3.14 (dd, J = 14.4, 6.6 Hz, 1H),
2.07–1.90 (m, 5H), 1.63–1.40 (m, 3H), 0.95 (t, J = 7.5 Hz,
3H); 13C NMR (CDCl3, 100 MHz): δ 152.5, 140.0, 139.9,
133.7, 132.3, 129.2, 128.2, 127.9, 115.0, 114.8, 59.5, 55.7,
50.0, 34.8, 26.7, 25.9, 20.5, 14.3; IR (neat): 3394 (w),
2924 (w), 2862 (w), 1690 (w), 1512 (s), 1450 (m), 1288
(s), 1242 (s), 1142 (s), 1080 (m), 1034 (s), 964 (w),
810 (s), 741 (s) cm−1; HRMS (ESI) m/z: [M + H]+ Calcd
for C22H30NO3S 388.1946, Found 388.1946.
(s) cm−1
;
HRMS (ESI) m/z: [M+H]+ Calcd for
C27H34NO4S 468.2209, Found 468.2209.
4-Fluoro-N-(1-(phenylsulfonyl)pentan-2-yl)aniline (6ae).
Compound 6ae was synthesized in 80% yield (77 mg,
0.24 mmol) as an orange solid. The crude product was puri-
fied using silica gel column chromatography (EtOAc:hex-
8-((4-Methoxyphenyl)amino)-9-(phenylsulfonyl)non-
anenitrile (6ha). Compound 6ha was synthesized in 76%
yield (91 mg, 0.23 mmol) as a brown oil. The crude prod-
uct was purified using silica gel column chromatography
1
anes = 1:3). mp 78–79 ꢀC; H NMR (CDCl3, 400 MHz): δ
1
(EtOAc:hexanes = 1:3). H NMR (CDCl3, 400 MHz): δ
7.86–7.83 (m, 2H), 7.64–7.60 (m, 1H), 7.51 (t, J = 7.8 Hz,
2H), 6.82–6.78 (m, 2H), 6.38–6.35 (m, 2H), 3.82–3.76 (m,
1H), 3.57 (br s, 1H), 3.29 (dd, J = 14.2, 4.6 Hz, 1H), 3.14
(dd, J = 14.2, 6.4 Hz, 1H), 1.90–1.81 (m, 1H), 1.60–1.47
(m, 1H), 1.45–1.30 (m, 2H), 0.89 (t, J = 7.3 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 155.9 (d, J = 236 Hz), 142.4,
139.8, 133.7, 129.2, 127.8, 115.8 (d, J = 23.1 Hz), 114.0
(d, J = 6.7 Hz), 59.4, 49.4, 37.3, 19.0, 13.7; IR (neat):
3387 (w), 2962 (w), 2932 (w), 1612 (w), 1520 (s), 1450
(w), 1296 (s), 1219 (m), 1134 (s), 1080 (s), 887 (w),
810 (s), 741 (s) cm−1; HRMS (ESI) m/z: [M + H]+ Calcd
for C17H21FNO2S 322.1277, Found 322.1277.
7.86 (dd, J = 8.5 Hz, 2H), 7.65 (t, J = 7.6 Hz, 1H), 7.54 (t,
J = 7.6 Hz, 2H), 6.72 (d, J = 8.7 Hz, 2H), 6.42 (d,
J = 9.1 Hz, 2H), 3.83–3.77 (m, 1H), 3.73 (s, 3H), 3.43 (br
s, 1H), 3.33 (dd, J = 14.2, 4.1 Hz, 1H), 3.11 (dd, J = 14.2,
7.3 Hz, 1H), 2.32 (t, J = 7.1 Hz, 2H), 2.01–1.92 (m, 1H),
1.66–1.53 (m, 3H), 1.51–1.25 (m, 6H); 13C NMR (CDCl3,
100 MHz): δ 152.3, 139.8, 139.6, 133.7, 129.2, 127.7,
119.8, 114.8, 114.5, 59.1, 55.5, 49.5, 34.9, 28.3, 25.4,
25.0, 16.9; IR (neat): 3379 (w), 2978 (m), 2932 (m), 2862
(m), 1512 (s), 1450 (m), 1389 (w), 1304 (s), 1242 (s), 1142
(s), 1080 (w), 1041 (m), 825 (s), 748 (s) cm−1; HRMS
(ESI) m/z: [M + H]+ Calcd for C22H29N2O3S 401.1899,
Found 401.1897.
4-Chloro-N-(1-(phenylsulfonyl)pentan-2-yl)aniline (6af).
Compound 6af was synthesized in 72% yield (73 mg,
0.22 mmol) as an orange solid. The crude product was puri-
fied using silica gel column chromatography (EtOAc:hex-
N-(5-((tert-Butyldimethylsilyl)oxy)-1-(phenylsulfonyl)pen-
tan-2-yl)-4-methoxyaniline (6ia). Compound 6ia was syn-
thesized in 75% yield (104 mg, 0.22 mmol) as a brown oil.
The crude product was purified using silica gel column
1
anes = 1:3). mp 96–97 ꢀC; H NMR (CDCl3, 400 MHz): δ
7.86 (dd, J = 8.2, 1.4 Hz, 2H), 7.65 (tt, J = 7.3, 1.4 Hz,
1H), 7.53 (t, J = 7.6 Hz, 2H), 7.05 (d, J = 8.7 Hz, 2H),
6.35 (d, J = 9.1 Hz, 2H), 3.86–3.80 (m, 1H), 3.68 (br s,
1H), 3.30 (dd, J = 14.6, 4.6 Hz, 1H), 3.17 (dd, J = 14.2,
6.9 Hz, 1H), 1.90–1.85 (m, 1H), 1.59–1.52 (m, 1H), 1.47–
1.35 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H); 13C NMR (CDCl3,
1
chromatography (EtOAc:hexanes = 1:3). H NMR (CDCl3,
400 MHz): δ 7.89 (d, J = 7.3 Hz, 2H), 7.65 (t, J = 7.3 Hz,
1H), 7.54 (t, J = 7.8 Hz, 2H), 6.73 (d, J = 8.7 Hz, 2H),
6.43 (d, J = 8.7 Hz, 2H), 3.82 (br s, 1H), 3.75 (s, 3H),
3.63–3.60 (m, 3H), 3.35 (dd, J = 14.6, 4.6 Hz, 1H), 3.17
Bull. Korean Chem. Soc. 2021, Vol. 42, 699–708
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Cu-catalyzed Hydroaminations of Allylic Sulfones With Aromatic Amines
KOREAN CHEMICAL SOCIETY
100 MHz): δ 144.7, 139.7, 133.8, 129.3, 129.1, 127.8,
122.3, 114.1, 59.5, 48.8, 37.2, 19.0, 13.7; IR (neat): 3433
(w), 2924 (w), 1597 (s), 1497 (s), 1396 (w), 1296 (s), 1257
(w), 1142 (s), 1080 (s), 802 (s), 748 (s) cm−1; HRMS
(ESI) m/z: [M + H]+ Calcd for C17H21ClNO2S 338.0982,
Found 338.0984.
19.0, 13.7; IR (neat): 3387 (w), 2970 (m), 2870 (m), 2338
(w), 1597 (s), 1481 (s), 1389 (w), 1304 (s), 1142 (s), 1080
(m), 841 (m), 748 (s) cm−1; HRMS (ESI) m/z: [M + H]+
Calcd for C17H21ClNO2S 338.0982, Found 338.0983.
3-Bromo-N-(1-(phenylsulfonyl)pentan-2-yl)aniline (6ak).
Compound 6ak was synthesized in 72% yield (82 mg,
0.22 mmol) as a brown oil. The crude product was purified
using silica gel column chromatography (EtOAc:hex-
anes = 1:3). 1H NMR (CDCl3, 400 MHz): δ 7.87 (d,
J = 6.9 Hz, 2H), 7.66 (t, J = 7.3 Hz, 1H), 7.54 (t,
J = 7.8 Hz, 2H), 6.96 (t, J = 8.0 Hz, 1H), 6.81 (dd, J = 7.3,
0.9 Hz, 1H), 6.53 (t, J = 2.1 Hz, 1H), 6.36 (dd, J = 8.2,
2.3 Hz, 1H), 3.85–3.80 (m, 1H), 3.74 (br s, 1H), 3.32 (dd,
J = 14.2, 4.6 Hz, 1H), 3.19 (dd, J = 14.2, 6.4 Hz, 1H),
1.95–1.86 (m, 1H), 1.61–1.53 (m, 1H), 1.50–1.34 (m, 2H),
0.92 (t, J = 7.3 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ
147.4, 139.6, 133.8, 130.7, 129.3, 127.8, 123.3, 120.7,
115.6, 111.6, 59.5, 48.7, 37.1, 19.0, 13.7; IR (neat): 3379
(w), 2970 (m), 2870 (m), 2353 (w), 1597 (s), 1474 (m),
1304 (s), 1142 (s), 1080 (m), 987 (w), 841 (m), 748 (s)
4-Bromo-N-(1-(phenylsulfonyl)pentan-2-yl)aniline (6ag).
Compound 6ag was synthesized in 63% yield (72 mg,
0.19 mmol) as a light yellow oil. The crude product was
purified using silica gel column chromatography (EtOAc:
1
hexanes = 1:3). H NMR (CDCl3, 400 MHz): δ 7.87 (d,
J = 8.2 Hz, 2H), 7.67 (t, J = 7.3 Hz, 1H), 7.55 (t,
J = 7.3 Hz, 2H), 7.20 (dd, J = 8.9, 1.1 Hz, 2H), 6.31 (dd,
J = 8.7, 0.9 Hz, 2H), 3.87–3.80 (m, 1H), 3.67 (br s, 1H),
3.30 (dd, J = 14.2, 3.7 Hz, 1H), 3.17 (dd, J = 14.2, 6.4 Hz,
1H), 1.92–1.88 (m, 1H), 1.61–1.56 (m, 1H), 1.46–1.36 (m,
2H), 0.92 (td, J = 7.3, 0.9 Hz, 3H); 13C NMR (CDCl3,
100 MHz): δ 145.1, 139.8, 133.8, 132.1, 129.3, 127.9,
114.6, 109.6, 59.5, 48.9, 37.3, 19.0, 13.7; IR (neat): 3387
(w), 2970 (m), 2870 (m), 2361 (m), 1690 (s), 1597 (s),
1489 (s), 1443 (m), 1304 (s), 1142 (s), 1080 (w), 1018 (w),
818 (s), 748 (s) cm−1; HRMS (ESI) m/z: [M + Na]+ Calcd
for C17H20BrNNaO2S 404.0296, Found 404.0297.
cm−1
;
HRMS (ESI) m/z: [M + H]+ Calcd for
C17H21BrNO2S 382.0476, Found 382.0475.
Acknowledgments. This research was supported by the
Basic Science Research Program through the National
3-Fluoro-N-(1-(phenylsulfonyl)pentan-2-yl)aniline (6ai).
Compound 6ai was synthesized in 85% yield (82 mg,
0.26 mmol) as a light yellow oil. The crude product was
purified using silica gel column chromatography (EtOAc:
Research
Foundation of
Korea
(NRF)
(NRF-
2020R1A2C1005817).
1
hexanes = 1:3). H NMR (CDCl3, 400 MHz): δ 7.88 (d,
J = 7.8 Hz, 2H), 7.66 (t, J = 7.8 Hz, 1H), 7.54 (t,
J = 7.8 Hz, 2H), 7.04 (td, J = 8.1, 6.6 Hz, 1H), 6.38 (td,
J = 8.3, 2.5 Hz, 1H), 6.21 (dd, J = 8.2, 2.7 Hz, 1H), 6.06
(dt, J = 11.4, 2.5 Hz, 1H), 3.86–3.75 (m, 2H), 3.33 (dd,
J = 14.2, 4.6 Hz, 1H), 3.19 (dd, J = 14.2, 6.4 Hz, 1H),
1.95–1.87 (m, 1H), 1.63–1.54 (m, 1H), 1.50–1.33 (m, 2H),
0.92 (t, J = 7.3 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ
164.0 (d, J = 243.8 Hz), 147.8 (d, J = 10.6 Hz), 139.6,
133.8, 130.5 (d, J = 10.6 Hz), 129.3, 127.9, 108.8 (d,
J = 2.0 Hz), 104.4 (d, J = 22.2 Hz), 99.7 (d, J = 25.0 Hz),
59.5, 48.8, 37.2, 19.0, 13.7; IR (neat): 3379 (w), 2970 (m),
2870 (m), 2361 (m), 1620 (s), 1497 (m), 1450 (m), 1304
(s), 1149 (s), 1088 (w), 841 (m), 756 (s) cm−1; HRMS
(ESI) m/z: [M + H]+ Calcd for C17H21FNO2S 322.1277,
Found 322.1274.
Conflict of interest
The authors declare no competing financial interests.
Supporting Information
Additional supporting information (1H NMR and 13C NMR
spectra for all products) is available in the online version of
this article.
Supporting Information. Additional supporting informa-
tion may be found online in the Supporting Information
section at the end of the article.
3-Chloro-N-(1-(phenylsulfonyl)pentan-2-yl)aniline (6aj).
Compound 6aj was synthesized in 78% yield (79 mg,
0.23 mmol) as a brown oil. The crude product was purified
using silica gel column chromatography (EtOAc:hex-
anes = 1:3). 1H NMR (CDCl3, 400 MHz): δ 7.87 (d,
J = 7.3 Hz, 2H), 7.66 (t, J = 7.7 Hz, 1H), 7.54 (t,
J = 7.7 Hz, 2H), 7.02 (t, J = 8.0 Hz, 1H), 6.66 (dd, J = 8.0,
2.1 Hz, 1H), 6.36–6.31 (m, 2H), 3.86–3.80 (m, 1H), 3.72
(br s, 1H), 3.33 (dd, J = 14.2, 4.6 Hz, 1H), 3.20 (dd,
J = 14.2, 6.9 Hz, 1H), 1.98–1.87 (m, 1H), 1.63–1.53 (m,
1H), 1.49–1.32 (m, 2H), 0.92 (t, J = 7.3 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 147.3, 139.6, 135.1, 133.9,
130.4, 129.4, 127.8, 117.8, 112.7, 111.2, 59.5, 48.7, 37.2,
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KOREAN CHEMICAL SOCIETY
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Bull. Korean Chem. Soc. 2021, Vol. 42, 699–708
© 2021 Korean Chemical Society, Seoul & Wiley-VCH GmbH
www.bkcs.wiley-vch.de
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