2-Methylquinoline promoted oxidative ring-opening of N-sulfonyl aziridines with DMSO: facile synthesis of α-amino aryl ketones

Article abstract of DOI:10.1016/j.tet.2016.10.041

2-Methylquinoline promoted room-temperature oxidative ring-opening of N-sulfonyl aziridines with DMSO has been developed, providing a mild and convenient method for the synthesis of a variety of different N-sulfonyl protected α-amino aryl ketones. The employment of 2-methylquinoline was crucial for the success of this mild transformation and good to excellent yields could be achieved.

Full text of DOI:10.1016/j.tet.2016.10.041

Accepted Manuscript
2-Methylquinoline promoted oxidative ring-opening of N-sulfonyl aziridines with
DMSO: facile synthesis of α-amino aryl ketones
Xianhui Zhang, Shuai-Shuai Li, Liang Wang, Lubin Xu, Jian Xiao, Zhen-Jiang Liu
PII:
S0040-4020(16)31076-6
10.1016/j.tet.2016.10.041
TET 28182
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 4 August 2016
Revised Date: 14 October 2016
Accepted Date: 17 October 2016
Please cite this article as: Zhang X, Li S-S, Wang L, Xu L, Xiao J, Liu Z-J, 2-Methylquinoline promoted
oxidative ring-opening of N-sulfonyl aziridines with DMSO: facile synthesis of α-amino aryl ketones,
Tetrahedron (2016), doi: 10.1016/j.tet.2016.10.041.
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ACCEPTED MANUSCRIPT
2-Methylquinoline Promoted Oxidative Ring-opening of
N-Sulfonyl Aziridines with DMSO: Facile Synthesis of α-Amino
Aryl Ketones
Xianhui Zhang,a,† Shuai-Shuai Li,c,† Liang Wang,b Lubin Xu,b Jian Xiaob,* and
Zhen-Jiang Liua,*
a
School of Chemical and Environmental Engineering, Shanghai Institute of
Technology, 100 Haiquan Road, Shanghai, 201418, China
E-mail: zjliu@sit.edu.cn
b College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University,
Qingdao, 266109, China
E-mail: chemjianxiao@163.com
c
Key Laboratory for Asymmetric Synthesis and Chiraltechnology of Sichuan
Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences,
Chengdu 610041, China
† These authors contributed equally to this work.
2-Methylquinoline promoted room-temperature oxidative ring-opening of
N-sulfonyl aziridines with DMSO has been developed, providing a mild and
convenient method for the synthesis of a variety of different N-sulfonyl protected
α-amino aryl ketones. The employment of 2-methylquinoline was crucial for the
success of this mild transformation and good to excellent yields could be
achieved.

ACCEPTED MANUSCRIPT
2-Methylquinoline Promoted Oxidative Ring-opening of
N-Sulfonyl Aziridines with DMSO: Facile Synthesis of
α-Amino Aryl Ketones
Xianhui Zhang,a,† Shuai-Shuai Li,c,† Liang Wang,b Lubin Xu,b Jian Xiaob,* and
Zhen-Jiang Liua,*
a
School of Chemical and Environmental Engineering, Shanghai Institute of
Technology, 100 Haiquan Road, Shanghai, 201418, China
E-mail: zjliu@sit.edu.cn
b College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University,
Qingdao, 266109, China
E-mail: chemjianxiao@163.com
c
Key Laboratory for Asymmetric Synthesis and Chiraltechnology of Sichuan
Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences,
Chengdu 610041, China
Abstract: 2-Methylquinoline promoted room-temperature oxidative ring-opening of
N-sulfonyl aziridines with DMSO has been developed, providing a mild and
convenient method for the synthesis of a variety of different N-sulfonyl protected
α-amino aryl ketones. The employment of 2-methylquinoline was crucial for the
success of this mild transformation and good to excellent yields could be achieved.
Key words: α-amino aryl ketones; 2-methylquinoline; oxidative ring-opening;
N-sulfonyl aziridines
† These authors contributed equally to this work.

ACCEPTED MANUSCRIPT
1. Introduction
α-Amino ketones belong to a privileged framework which constitute the core
structures of a large variety of biologically and pharmacologically significant natural
products and medicines such as the proteasome inhibitor epoxomicin,1
anti-psychological disorders medicine bupropion and brephedrone.2 They can also
serve as useful precursors for preparing a vast number of natural products as well as
biologically active β-amino alcohols.3 Due to the significance of this structural motif,
the synthesis of α-amino ketone derivatives has attracted considerable attention from
synthetic community and an array of methodologies have been developed in recent
decades to prepare such skeletons. For instance, hypervalent iodine reagents have
been employed to access α-amino ketones via umpolung of silyl enol ethers, followed
by nucleophilic addition with amines.4 The fascinating moiety could also be
constructed
via
rhodium
catalyzed
denitrogenative
hydration
of
N-sulfonyl-1,2,3-triazoles.5 Very recently, hydrazones were exploited as precursors to
prepare sulfonylamino ketones via Cs2CO3-promoted N-N bond cleavage.6
Remarkably, α-amino ketones could also be accessed via the direct oxidative
ring-opening of aziridines by DMSO,7 NBS combined with CAN or β-CD,8 IBX in
the presence of β-CD,9 or pyridine N-oxide.10 Among the oxidants developed in the
oxidative ring-opening of aziridines, DMSO, as a cheaper and readily available one,11
has received much attention. As early as 1967, Heine and Newton have reported that
the direct oxidative ring-opening of N-aroylaziridines in DMSO gave N-aroyl
α-amino ketones, but the required aziridines are not easily accessible.7a Later Nozaki
and co-workers showed that the relatively more readily available
N-alkoxycarbonylaziridines undergo oxidative ring opening in DMSO to give
N-acyl-α-aminoketones, however, the reaction leads to mixtures of regioisomeric
products in some cases.7b-c In addition, these reports suffer from harsh reaction
conditions, such as high reaction temperatures (117 or 120 oC) and long reaction times
(17 or 24 h).7a-c Recently, Du Bois reported the oxidative ring-opening of
N-alkoxysulfonyl aziridines in DMSO to produce N-alkoxysulfonylated α-amino
ketones under mild conditions, however, only limited amounts of N-alkoxysulfonyl
1

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aziridines could be obtained and the substrate scope was largely restricted.7d Trost and
Dong recently reported a single example of the ring-opening of cycloalkyl-substituted
N-tosyl aziridine in DMSO to afford α-amino ketone, but an extra expensive Lewis
acid catalyst was needed.7e More recently, Ghorail and co-workers also reported only
a single example for the ring-opening of 2-phenyl-N-tosylaziridine by DMSO at 70 oC
to give α-amino ketone.7f Although some advances have been made for the oxidative
ring-opening of various N-protected aziridines in DMSO, it is still highly desirable to
develop a general and regiospecific strategy for the ring-opening of easily available
aziridines, such as N-sulfonyl aryl aziridines, to prepare α-amino ketones under milder
conditions.
As a continuation of our research interest in development of efficient and green
methodology to construct biologically and medicinally important molecules,12,13
herein, we report our recent findings on the 2-methylquinoline promoted
room-temperature oxidative ring-opening of N-sulfonyl aziridines with DMSO as an
oxidizing agent. The title reaction proceeds regiospecifically, affording the
corresponding α-amino aryl ketones in good to excellent yields under mild conditions.
2. Results and discussion
SO2Ph
N
Ph
H
N
O
N
N
N
Ph
SO2Ph
X
Ph
PhSO
2NH
C(sp3)-H
DMSO, r.t.
A
1a
2a (88%)
Functionalization
Scheme 1. Unexpected 2-methylquinoline promoted oxidative ring-opening of
N-sulfonyl aziridine in DMSO at room temperature
During our studies on a research project of the C(sp3)-H functionalization of
azaarenes,13 initially, 2-methylquinoline and N-sulfonyl aziridine 1a were selected as
model substrates to investigate the feasibility of the C(sp3)-H functionalization of
azaarenes with aziridines. Unexpectedly, no desired product A was obtained and
2

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α-sulfonylamino ketone 2a was isolated in 88% yield when DMSO was used as
solvent at room temperature, in which DMSO also served as an oxidant7,11,14 (Scheme
1). After a careful search on the literatures, it was found that Trost and Ghorail
recently have independently reported a sole example of the oxidative ring-opening of
N-tosyl aziridine with DMSO to form α-amino ketone.7e-f To investigate this
interesting finding systematically, the reaction conditions were then screened using
the ring-opening of 2-phenyl-N-phenylsulfonylaziridine 1a as a model reaction. The
results are summarized in Table 1. Firstly, other organic bases such as quinoline,
2,6-dimethylpyridine, pyridine and triethylamine were checked, however, no product
2a was furnished with 2-phenyl-N-phenylsulfonylaziridine 1a intact (Table 1, entries
2-5). Some inorganic bases, e.g. K2CO3, Na2CO3 and NaOH, were also exploited,
whereas no reaction was observed (Table 1, entries 6-8). Decreasing the amount of
2-methylquinoline to 1 equivalent, good yield still could be obtained (Table 1, entry
9). However, the yield was decreased drastically when 0.5 equivalent of
2-methylquinoline was used, and only trace of 2a was afforded when the amount of
2-methylquinoline was further decreased to 0.1 equivalent (Table 1, entries 10-11). A
blank experiment also confirmed that no reaction occurred in the absence of
2-methylquinoline at room temperature (Table 1, entry 12). Although the reaction also
works under the conditions of Ghorail, a decreased yield was given (Table 1, entry 13).
Thus, the employment of 2-methylquinoline was crucial for the success of this
oxidation process at room temperature. At last, 2 equivalent of 2-methylquinoline was
selected for the substrate scope investigation. Compared to the reports by Trost and
Ghorail,7e-f the current reaction conditions are much simpler and milder.
Table 1. Optimization of reaction conditionsa
O
H
O
S
O
S
N
N
DMSO
r.t.
O
O
2a
1a
Entry
Additives
Time (h)
Yield (%)b
3

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1
2
2-methylquinoline
quinoline
10
10
10
10
10
10
10
10
10
10
10
10
10
88
NR
NR
NR
NR
NR
NR
NR
82
3
2,6-dimethylpyridine
pyridine
4
5
Et3N
6
K2CO3
7
Na2CO3
8
NaOH
9c
10d
11e
12
13f
2-methylquinoline
2-methylquinoline
2-methylquinoline
-
45
trace
NR
61
-
a Reaction condition: 0.1 mmol of 1a, 1.0 ml of DMSO, 2 equiv. of base, all reactions proceeded at
b
room temperature unless stated otherwise.
Yields of products isolated after column
chromatography. c 1.0 equiv. of 2-methylquinoline. d 0.5 equiv. of 2-methylquinoline. e 0.1 equiv. of
2-methylquinoline. f The reaction was run at 70 oC.
With the optimal reaction conditions in hand, a variety of electronically and
sterically diverse aziridines were subjected to this direct oxidative ring-opening
reaction to investigate the substrate scope. As shown in Scheme 2, all the substrates
bearing electron-donating and electron-withdrawing groups were well tolerated to
furnish the corresponding α-amino aryl ketones in good to excellent yields.
Remarkably, the electronic characteristics of the substituted aryl sulfonyl group had
trivial impact on the reaction efficiency, and the corresponding products 2b-h could
be furnished in high yields when the substrates 1b-h para-substituted with
electron-donating and withdrawing groups were subjected to the reactions. The
naphthalene sulfonyl substituted substrate 1i was also suitable for this transformation,
affording the corresponding product 2i in 78% yield. Aziridines protected by alkyl
4

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sulfonyl groups (1j-l) were ideal substrates for the reaction, resulting in the desired
products 2j-l in a little bit lower yields. Subsequently, the substituent effect of the
para-substituted groups on the aryl rings of aziridines, e.g. alkyls or halogens, were
investigated. Fortunately, the corresponding products 2m-2p were isolated in 73%-87%
yields. As expected, the electron-withdrawing groups e.g. chlorine and bromine, were
beneficial to the reaction, furnishing the desired α-amino aryl ketones in higher yields
(2o-p). It should be noted that N-aroylaziridines didn’t work under our optimal
reaction conditions. Furthermore, the model reaction could be scaled up to Gram
quantity (12.7 mmol), and a good yield could be obtained (Scheme 3), indicating the
potential value for the application in synthesis.15
5

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Scheme 2. Substrate scope of aziridines.
Scheme 3. Scale up the reaction.
Referring to the oxidizing mechanism by DMSO in the literature,11 a plausible
mechanism was proposed in Scheme 4.16 As the aziridine is a highly strained and
polarized 3-membered heterocyclic ring, it is highly reactive and readily attacked by
nucleophiles. The aryl-substituted N-sulfonyl aziridines are more easily polarized to
the intermediate 1 other than 1′ on the basis of the stability of the polarized cations.
Therefore, the nucleophilic oxygen atom of DMSO regiospecifically attacks the
benzylic carbon of the N-sulfonyl aziridine to furnish the zwitterionic intermediate 5,
which is protonated by H2O to afford intermediate 6. The methyl group of highly
polarized intermediate 6 undergoes deprotonation by 2-methylquinoline, to furnish the
alkoxysulfonium ylide 7, which is followed by intramolecular deprotonation to give
the final α-sulfonylamino aryl ketones 2. From the optimizing results, it could be seen
that 2-methylquinoline was important for the reaction running at room temperature,
possibly due to the appropriate alkalinity of 2-methylquinoline.17 However, the exact
role of 2-methylquinoline in the reaction is still unclear at present.
6

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Scheme 4. Plausible reaction mechanism ( B: = 2-methylquinoline)
3. Conclusions
In conclusion, we have demonstrated that 2-methylquinoline is an efficient
promoter for the regiospecifically oxidative ring-opening of N-sulfonyl aziridines
with DMSO. The reaction could be performed at room temperature, and a variety of
α-amino aryl ketones could be obtained in good to excellent yields under this mild
and convenient reaction condition. Further studies to clarify the role of
2-methylquinoline and to continue expanding the substrate scope of this methodology
are currently in progress in our laboratories.
4. Experimental section
4.1. General
1H NMR spectra were recorded on a Bruker AMX 500 spectrometer (CDCl3 as
solvent). Chemical shifts were reported in ppm using tetramethylsilane (TMS, δ (ppm)
= 0.00 ppm) as the internal standard, and relative to the signal of chloroform-d (7.26,
singlet). The number of protons for a given resonance was indicated by nH. Coupling
constants were reported as a J value in Hz. The following abbreviations were used to
indicate the multiplicity: singlet (s), doublet (d), triplet (t), quartet (q), doublet of
doublets (dd), and multiplet (m). 13C NMR spectra were reported in ppm using
7

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solvent CDCl3 (δ (ppm) = 77.10 ppm) as an internal standard. HRMS analyses were
performed on a Waters XEVO QTOF mass spectrometer. All the chemical reagents,
unless otherwise noted, were purchased from commercial companies and used
without further purification. All reactions were performed in flask and monitored by
TLC (0.2 mm silica gel-coated HSGF 254 plate). The reaction mixtures were purified
by flash column chromatography (200-300 mesh silica gel) eluted with the gradient of
petroleum ether and ethyl acetate. The NMR Spectra of the known α-sulfonylamino
ketone derivatives were consistent with previous reports.
4.2. General procedure for 2-methylquinoline promoted oxidative ring-opening
of N-sulfonyl aziridines with DMSO.
1 (0.1 mmol) and 2-methylquinoline (0.2 mmol) were dissolved in DMSO (1 mL),
and the resulting solution was stirred at room temperature. The reaction was
monitored by TLC until starting material 1 was consumed up. The resultant solution
was dissolved in water, then extracted and concentrated under the reduced pressure to
give the residue, which was further purified through flash column chromatography on
silica gel to afford the pure product 2.
1
4.2.1. N-(2-oxo-2-phenylethyl)benzenesulfonamide (2a).[18a] White solid; H NMR
(500 MHz, CDCl3) δ 7.95-7.91 (m, 2H), 7.87 (dd, J = 8.3, 1.1 Hz, 2H), 7.63 (t, J = 7.4
Hz, 1H), 7.60-7.57 (m, 1H), 7.55-7.46 (m, 4H), 5.76 (t, J = 3.7 Hz, 1H), 4.51 (d, J =
5.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 192.5, 139.2, 134.5, 133.7, 132.9, 129.2,
129.0, 127.9, 127.1, 48.7.
1
4.2.2. 4-fluoro-N-(2-oxo-2-phenylethyl)benzenesulfonamide (2b). White solid; H
NMR (500 MHz, CDCl3) δ 7.95-7.89 (m, 2H), 7.85 (d, J = 7.0 Hz, 2H), 7.61 (t, J =
6.6 Hz, 1H), 7.49 (t, J = 7.0 Hz, 2H), 7.33 (d, J = 21.7 Hz, 2H), 5.72 (t, J = 5.0 Hz,
1H), 4.49 (d, J = 5.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 192.4, 166.2, 134.6,
129.9, 129.9, 129.1, 128.75, 128.6, 127.9, 127.2, 126.9, 116.6, 116.4, 48.6; HRMS
(ESI): calcd. for C14H12FNO3S [M+H]+: 294.3201, found: 294.3204.
4.2.3. 4-chloro-N-(2-oxo-2-phenylethyl)benzenesulfonamide (2c).[18b] White solid;
8

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1H NMR (500 MHz, CDCl3) δ 7.87-7.82 (m, 4H), 7.65-7.60 (m, 1H), 7.51-7.45 (m,
4H), 5.69 (t, J = 4.0 Hz, 1H), 4.48 (d, J = 4.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ
192.3, 139.5, 137.8, 134.6, 133.7, 129.5, 129.1, 128.6, 127.9, 48.6.
4.2.4. 4-bromo-N-(2-oxo-2-phenylethyl)benzenesulfonamide (2d).[18c] White solid;
1H NMR (500 MHz, CDCl3) δ 7.88 (d, J = 7.9 Hz, 2H), 7.78 (d, J = 7.9 Hz, 2H), 7.67
(t, J = 8.0 Hz, 3H), 7.50 (t, J = 7.5 Hz, 2H), 5.69 (t, J = 3.2 Hz, 1H), 4.52-4.44 (d, J =
3.2 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 192.3, 138.2, 134.6, 133.6, 132.5, 129.1,
128.7, 127.9, 127.9, 48.6.
4.2.5.
N-(2-oxo-2-phenylethyl)-4-(trifluoromethyl)benzenesulfonamide
(2e).
White solid; 1H NMR (500 MHz, CDCl3) δ 8.04 (d, J = 7.5 Hz, 2H), 7.86 (d, J = 7.0
Hz, 2H), 7.78 (d, J = 7.5 Hz, 2H), 7.65-7.59 (m, 1H), 7.48 (t, J = 6.7 Hz, 2H), 5.72 (t,
J = 5.0 Hz, 1H), 4.49 (d, J = 5.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 192.1, 143.0,
134.6, 133.6, 127.9, 127.7, 126.5, 126.4, 126.4, 126.3, 48.6; HRMS (ESI): calcd. for
C15H12F3NO3S [M+H]+: 344.0602, found: 344.0603.
4.2.6. 4-methyl-N-(2-oxo-2-phenylethyl)benzenesulfonamide (2f).[18c] White solid;
1H NMR (500 MHz, CDCl3) δ 7.88-7.83 (m, 2H), 7.79 (d, J = 8.6 Hz, 2H), 7.65-7.62
(m, 3H), 7.52 (t, J = 7.8 Hz, 2H), 5.73 (t, J = 5.0 Hz, 1H), 4.49 (d, J = 5.0 Hz, 2H),
2.42 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 190.6, 142.8, 140.1, 135.1, 131.1, 128.9,
128.4, 128.2, 126.2, 47.7, 20.5.
4.2.7. 4-(tert-butyl)-N-(2-oxo-2-phenylethyl)benzenesulfonamide (2g).[18b] White
solid; 1H NMR (500 MHz, CDCl3) δ 7.88 (d, J = 7.4 Hz, 2H), 7.84 (d, J = 8.5 Hz, 2H),
7.64 (t, J = 7.4 Hz, 1H), 7.51 (dd, J = 17.2, 8.2 Hz, 4H), 5.65 (t, J = 5.0 Hz, 1H), 4.48
(d, J = 5.0 Hz, 2H), 1.31 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 192.5, 156.7, 136.0,
134.4, 133.8, 128.9, 127.9, 127.1, 126.2, 48.6, 31.1.
4.2.8. 4-methoxy-N-(2-oxo-2-phenylethyl)benzenesulfonamide (2h).[18c] White
9

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1
solid; H NMR (500 MHz, CDCl3) δ 7.90-7.82 (ddd, J = 9.9, 6.6, 2.0 Hz, 4H), 7.63
-7.58 (m, 1H), 7.52-7.47 (q, J = 7.6 Hz, 2H), 6.97-6.93 (m, 2H), 5.63 (t, J = 5.0 Hz,
1H), 4.45 (d, J = 5.0 Hz, 2H), 3.84 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 192.6,
163.1, 134.4, 133.8, 130.7, 129.3, 128.9, 127.8, 114.4, 55.6, 48.6.
1
4.2.9. N-(2-oxo-2-phenylethyl)naphthalene-1-sulfonamide (2i).[18c] White solid; H
NMR (500 MHz, CDCl3) δ 8.47 (s, 1H), 7.98-7.93 (m, 2H), 7.91-7.85 (m, 2H),
7.86-7.82 (dd, J = 8.3, 1.0 Hz, 2H), 7.66-7.56 (m, 3H), 7.47 (t, J = 7.8 Hz, 2H),
5.82-5.75 (m, 1H), 4.51 (d, J = 5.0 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 192.4,
135.9, 134.9, 134.4, 133.7, 132.1, 129.7, 129.2, 128.9, 128.9, 128.6, 127.9, 127.9,
127.6, 122.3, 48.7.
1
4.2.10. N-(2-oxo-2-phenylethyl)methanesulfonamide (2j).[18c] Yellow liquid; H
NMR (500 MHz, CDCl3) δ 8.00-7.95 (m, 2H), 7.67 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.8
Hz, 2H), 5.45 (t, J = 5.0 Hz, 1H), 4.71 (d, J = 5.0 Hz, 2H), 3.04 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 193.4, 134.5, 133.9, 129.1, 127.9, 49.2, 40.8.
4.2.11. N-((ethylsulfonyl)methyl)aniline (2k).[18b] Yellow liquid; 1H NMR (500 MHz,
CDCl3) δ 7.95 (dd, J = 8.2, 1.0 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.8 Hz,
2H), 5.31 (t, J = 5.0 Hz, 1H), 4.67 (d, J = 5.0 Hz, 2H), 3.10 (q, J = 7.4 Hz, 2H), 1.43
(t, J = 7.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 193.3, 134.5, 133.8, 129.1, 127.9,
49.2, 45.8, 8.3.
1
4.2.12. N-(2-oxo-2-phenylethyl)butane-1-sulfonamide (2l).[18c] Yellow liquid; H
NMR (500 MHz, CDCl3) δ 7.98-7.93 (m, 2H), 7.65 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.8
Hz, 2H), 5.29 (t, J = 5.0 Hz,, 1H), 4.66 (d, J = 5.0 Hz, 2H), 3.09-3.03 (m, 2H),
1.90-1.80 (ddd, J = 12.2, 10.2, 6.7 Hz, 2H), 1.50-1.42 (dq, J = 14.9, 7.5 Hz, 2H), 0.95
(t, J = 7.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 193.3, 134.5, 133.9, 129.1, 127.9,
53.1, 49.2, 25.6, 21.5, 13.6.
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4.2.13. N-(2-(4-(tert-butyl)phenyl)allyl)-4-methylbenzenesulfonamide (2m). White
1
solid; H NMR (500 MHz, CDCl3) δ 7.85-7.76 (ddd, J = 8.3, 4.0, 1.9 Hz, 4H),
7.50-7.44 (m, 2H), 7.30 (d, J = 8.0 Hz, 2H), 5.68 (t, J = 5.0 Hz, 1H), 4.44 (d, J = 5.0
Hz, 2H), 2.39 (s, 3H), 1.32 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 192.07, 158.50,
143.71, 136.16, 131.23, 129.81, 127.86, 127.19, 125.94, 48.55, 35.30, 30.98, 21.50;
HRMS (ESI): calcd. for C19H23NO3S [M+H]+: 346.4645, found: 346.4647.
4.2.14. 4-methyl-N-(2-oxo-2-(p-tolyl)ethyl)benzenesulfonamide (2n).[18c] White
1
solid; H NMR (500 MHz, CDCl3) δ 7.88-7.83 (m, 2H), 7.77 (d, J = 8.6 Hz, 2H),
7.65-7.62 (m, 2H), 7.51 (t, J = 7.8 Hz, 2H), 5.73 (t, J = 5.0 Hz, 1H), 4.49 (d, J = 5.0
Hz, 2H), 2.42 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 190.6, 142.8, 140.1, 135.1,
131.1, 128.9, 128.4, 128.2, 126.2, 47.7, 20.5.
4.2.15. N-(2-(4-chlorophenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (2o).[18d]
1
White solid; H NMR (500 MHz, CDCl3) δ 7.74-7.68 (m, 4H), 7.39-7.35 (m, 2H),
7.21 (d, J = 8.0 Hz, 2H), 5.55 (t, J = 5.0 Hz, 1H), 4.36 (d, J = 5.0 Hz, 2H), 2.33 (s,
3H); 13C NMR (125 MHz, CDCl3) δ 190.5, 142.8, 140.0, 135.1, 131.1, 128.8, 128.3,
128.2, 126.1, 47.6, 20.5.
4.2.16. N-(2-(4-bromophenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (2p).[18a]
1
White solid; H NMR (500 MHz, CDCl3) δ 7.74-7.68 (dd, J = 11.6, 5.0 Hz, 4H),
7.39-7.35 (m, 2H), 7.23 (d, J = 8.0 Hz, 2H), 5.55 (t, J = 5.0 Hz, 1H), 4.36 (d, J = 5.0
Hz, 2H), 2.33 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 190.5, 142.8, 140.0, 135.1,
131.1, 128.8, 128.3, 126.2, 47.6, 20.5.
Acknowledgements
We are grateful to the National Natural Science Foundation of China (Nos. 21102142,
21102093). Financial supports from Talents of High Level Scientific Research
Foundation (Nos. 6631112323, 6631115015, 6631110309) of Qingdao Agricultural
University, The Innovation Program of Shanghai Municipal Education Commission
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(No. 14YZ144) and Chemical Engineering and Technology (Perfume and Aroma
Technology) of Shanghai Plateau Discipline are also gratefully acknowledged. We
thank Prof Teck-Peng Loh (University of Science and Technology of China and
Nanyang Technological University) for HRMS determination.
References and notes
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