Carbon-Phosphorus Bond Formation on Anilines Mediated by a Hypervalent Iodine Reagent

Article abstract of DOI:10.1021/acs.joc.7b01595

Substituted anilines containing a sulfonyl group may be oxidized in situ in the presence of methanol and a hypervalent iodine reagent to form an active iminium species. Subsequent addition of phosphines or phosphites in the same pot produces meta-substitu

Full text of DOI:10.1021/acs.joc.7b01595

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Note
Carbon-Phosphorous Bond Formation on Anilines
Mediated by a Hypervalent Iodine Reagent
Elsa Deruer, Siomenan Coulibali, Saad Boukercha, and Sylvain Canesi
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01595 • Publication Date (Web): 15 Aug 2017
Downloaded from http://pubs.acs.org on August 18, 2017
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The Journal of Organic Chemistry
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Carbon-Phosphorous Bond Formation on Anilines
Mediated by a Hypervalent Iodine Reagent
Elsa Deruer, Siomenan Coulibali, Saad Boukercha and Sylvain Canesi*
Laboratoire de Méthodologie et Synthèse de Produits Naturels, Université du Québec à Montréal, C.P.
8888, Succ. CentreꢀVille, Montréal, H3C 3P8 Québec, Canada.
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canesi.sylvain@uqam.ca
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
O2
S
O2
S
O2
S
O2
S
HN
R4
R'3
HN
R4
H
HN
R4
N
R4
R3
R2
R3
R2
R3
R2
PhI(OAc)2/MeOH
then PR'3
R3
R2
or
PR'3
P
R'3
R1
O
R1
R1
OMe
R1
Abstract: Substituted anilines containing a sulfonyl group may be oxidized in situ in the presence of
methanol and a hypervalent iodine reagent to form an active iminium species. Subsequent addition of
phosphines or phosphites in the same pot produces metaꢀsubstituted anilines in good yields. This formal
CꢀH bond functionalization is a direct and efficient means of selectively substituting the metaꢀposition
of anilines to produce aromatic phosphonium ions or phosphonates.
Methods for selective and mild activation of aromatic CꢀH bonds have elicited strong interest in the
scientific community since these methods enable oneꢀstep formation of more highlyꢀfunctionalized
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systems without preꢀactivation. However, most of these efficient processes are restricted in scope and
require catalytic amounts of a heavy metal.1 Therefore, the discovery of novel, efficient, and
environmentally benign methodologies enabling similar transformations remains an active field of
research. As an alternative to methods requiring metal catalysts, formal CꢀH bond activation methods
mediated by hypervalent iodine reagents2 have been developed for electronꢀrich aromatic systems.
Several methods using iodanes have recently been reported in the literature, examples of which include
the noteworthy work of Kita,3 Gaunt,4 and Fan5 and coꢀworkers. Indeed, aromatic sulfonamides appear
to be competent substrates, enabling selective coupling or nucleophilic addition at any position on the
aromatic ring. The direct oxidation of anilines containing a sulfonyl group 1 in the presence of a
nucleophile may occur at the para or the ortho positions depending on the nature of the nucleophile.
With a hindered carbonꢀbased nucleophile, the reaction occurs at the most accessible ortho position,6
leading to 3. In contrast, with smaller nucleophiles such as alcohols (methanol) the attack occurs at the
most substituted position (para) to yield the dienimide7 4. This functionalized system (Nu = MeO) may
be strategically involved in a further 1,4ꢀadditionꢀrearomatization to produce a metaꢀsubstituted
aromatic in an indirect manner.8 Depending on the strategy and the nucleophile used, any position of an
aniline may be selectively attacked, Scheme 1.
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R2
O2S
R2
O2S
R2
O2S
R2
O2S
NH
N
NH
N
4
Nu
3
PhI(OAc)2
Nu
a
+
b
R1 Nu
1
R1
2
R1
N
ortho-
adduct
R1
para-
adduct
R2
R2
O2S
R2
O2S
5
O2S
NH
NH
R1
6
meta-
adduct
Nu1
H
H
MeOH
R1 OMe
Nu = OMe
Nu1
R1 OMe
H
Nu1
7
Scheme 1. Selective Substitution of Aniline derivatives
One interesting avenue would be to develop a method for oneꢀpot metaꢀactivation of the aniline
derivative 7. For this purpose, a reactive nucleophile stable under acidic and protic conditions (in the
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The Journal of Organic Chemistry
presence of methanol and acetic acid) is required. Candidates of choice include elements in the third
period of the periodic table, which are recognized for their nucleophilicity and poor basicity. In addition,
metalꢀfree direct carbonꢀphosphorous bond formation on unactivated aromatics is not often reported in
the literature. Phosphonium salts are interesting reagents involved in noteworthy transformations9 such
as the Wittig reaction; they may also be employed as phase transfer catalysts10 or as potentially chiral
cationic counterions.11
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In this paper, we describe a formal CꢀH bond functionalization mediated by an iodaneꢀ(III) species and
methanol to selectively produce good yields of metaꢀsubstituted anilines through a phosphorous moiety.
This oxidative process involves the inꢀsitu formation of a dienimine intermediate, which is trapped by a
phosphorous nucleophile followed by a domino rearomatization. This transformation represents an
aromatic variant of the MichaelisꢀArbuzov reaction12 on an unactivated aromatic sp2 center.
Iodanes13 catalyze remarkable transformations in electronꢀrich aromatic systems, including
dearomatization processes and cross coupling transformations. Our interest in producing carbonꢀcarbon
bonds6c in such systems led us to explore new coupling routes with the formation of carbonꢀheteroatom
bonds. Carbonꢀoxygen and carbonꢀnitrogen bond formation has been extensively reported in the
literature,13 and we were therefore motivated to investigate less wellꢀexplored techniques such as the
direct functionalization of aromatic CꢀH bonds using a phosphorous group.14 However, due to the direct
reactivity of phosphines with iodanes to produce phosphonium oxides, it was obvious that these reagents
could not be mixed. A previous report indicated that activation of aniline derivatives with iodanes in the
presence of methanol would generate a dienimine species7 that could readily be transformed into an
iminium species by the acid released from the hypervalent iodine reagent reduction. This intermediate 9
appears to be an excellent Michael acceptor. A nucleophilic species insensitive to the acidic conditions
generated during the oxidation could be added to the same pot to initiate a 1,4ꢀ addition process with the
dearomatized species 9. Phosphines and phosphites are valuable nucleophiles in this process, leading to
enamines 10 which may subsequently be transformed into phosphonium ions 11 through a
rearomatization process beginning with methanol elimination, Scheme 2.
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O2
S
O2
S
O2
S
O2
S
1
2
3
4
5
6
HN
R3
HN
R3
AcO
H
HN
R3
N
R3
R2
R2
MeOH
R2
PhI(OAc)2/MeOH
then PR3
R2
H
R
R
R
R
R
P
P
R
R
P R
R
R1
10
O
H
8
11
R1
R1
R1
O
9
7
8
9
Scheme 2. metaꢀCarbonꢀPhosphorous Bond Formation
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Several conditions including a variety of phosphines, sulfonamides, solvents, and iodanes were
investigated. DIB was chosen as the hypervalent iodine reagent of choice but PIFA (a perfluorinated and
more expensive analog) may also be used with similar yields. However, DIB appears to be a milder and
safer reagent in the presence of sensitive functional groups. Methanol was selected as the solvent of
choice but the reaction may also be performed in ethanol or TFE at the cost of slightly lower yields. A
series of representative experimental conditions is summarized in Table 1.
O2
S
O2
S
O2
S
H
HN
R1
HN
R1
1) PhI(OAc)2/R'OH
then PR3, 10 min.
N
R1
R2
R2
R2
Cl
2) NaHCO3/brine
PR3
work-up
13
14
12
OR'
entry
R
yield (%)
R2
R'
R1
Me
a
b
c
d
e
f
Ph*
Ph*
36
56
85
78
94
95
88
84
H
Me
Me
Me
Me
Me
Me
Et
2ꢀNO2ꢀPh
Me
Me
Me
Me
Me
Me
Me
Me
nꢀBu
nꢀBu
n-Bu
n-Bu
nꢀBu
nꢀBu
4ꢀTol
2-NO2-Ph
4-NO2-Ph
Me
g
h
Me
CF3CH2
*48 h are required
Table 1. Conditions Optimization
The best results were obtained using electronꢀpoor sulfonamides such as nosylamides, probably due to
their electronꢀwithdrawing effect on the Michaelꢀacceptor moiety. A positive point is these
sulfonamildes can be easily removed using a Fukuyama’s process.15 Aliphatic phosphines such as PBu3
were much more reactive than the less nucleophilic aromatic derivative PPh3. Phosphites were also
competent reagents for this transformation. In our trials methanol was the best and least expensive
solvent for this transformation, enabling direct functionalization of the metaꢀposition. With these
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conditions in hand, several substituted nosylamides were transformed into phosphonium salts in good to
excellent yields. In the case of nonꢀsymmetrical anilines, coupling occurred on the less hindered alkene
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3
4
5
6
for steric reasons, Table 2.
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O2
S
O2
S
O2
S
1) PhI(OAc)2/R'OH
H
HN
R4
HN
R4
N
R4
then PBu3, 10 min.
(1.5 equiv.), rt
R3
R2
R3
R2
R3
R2
Cl
PBu3
17
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2) NaHCO3/brine
16
15
work-up
R1
OMe
R1
R1
entry
R3
R4
yield (%)
R1
R2
a
b
c
d
e
f
H
Me
Me
H
84
94
95
95
79
75
90
65
68
82
Me
Me
H
H
H
H
H
H
Br
2ꢀNO2ꢀPh
2ꢀNO2ꢀPh
4ꢀNO2ꢀPh
2ꢀNO2ꢀPh
2ꢀNO2ꢀPh
2ꢀNO2ꢀPh
Me
Me
OMe
Et
H
H
nꢀBu
Me
g
h
i
H
H
CH2ꢀCO2Me
Me
H
H
H
CH2ꢀCH2ꢀOTBS
OMe
Me
CH=CH=CH=CH
j
2ꢀNO2ꢀPh
Table 2. Phosphonium Salt Formation
As the process appears quite efficient in generating aromatic phosphonium ions, we were interested in
extending the transformation to the formation of phosphonates. The introduction of phosphites to the
reaction resulted in formation of the expected aryl phosphonates in good yields. In the case of
compounds with structure 20b, the reaction was carried out in ethanol rather than methanol. This change
avoided partial transꢀesterification of the phosphonate moiety, but reduced the yield. Representative
experimental conditions are described in Table 3.
NO2
O2
S
NO2
O2
S
O2
S
20
R3
H
HN
HN
N
R4
R3
R2
PhI(OAc)2/MeOH
R3
R2
then P(OR)3
(1.5 equiv.)
R2
P(OR)2
19
18
R1
O
OMe
R1
R1
entry
R3
R
yield (%)
R1
R2
a
Me
Me
H
Me
Et
95
70
95
71
Me
Me
H
H
H
b*
c
Me
Me
OMe
OMe
d
CH=CH=CH=CH
* EtOH has been used instead of MeOH to avoid partial trans-esterification
Table 3. Phosphonate Formation Conditions
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In order to confirm the mechanism of this transformation and the efficiency of the one pot process, the
results were compared to a twoꢀstep approach in which dienimine 21 was isolated and the 1,4ꢀaddition
rearomatization representing the second part of the cascade was carried out separately under aprotic
conditions (acetonitrile) at 82 °C. The expected metaꢀsubstituted anilines were obtained in fair to good
yields. While the same products were formed in each protocol, the oneꢀpot transformation occurred
more rapidly and in better yield (examples 22a, 22b and 22e), demonstrating that the process is more
efficient under protic conditions mediated by an iminium species 16 as Michael acceptor, Table 4.
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O2
S
O2
S
HN
R
N
R
P(Bu)
3, (2 equiv.)
CH3CN, 1 h, 82 °C
R3
R2
R3
R2
Cl
21
then NaHCO3/brine
P(Bu)3
22
work-up
OMe
R1
R1
entry
R3
R
yield (%)
R1
R2
a
b
c
d
e
f
Me
Me
H
Me
66
79
60
72
81
59
56
80
Me
Me
Et
H
H
H
H
H
H
H
2ꢀNO2ꢀPh
Me
H
Et
Me
Me
Me
Me
OMe
H
2ꢀNO2ꢀPh
Me
H
g
h
H
Tol.
Me
CH=CH=CH=CH
Table 4. Tributylꢀphosphine 1,4ꢀadditionꢀRearomatization Domino Process
We have developed a selective oxidative method enabling production of a carbonꢀphosphorous bond
at the metaꢀposition of aniline derivatives. This process occurs in one pot via the formation of a
dieniminium intermediate that is readily transformed into the substituted aromatic system through a
domino 1,4ꢀaddition and rearomatization process. This transformation is equivalent to a CꢀH bond
functionalization without the need for metal catalysts.
Experimental Section:
Unless otherwise indicated, 1H and 13C NMR spectra were recorded at 300 and 75 MHz, respectively, in
CDCl3 solutions. Chemical shifts are reported in ppm on the δ scale. Multiplicities are described as s
(singlet), d (doublet), dd, ddd, etc. (doublet of doublets, doublet of doublets of doublets, etc.), t (triplet),
q (quartet), quin (quintuplet), m (multiplet), and further qualified as app (apparent), br (broad). Coupling
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constants, J, are reported in Hz. HRMS were measured in the electrospray (ESI) mode on a LCꢀMSD
TOF mass analyzer.
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2
3
4
5
a) General procedure for the preparation of sulfonamide products 12/15
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9
To a solution of the corresponding aniline (1 mmol, 1.0 equiv.) and pyridine (2.4 mmol, 2.4 equiv.) in
CH2Cl2 (10 mL) at 0 °C the corresponding sulfonyl chloride or nitrobenzenesulfonyl chloride (1.1
mmol, 1.1 equiv.) was added slowly. The reaction mixture was allowed to warm to room temperature
and stirred overnight. After complete conversion of the starting material (followed by TLC), the reaction
was quenched with a solution of HCl (1M). The phases were separated and the aqueous phase extracted
with CH2Cl2. The organic layers was washed with brine then, the organic phases were dried over
Na2SO4, filtered and concentrated under vacuum. The residue was purified by silica gel chromatography
(DCM/hexanes or EtOAc/hexanes)/recrystallization in ethanol or without purification to give the desired
sulfonamides products 12/15.
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b) General procedure for the formation of phosphonium/phosphonate product 14/17/20:
Iodobenzene diacetate (“DIB”, 0.15 mmol, 1.5 equiv.) was added to a vigorously stirred solution of
sulfonamide 12/15/18 (0.1 mmol, 1 equiv.) in a minimum of MeOH (0.5 mL) at room temperature. The
mixture was then stirred for 5 min, and phosphine or phosphite (0.15 mmol, 1.5 equiv.) was added (the
reaction was followed by TLC with a mixture of ethyl acetate/hexane, 10 min. with PBu3 or phosphite
and 48 hours with PPh3). The crude was concentrated under vacuum and the residue was quenched with
a saturated solution of NaHCO3. The phases were separated and the aqueous phase extracted with
CH2Cl2. The organic layers was washed with brine then, the organic phases were dried over Na2SO4,
filtered and concentrated under vacuum. The residue was purified by silica gel chromatography with a
mixture of CH2Cl2/MeOH excepted for compounds 20a-d (mixture of ethyl acetate/hexane) to give
corresponding phosphonium/phosphonate products 14/17/20.
c) General procedure for the formation of compounds 21:
Iodobenzene diacetate («DIB», 2 mmol, 2 equiv.) was added to a vigorously stirred solution of
sulfonamide (1 mmol, 1 equiv.) in MeOH (5 mL) at 0°C. The mixture was then stirred for 5 min.
(followed by TLC with a mixture of ethylacetate/hexane) and then concentrated under vacuum. The
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residue was purified by silica gel chromatography with a mixture of ethyl acetate/hexane to give product
1
2
3
21.
4
5
6
d) General procedure for the formation of phosphonium product 22:
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8
9
To a solution of 21 (0.1 mmol, 1 equiv.) in acetonitrile (1 mL) was added tributylphosphine (2.0 mmol,
2.0 equiv.). The mixture was then stirred at 82°C between 20 min. and 2 hours. After completion, the
reaction mixture was concentrated under reduced pressure. The residue was purified by silica gel
chromatography with a mixture of CH2Cl2/MeOH or by recrystallization in diethyl ether to afford 22.
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N-p-tolylmethanesulfonamide (12a)16: was obtained without purification as a white solid: 0.9 mmol,
167 mg, 90% yield; 1H NMR (300 MHz, CDCl3) δ 7.15 (br, 4H), 7.08 (s, 1H), 2.98 (s, 3H), 2.32 (s, 3H);
13C NMR (75 MHz, CDCl3) δ 135.6, 134.2, 130.3, 121.7, 39.0, 20.9.
N-(2,4-dimethylphenyl)-2-nitrobenzenesulfonamide (12b): was obtained without purification as a
brown solid: 0.95 mmol, 291 mg, 95% yield; Mp: 102ꢀ104 °C; 1H NMR (300 MHz, CDCl3) δ 7.87 (d, J
= 7.2 Hz, 1H), 7.82 – 7.67 (m, 2H), 7.61 (dt, J = 7.6, 3.8 Hz, 1H), 7.05 (br, 1H), 7.03 (s, 1H), 6.97 (br,
13
1H), 6.91 (d, J = 8.0 Hz, 1H), 2.27 (s, 3H), 2.16 (s, 3H); C NMR (75 MHz, CDCl3) δ 148.0, 137.5,
133.9, 133.5, 132.8, 131.9, 131.5, 131.1, 127.5, 126.2, 125.3, 20.98, 17.83; LRMS (ESI): Calc. for
C14H15N2O4S (M+H)+: 307; found: 307.
N-(2,4-dimethylphenyl)methanesulfonamide (12c)17: was obtained without purification as a white
solid : 0.94 mmol, 187 mg, 94% yield; Mp: 131ꢀ133 °C; 1H NMR (300 MHz, CDCl3) δ 7.29 (d, J = 8.0
Hz, 1H), 7.04 (s, 1H), 7.01 (d, J = 8.2 Hz, 1H), 6.67 (s, 1H), 2.98 (s, 3H), 2.31 (s, 3H), 2.30 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 136.5, 132.0, 131.9, 127.8, 124.5, 39.7, 20.9, 18.1.
N-(2,4-dimethylphenyl)-4-methylbenzenesulfonamide (12d)18: was obtained by silica gel
chromatography with a mixture of EtOAc/Hexane (1:1) as a white solid: 0.88 mmol, 242 mg, 88% yield;
Mp: 93ꢀ94 °C; 1H NMR (300 MHz, CDCl3) δ 7.62 (d, J = 8.3 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 7.15 (d,
J = 8.0 Hz, 1H), 6.95 – 6.87 (m, 2H), 6.75 (s, 1H), 2.38 (s, 3H), 2.25 (s, 3H), 1.98 (s, 3H); 13C NMR (75
MHz, CDCl3) δ 143.7, 136.9, 136.3, 132.3, 131.8, 131.5, 129.6, 127.5, 127.3, 125.3, 21.6, 20.9, 17.6.
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N-(2,4-dimethylphenyl)-4-nitrobenzenesulfonamide (12f): was obtained by recrystallization in
ethanol as a white solid : 0.95 mmol, 291 mg, 95% yield; Mp: 133ꢀ134 °C; 1H NMR (300 MHz, CDCl3)
δ 8.27 (d, J = 8.8 Hz, 2H), 7.90 (d, J = 8.8 Hz, 2H), 7.08 (d, J = 8.7 Hz, 1H), 7.00 – 6.89 (m, 2H), 6.77
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(s, 1H), 2.27 (s, 3H), 1.97 (s, 3H); C NMR (75 MHz, CDCl3) δ 150.2, 145.5, 137.6, 133.0, 132.0,
130.6, 128.6, 127.9, 125.9, 124.3, 21.0, 17.7. LRMS (ESI): Calc. for C14H15N2O4S (M+H)+: 307; found:
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307.
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(2-methyl-5-(methylsulfonamido)phenyl)triphenylphosphonium chloride (14a): was obtained by
silica gel chromatography with a mixture of CH2Cl2/MeOH (9:1) as a brown solid: 0.036 mmol, 16.1
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mg, 36% yield; Mp: 67ꢀ69 °C; H NMR (300 MHz, CDCl3) δ 7.79 (t, J = 6.9 Hz, 3H), 7.71 – 7.51 (m,
13H), 7.20 (t, J = 7.9 Hz, 1H), 6.94 (dd, J = 18.0, 1.9 Hz, 1H), 2.83 (s, 3H), 1.78 (s, 3H); 13C {1H} NMR
(75 MHz, CDCl3) δ 150.5, 150.3, 135.0, 135.0, 134.4, 134.3, 134.2, 134.1, 130.6, 130.4, 129.1, 129.0,
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128.3, 128.2, 126.8, 126.8, 120.0, 118.9, 114.0, 112.8, 39.7, 22.1, 22.0; P NMR (122 MHz, CDCl3) δ
22.6 (br); HRMS (ESI): Calc. for C26H25NO2PS+ (M)+: 446.1338; found: 446.1324.
(2,4-dimethyl-5-(2-nitrophenylsulfonamido)phenyl)triphenylphosphonium chloride (14b): was
obtained by silica gel chromatography with a mixture of CH2Cl2/MeOH (97:03) as an yellow solid:
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0.056 mmol, 31.8 mg, 56% yield; Mp: 247ꢀ249 °C; H NMR (300 MHz, CDCl3) δ 7.86 – 7.70 (m, 4H),
7.68 – 7.57 (m, 6H), 7.55 (s, 2H), 7.54 – 7.48 (m, 4H), 7.31 – 7.25 (m, 2H), 7.24 – 7.16 (m, 2H), 7.11
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(d, J = 7.3 Hz, 1H), 3.28 (s, 1H), 2.29 (s, 3H), 1.75 (s, 3H); C {1H} NMR (75 MHz, CDCl3) δ 148.1,
147.2, 147.0, 141.6, 139.9, 135.1, 134.9, 134.8, 134.8, 134.2, 134.1, 131.0, 130.8, 130.5, 130.4, 130.2,
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129.9, 128.6, 128.4, 122.7, 120.3, 119.1, 110.2, 109.0, 22.1, 19.4; P NMR (122 MHz, CDCl3) δ 21.8
(br); HRMS (ESI): Calc. for C32H28N2O4PS+ (M)+: 567.1502; found: 567.1496.
Tributyl(2,4-dimethyl-5-(methylsulfonamido)phenyl)phosphonium chloride (14c): was obtained by
silica gel chromatography with a mixture of CH2Cl2/MeOH (97:03) as an orange solid: 0.085 mmol, 34
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mg, 85% yield; Mp: 162ꢀ163 °C; H NMR (300 MHz, CDCl3) δ 7.76 (d, J = 15.2 Hz, 1H), 7.04 (d, J =
6.2 Hz, 1H), 4.13 (br, 1H), 2.82 (s, 3H), 2.51 – 2.37 (m, 6H), 2.35 (s, 3H), 2.28 (s, 3H), 1.56 – 1.30 (m,
12H), 0.89 (br, 9H); 13C {1H} NMR (75 MHz, CDCl3) δ 147.2, 147.0, 139.9, 139.8, 135.2, 135.0, 129.2,
129.1, 124.5, 124.4, 109.9, 108.9, 40.0, 24.2, 24.1, 24.1, 24.0, 23.8, 21.1, 21.1, 21.0, 20.9, 20.5, 20.5,
19.3, 19.3, 13.5; 31P NMR (122 MHz, CDCl3) δ 30.0 (br); HRMS (ESI): Calc. for C21H39NO2PS+ (M)+:
400.2434; found: 400.2415.
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Tributyl(2,4-dimethyl-5-(4-methylphenylsulfonamido)phenyl)phosphonium chloride (14d): was
obtained by silica gel chromatography with a mixture of CH2Cl2/MeOH (9:1) as a yellow solid: 0.078
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mmol, 37.2 mg, 78% yield; Mp: 163ꢀ164 °C; H NMR (300 MHz, CDCl3) δ 7.73 (d, J = 8.1 Hz, 2H),
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7.21 (d, J = 15.3 Hz, 1H), 7.06 (d, J = 8.0 Hz, 2H), 6.99 (d, J = 6.5 Hz, 1H), 2.33 (s, 3H), 2.31 – 2.22
(m, 12H), 1.44 – 1.30 (m, 6H), 1.29 – 1.16 (m, 6H), 0.87 (t, J = 7.2 Hz, 9H); 13C {1H} NMR (75 MHz,
CDCl3) δ 147.0, 146.9, 143.2, 139.6, 139.6, 134.8, 134.6, 128.7, 128.6, 127.2, 124.5, 124.3, 109.6,
108.6, 23.9, 23.8, 23.7, 23.7, 21.4, 20.7, 20.7, 20.6, 19.9, 19.3, 13.5; 31P NMR (122 MHz, CDCl3) δ 29.5
(br); HRMS (ESI): Calc. for C27H43NO2PS+ (M)+: 476.2747; found: 476.2726.
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Tributyl(2,4-dimethyl-5-(2-nitrophenylsulfonamido)phenyl)phosphonium chloride (14e): was
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obtained as an yellow solid: 0.095 mmol, 48.2 mg, 95% yield; Mp: 159ꢀ161 °C; H NMR (300 MHz,
CDCl3) δ 8.00 (d, J = 6.7 Hz, 1H), 7.43 – 7.27 (m, 4H), 6.99 (d, J = 6.2 Hz, 1H), 2.32 (m, 12H), 1.51 –
1.14 (m, 12H), 0.84 (t, J = 7.0 Hz, 9H); 13C {1H} NMR (75 MHz, CDCl3) δ 149.3, 147.2, 147.1, 139.5,
139.4, 139.3, 134.9, 134.7, 130.6, 130.6, 130.1, 129.1, 129.0, 123.8, 123.7, 122.5, 109.8, 108.8, 23.8,
23.6, 20.8, 20.8, 20.5, 19.9, 19.2, 13.5; HRMS (ESI): Calc. for C26H40N2O4PS+ (M)+: 507.2441; found:
507.2418.
Tributyl(2,4-dimethyl-5-(4-nitrophenylsulfonamido)phenyl)phosphonium chloride (14f): was
obtained by silica gel chromatography with a mixture of CH2Cl2/MeOH (97:03) as a dark orange solid:
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0.095 mmol, 48.2 mg, 95% yield; Mp: 152ꢀ154 °C; H NMR (300 MHz, CDCl3) δ 8.13 (d, J = 8.7 Hz,
2H), 8.02 (d, J = 8.8 Hz, 2H), 7.54 (d, J = 15.4 Hz, 1H), 7.04 (d, J = 6.6 Hz, 1H), 2.27 (br, 12H), 1.51 –
1.28 (m, 12H), 0.91 (t, J = 7.0 Hz, 9H); 13C {1H} NMR (75 MHz, CDCl3) δ 153.4, 148.2, 146.7, 146.5,
140.3, 135.3, 135.1, 129.8, 129.7, 127.7, 125.0, 124.9, 123.4, 109.6, 108.6, 23.9, 23.9, 23.7, 20.9, 20.8,
20.2, 19.1, 13.4; 31P NMR (122 MHz, CDCl3) δ 29.6 (br); HRMS (ESI): Calc. for C26H40N2O4PS+ (M)+:
507.2441; found: 507.2445.
2-nitro-N-(p-tolyl)benzenesulfonamide (15a)19: was obtained by silica gel chromatography with a
mixture of EtOAc/Hexane (1:9) as an orange solid: 0.90 mmol, 263 mg, 90% yield; 1H NMR (300 MHz,
CDCl3) δ 7.88 – 7.75 (m, 2H), 7.68 (td, J = 7.8, 1.4 Hz, 1H), 7.56 (td, J = 7.7, 1.2 Hz, 1H), 7.17 (s, 1H),
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7.06 (s, 4H), 2.28 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 148.3, 136.8, 134.0, 132.8, 132.6, 132.3, 131.9,
130.1, 125.3, 123.8, 21.0.
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N-(4-methoxyphenyl)-2-nitrobenzenesulfonamide (15d)20: was obtained by silica gel chromatography
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with a mixture of CH2Cl2/Hexane (5:5) as an yellow solid: 0.85 mmol, 262 mg, 85% yield; H NMR
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(300 MHz, CDCl3) δ 7.84 (dd, J = 7.9, 1.1 Hz, 1H), 7.75 – 7.64 (m, 2H), 7.55 (td, J = 7.7, 1.2 Hz, 1H),
7.13 (s, 1H), 7.10 – 7.04 (m, 2H), 6.80 – 6.72 (m, 2H), 3.74 (s, 3H); 13C NMR (75 MHz, CDCl3) δ
158.7, 148.3, 134.0, 132.6, 132.2, 131.9, 127.9, 126.3, 125.3, 114.6, 55.5.
N-(4-ethylphenyl)-2-nitrobenzenesulfonamide (15e)21: was obtained without purification as a brown
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solid : 0.95 mmol, 291 mg, 95% yield; H NMR (300 MHz, CDCl3) δ 7.87 – 7.77 (m, 2H), 7.68 (t, J =
7.4 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.08 (br, 4H), 2.58 (q, J = 7.6 Hz, 2H), 1.17 (t, J = 7.6 Hz, 3H);
13C NMR (75 MHz, CDCl3) δ 148.3, 143.1, 134.0, 133.0, 132.6, 132.4, 131.9, 128.9, 125.3, 123.8, 28.3,
15.4.
N-(4-butylphenyl)-2-nitrobenzenesulfonamide (15f): was obtained without purification as a dark red
solid : 0.95 mmol, 317 mg, 95% yield; Mp: 100ꢀ102 °C; 1H NMR (300 MHz, CDCl3) δ 7.91 – 7.77 (m,
2H), 7.70 (t, J = 7.4 Hz, 1H), 7.57 (t, J = 7.4 Hz, 1H), 7.26 (br, 1H), 7.09 (br, 4H), 2.55 (t, J = 7.5 Hz,
2H), 1.53 (dd, J = 14.5, 7.3 Hz, 2H), 1.31 (dd, J = 14.3, 7.1 Hz, 2H), 0.91 (t, J = 7.1 Hz, 3H); 13C NMR
(75 MHz, CDCl3) δ 148.3, 141.8, 134.0, 133.0, 132.6, 132.4, 131.9, 129.5, 125.3, 123.7, 35.1, 33.5,
22.3, 14.0; LRMS (ESI): Calc. for C16H19N2O4S (M+H)+: 319; found: 319.
N-(3-bromo-4-methylphenyl)methanesulfonamide (15g)6d: was obtained without purification as a
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brown solid : 0.95 mmol, 250 mg, 95% yield; H NMR (300 MHz, CDCl3) δ 7.45 (d, J = 2.2 Hz, 1H),
7.23 – 7.16 (m, 2H), 7.12 (dd, J = 8.2, 2.2 Hz, 1H), 3.02 (s, 3H), 2.35 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 135.6, 135.3, 131.6, 125.4, 124.9, 120.2, 39.4, 22.4.
Methyl 2-(4-(methylsulfonamido)phenyl)acetate (15h)2f: was obtained without purification as a
brown solid: 0.90 mmol, 218 mg, 90%; Mp: 114ꢀ116 °C; 1H NMR (300 MHz, CDCl3) δ 7.25 (d, J = 8.7
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Hz, 2H), 7.18 (d, J = 8.6 Hz, 2H), 7.13 (br, 1H), 3.70 (s, 3H), 3.60 (s, 2H), 2.98 (s, 3H); C NMR (75
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MHz, CDCl3) δ 172.2, 136.0, 131.2, 130.7, 121.1, 52.3, 40.5, 39.3.
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N-(4-(2-((tert-butyldimethylsilyl)oxy)ethyl)phenyl)methanesulfonamide (15i)6c: was obtained by
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silica gel chromatography with a mixture of EtOAc/Hexane (2:8) as an yellow oil: 0.95 mmol, 313 mg,
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95% yield; H NMR (300 MHz, CDCl3) δ 7.23 – 7.11 (m, 4H), 6.83 (s, 1H), 3.78 (t, J = 6.8 Hz, 2H),
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2.97 (s, 3H), 2.79 (t, J = 6.8 Hz, 2H), 0.85 (s, 9H), ꢀ0.03 (s, 6H); C NMR (75 MHz, CDCl3) δ 137.1,
134.8, 130.5, 121.4, 64.4, 53.6, 39.0, 39.2, 29.8, 26.0, 18.4, ꢀ5.3.
N-(4-methoxynaphthalen-1-yl)-2-nitrobenzenesulfonamide (15j)22: was obtained without purification
as a brown solid: 0.95 mmol, 311 mg, 95% yield; 1H NMR (300 MHz, Acetoneꢀd6) δ 9.17 (br, 1H), 8.21
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(d, J = 7.7 Hz, 1H), 8.08 – 7.72 (m, 7.3 Hz, 4H), 7.75 – 7.54 (m, 2H), 7.57 – 7.27 (m, 4H); C NMR
(75 MHz, Acetoneꢀd6) δ 149.0, 135.3, 135.2, 133.4, 133.2, 132.4, 131.7, 131.3, 129.0, 128.9, 127.3,
127.2, 126.3, 126.1, 125.8, 123.6.
Tributyl(2-methyl-5-(2-nitrophenylsulfonamido)phenyl)phosphonium) chloride (17a): was
obtained by silica gel chromatography with a mixture of CH2Cl2/MeOH (97:03) as a brown solid: 0.084
mmol, 41.5 mg, 84% yield; Mp: 37ꢀ40 °C; 1H NMR (300 MHz, CDCl3) δ 8.11 (dd, J = 8.0, 1.4 Hz, 1H),
7.48 – 7.34 (m, 3H), 7.34 – 7.34 (m, 1H), 7.28 (s, 1H), 7.04 (t, J = 7.3 Hz, 1H), 4.13 (s, 1H), 2.49 – 2.36
(m, 6H), 2.34 (s, 3H), 1.49 – 1.22 (m, 12H), 0.85 (t, J = 7.0 Hz, 9H); 13C {1H} NMR (75 MHz, CDCl3)
δ 149.2, 147.4, 147.3, 138.2, 133.8, 133.6, 130.9, 130.7, 130.6, 130.2, 130.1, 127.8, 125.9, 125.8, 122.8,
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114.1, 113.1, 23.8, 23.6, 20.9, 20.4, 19.7, 13.5; P NMR (122 MHz, CDCl3) δ 30.4 (br); HRMS (ESI):
Calc. for C25H38N2O4PS+ (M)+: 493.2284; found: 493.2312.
Tributyl(2-methoxy-5-(2-nitrophenylsulfonamido)phenyl)phosphonium chloride (17d): was
obtained by silica gel chromatography with a mixture of CH2Cl2/MeOH (97:03) as an orange solid:
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0.095 mmol, 48.4 mg, 95% yield; Mp: 45ꢀ47 °C; H NMR (300 MHz, CDCl3) δ 8.16 (dd, J = 7.5, 1.2
Hz, 1H), 7.54 – 7.37 (m, 3H), 7.35 (d, J = 1.2 Hz, 1H), 7.32 (dd, J = 5.9, 1.9 Hz, 1H), 6.82 (dd, J = 9.0,
6.4 Hz, 1H), 3.81 (s, 3H), 2.45 – 2.09 (m, 6H), 1.47 – 1.18 (m, 12H), 0.83 (t, J = 6.9 Hz, 9H); 13C {1H}
NMR (75 MHz, CDCl3) δ 155.5, 149.0, 140.7, 140.5, 137.1, 131.2, 131.1, 130.9, 130.7, 126.7, 126.6,
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122.8, 112.5, 112.4, 103.7, 102.6, 56.2, 23.8, 23.7, 23.6, 19.6, 18.9, 13.4; P NMR (122 MHz, CDCl3)
δ 29.7 (br); HRMS (ESI): Calc. for C25H38N2O5PS+ (M)+: 509,2234; found: 509.2235.
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Tributyl(2-ethyl-5-(2-nitrophenylsulfonamido)phenyl)phosphonium chloride (17e): was obtained
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by silica gel chromatography with a mixture of CH2Cl2/MeOH (97:03) as a brown solid: 0.079 mmol,
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40.1 mg, 79% yield; Mp: 130ꢀ131 °C; H NMR (300 MHz, CDCl3) δ 8.08 (dd, J = 6.2, 2.1 Hz, 1H),
7.46 – 7.34 (m, 3H), 7.31 (d, J = 8.5 Hz, 1H), 7.18 (dd, J = 15.5, 2.3 Hz, 1H), 7.14 – 7.08 (m, 1H), 3.47
(s, 1H), 2.57 (q, J = 7.3 Hz, 2H), 2.45 – 2.30 (m, J = 15.9, 11.8 Hz, 6H), 1.47 – 1.23 (m, 12H), 1.18 (t, J
= 7.4 Hz, 3H), 0.84 (t, J = 7.0 Hz, 9H); 13C {1H} NMR (75 MHz, CDCl3) δ 149.2, 148.1, 147.9, 138.67,
136.3, 136.2, 131.5, 131.3, 130.9, 130.6, 128.2, 128.1, 125.3, 125.1, 122.8, 113.2, 112.2, 26.4, 26.3,
23.9, 23.9, 23.8, 23.6, 21.0, 20.3, 15.7, 13.5; 31P NMR (122 MHz, CDCl3) δ 29.9 (br); HRMS (ESI):
Calc. for C26H40N2O4PS+ (M)+: 507.2441; found: 507.2447.
Tributyl(2-butyl-5-(2-nitrophenylsulfonamido)phenyl)phosphonium chloride (17f): was obtained
by silica gel chromatography with a mixture of CH2Cl2/MeOH (97:03) as a brown oil: 0.075 mmol, 40.2
mg, 75% yield; 1H NMR (300 MHz, CDCl3) δ 8.10 (dd, J = 6.2, 1.7 Hz, 1H), 7.47 – 7.34 (m, 3H), 7.31
(d, J = 8.5 Hz, 1H), 7.20 (dd, J = 15.2, 1.7 Hz, 1H), 7.11 (dd, J = 8.3, 6.6 Hz, 1H), 3.34 (s, 1H), 2.50 (t,
J = 7.3 Hz, 2H), 2.43 – 2.29 (m, 6H), 1.54 – 1.24 (m, 16H), 0.97 – 0.74 (m, 12H); C {1H} NMR (75
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MHz, CDCl3) δ 149.2, 148.0, 147.8, 138.6, 135.1, 135.0, 132.0, 131.8, 130.9, 130.6, 130.5, 128.1,
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125.4, 125.3, 122.8, 113.3, 112.3, 34.0, 33.3, 24.0, 23.9, 23.9, 23.6, 22.8, 21.1, 20.5, 14.1, 13.5; P
NMR (122 MHz, CDCl3) δ 30.2 (br); HRMS (ESI): Calc. for C28H44N2O4PS+ (M)+: 535.2754; found:
535.2730.
(3-bromo-2-methyl-5-(methylsulfonamido)phenyl)tributylphosphonium chloride (17g): was
obtained by silica gel chromatography with a mixture of CH2Cl2/MeOH (98:02 to 95:05) as an yellow
solid: 0.090 mmol, 41.9 mg, 90% yield; Mp: 50ꢀ52 °C; 1H NMR (300 MHz, CDCl3) δ 8.06 (s, 1H), 7.83
(d, J = 14.2 Hz, 1H), 5.77 (br, 1H), 3.00 (s, 3H), 2.69 – 2.55 (m, 6H), 2.52 (s, 3H), 1.56 – 1.35 (m, 12H),
0.92 (t, J = 6.9 Hz, 9H); C {1H} NMR (75 MHz, CDCl3) δ 142.9, 142.7, 132.4, 132.3, 129.4, 129.2,
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128.9, 125.6, 125.5, 117.9, 116.9, 39.8, 24.2, 24.1, 23.9, 23.7, 21.7, 21.7, 20.9, 20.3, 13.5; 31P NMR
(122 MHz, CDCl3) δ 33.1 (br); HRMS (ESI): Calc. for C20H36BrNO2PS+ (M)+: 464.1382; found:
464.1376.
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Tributyl(2-(2-methoxy-2-oxoethyl)-5-(methylsulfonamido)phenyl)phosphonium chloride (17h): by
silica gel chromatography with a mixture of CH2Cl2/MeOH (98:02 to 95:05) as a brown foam: 0.065
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mmol, 28.9 mg, 65% yield; H NMR (300 MHz, CDCl3) δ 7.91 (d, J = 14.9 Hz, 1H), 7.79 (d, J = 8.5
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Hz, 1H), 7.40 (dd, J = 8.6, 5.9 Hz, 1H), 6.23 (br, 1H), 3.74 (s, 2H), 3.70 (s, 3H), 3.01 (s, 3H), 2.65 –
2.53 (m, 6H), 1.54 – 1.36 (m, 12H), 0.91 (t, J = 6.9 Hz, 9H); 13C {1H} NMR (75 MHz, CDCl3) δ 170.6,
143.3, 143.1, 134.6, 134.5, 129.9, 129.8, 126.1, 126.0, 125.4, 116.8, 115.8, 52.8, 39.8, 39.3, 29.8, 24.1,
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24.0, 23.9, 23.7, 21.1, 20.5, 13.5; P NMR (122 MHz, CDCl3) δ 31.9 (br); HRMS (ESI): Calc. for
C22H39NO4PS+ (M)+: 444.2332; found: 444.2318.
Tributyl(2-(2-((tert-butyldimethylsilyl)oxy)ethyl)-5-(methylsulfonamido)-phenyl)-phosphonium
chloride (17i): was obtained was obtained by silica gel chromatography with a mixture of
CH2Cl2/MeOH (98:02 to 95:05) as an yellow foam: 0.068 mmol, 36.1 mg, 68% yield; 1H NMR (300
MHz, CDCl3) δ 10.72 (s, 1H), 8.49 (d, J = 15.3 Hz, 1H), 7.93 (d, J = 8.6 Hz, 1H), 7.43 (dd, J = 8.6, 5.8
Hz, 1H), 3.89 (t, J = 6.2 Hz, 2H), 3.10 (s, 3H), 2.89 (t, J = 6.1 Hz, 2H), 2.64 – 2.51 (m, 6H), 1.63 – 1.46
(m, 12H), 0.97 (t, J = 6.8 Hz, 9H), 0.84 (s, 9H), 0.01 (s, 6H); 13C {1H} NMR (75 MHz, CDCl3) δ 139.4,
139.2, 138.0, 137.9, 132.9, 132.8, 125.9, 125.7, 125.3, 117.1, 116.0, 63.1, 39.7, 36.7, 34.8, 31.7, 29.8,
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29.2, 26.0, 25.8, 25.4, 24.2, 24.0, 23.8, 23.6, 22.7, 21.5, 20.8, 18.4, 14.2, 13.6, 11.5, ꢀ3.46, ꢀ5.27; P
NMR (122 MHz, CDCl3) δ 31.5 (br); HRMS (ESI): Calc. for C27H53NO3PSSi+ (M)+: 530.3248; found:
530.3228.
Tributyl(1-methoxy-4-(2-nitrophenylsulfonamido)naphthalen-2-yl)phosphonium chloride (17j):
was obtained by recrystallization in diethyl ether as an yellow solid: 0.082 mmol, 45.9 mg, 82% yield;
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Mp: 51ꢀ52 °C; H NMR (300 MHz, CDCl3) δ 8.89 (dd, J = 6.9, 2.7 Hz, 1H), 8.14 (dd, J = 6.1, 1.9 Hz,
1H), 7.86 (dd, J = 6.7, 2.6 Hz, 1H), 7.58 – 7.48 (m, 2H), 7.38 – 7.28 (m, 3H), 7.15 (d, J = 13.7 Hz, 1H),
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3.98 (s, 3H), 2.46 – 2.25 (m, 6H), 1.52 – 1.24 (m, 12H), 0.88 (t, J = 7.0 Hz, 9H); C {1H} NMR (75
MHz, CDCl3) δ 152.0, 149.5, 145.3, 145.1, 139.1, 134.7, 130.6, 130.5, 130.1, 127.4, 127.3, 126.9,
126.9, 122.5, 121.8, 110.3, 110.2, 103.9, 102.8, 63.8, 23.9, 23.8, 23.8, 23.7, 20.3, 19.6, 13.5; 31P NMR
(122 MHz, CDCl3) δ 29.7 (br); HRMS (ESI): Calc. for C29H40N2O5PS+ (M)+: 559.2390; found:
559.2389.
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Dimethyl (2,4-dimethyl-5-(2-nitrophenylsulfonamido)phenyl)phosphonate (20a): was obtained by
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silica gel chromatography with a mixture of ethyl acetate/hexane (4:6 to 78:22) as an yellow solid: 0.095
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mmol, 39.4 mg, 95% yield; Mp: 137ꢀ139 °C; H NMR (300 MHz, CDCl3) δ 7.88 (d, J = 7.7 Hz, 1H),
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7.82 – 7.69 (m, 2H), 7.61 (t, J = 7.6 Hz, 1H), 7.52 (d, J = 15.0 Hz, 1H), 7.09 (d, J = 6.0 Hz, 1H), 3.70 (s,
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3H), 3.66 (s, 3H), 2.46 (s, 3H), 2.24 (s, 3H); C {1H} NMR (75 MHz, CDCl3) δ 148.1, 141.5, 141.3,
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139.9, 139.8, 134.6, 134.4, 134.1, 133.2, 132.7, 131.7, 131.6, 131.6, 131.5, 131.4, 125.6, 125.5, 123.2,
52.7, 52.7, 20.7, 20.7, 18.1; 31P NMR (122 MHz, CDCl3) δ 20.9 (br); HRMS (ESI): Calc. for
C16H23N3O7PS (M+NH4)+: 432.0989; found: 432.0988.
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Diethyl (2,4-dimethyl-5-(2-nitrophenylsulfonamido)-phenyl)phosphonate (20b): was obtained by
silica gel chromatography with a mixture of ethyl acetate/hexane (4:6 to 6:4) as a white solid: 0.070
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mmol, 31.0 mg, 70% yield; Mp: 155ꢀ157 °C; H NMR (300 MHz, CDCl3) δ 7.89 (dd, J = 7.9, 1.0 Hz,
1H), 7.80 (dd, J = 7.8, 1.3 Hz, 1H), 7.73 (td, J = 7.8, 1.4 Hz, 1H), 7.61 (td, J = 7.7, 1.1 Hz, 1H), 7.53 (d,
J = 14.9 Hz, 1H), 7.15 (s, 1H), 7.09 (d, J = 6.0 Hz, 1H), 4.12 – 3.91 (m, 4H), 2.49 (s, 3H), 2.27 (s, 3H),
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1.28 (t, J = 7.1 Hz, 6H); C {1H} NMR (75 MHz, CDCl3) δ 148.2, 141.4, 141.2, 139.6, 134.6, 134.4,
134.1, 133.3, 132.8, 131.6, 131.6, 131.4, 131.3, 131.3, 127.1, 125.6, 124.6, 124.6, 62.2, 62.2, 20.8, 20.8,
18.1, 16.5, 16.4; 31P NMR (122 MHz, CDCl3) δ 17.9 (br); HRMS (ESI): Calc. for C18H24N2O7PS+
(M+H)+: 443,1036; found: 443.1046.
Dimethyl (2-methoxy-5-(2-nitrophenylsulfonamido)phenyl)-phosphonate (20c): was obtained by
silica gel chromatography with a mixture of ethyl acetate/hexane (75:25 to 95:05) as a white solid: 0.095
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mmol, 39.6 mg, 95% yield; Mp: 147ꢀ148 °C; H NMR (300 MHz, CDCl3) δ 7.80 (td, J = 9.1, 0.9 Hz,
3H), 7.68 (td, J = 7.8, 1.2 Hz, 1H), 7.60 – 7.52 (m, 1H), 7.50 – 7.41 (m, 1H), 6.90 – 6.84 (m, 1H), 3.85
(s, 3H), 3.75 (s, 3H), 3.71 (s, 3H); 13C {1H} NMR (75 MHz, CDCl3) δ 160.0, 148.4, 134.1, 132.6, 132.4,
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131.7, 130.7, 130.6, 128.5, 128.3, 125.4, 117.9, 115.4, 112.3, 112.2, 56.4, 53.2, 53.2; P NMR (122
MHz, CDCl3); HRMS (ESI): Calc. for C15H18N2O8PS (M+H)+: 417.0516; found: 417.0511.
Dimethyl (1-methoxy-4-(2-nitrophenylsulfonamido)naphthalen-2-yl)phosphonate (20d): was
obtained by silica gel chromatography with a mixture of ethyl acetate/hexane (4:6 to 6:4) as a white
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solid: 0.069 mmol, 32.2 mg, 69% yield; Mp: 51ꢀ53 °C; H NMR (300 MHz, CDCl3) δ 8.24 – 8.09 (m,
2H), 7.91 (d, J = 7.9 Hz, 1H), 7.77 – 7.63 (m, 3H), 7.62 – 7.44 (m, 4H), 4.09 (s, 3H), 3.80 (s, 3H), 3.76
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(s, 3H); 13C {1H} NMR (75 MHz, CDCl3) δ 160.7, 148.3, 134.6, 134.1, 133.0, 132.8, 131.6, 129.6,
128.9, 128.7, 127.4, 127.3, 125.5, 123.7, 123.6, 118.0, 115.5, 64.2, 53.2, 53.1; 31P NMR (122 MHz,
CDCl3) δ 29.7 (br); HRMS (ESI): Calc. for C19H19N2NaO8PS (M+Na)+: 489.0492; found: 489.0499.
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(E)-N-(4-methoxy-2,4-dimethylcyclohexa-2,5-dien-1-ylidene)methanesulfonamide
(21a)8:
was
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obtained by silica gel chromatography with a mixture of EtOAc/Hexane (15:85) as a white foam: 0.86
mmol, 197 mg, 86% yield; 1H NMR (300 MHz, CDCl3) δ 7.34 (dd, J = 10.2, 2.7 Hz, 1H), 6.66 (dd, J =
10.2, 2.4 Hz, 1H), 6.48 (s, 1H), 3.16 (d, J = 2.6 Hz, 3H), 3.09 (d, J = 2.7 Hz, 3H), 1.92 (s, 3H), 1.32 (d, J
= 2.4 Hz, 3H).
(E)-N-(4-methoxy-2,4-dimethylcyclohexa-2,5-dien-1-ylidene)-2-nitrobenzenesulfonamide
(21b):
was obtained by silica gel chromatography with a mixture of EtOAc/Hexane (15:85) as a white foam:
0.69 mmol, 232 mg, 69% yield, 1H NMR (300 MHz, CDCl3) δ 8.35 – 8.22 (m, 1H), 7.85 (d, J = 8.8 Hz,
1H), 7.80 – 7.67 (m, 2H), 7.49 (d, J = 10.2 Hz, 1H), 6.80 (dd, J = 10.2, 2.4 Hz, 1H), 6.57 (s, 1H), 3.16
(s, 3H), 1.89 (s, 3H), 1.39 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 165.9, 153.6, 149.1, 136.4, 135.0,
133.8, 132.6, 129.8, 124.9, 124.6, 73.2, 53.7, 26.0, 17.6; LRMS Calc. for C15H17N2O5S (M+H)+: 337;
found: 337.
N-(4-ethyl-4-methoxycyclohexa-2,5-dien-1-ylidene)methanesulfonamide (21c)8: was obtained by
silica gel chromatography with a mixture of EtOAc/Hexane (15:85) as an yellow oil: 0.85 mmol, 194
mg, 85% yield; 1H NMR (300 MHz, CDCl3) δ 7.44 (dd, J = 10.6, 1.8 Hz, 1H), 6.74 – 6.57 (m, 2H), 6.43
(dd, J = 10.3, 1.8 Hz, 1H), 3.16 (s, 6H), 1.73 (q, J = 7.6 Hz, 2H), 0.80 (t, J = 7.6 Hz, 3H); 13C NMR (75
MHz, CDCl3) δ 164.4, 152.0, 150.5, 131.4, 125.3, 76.5, 53.5, 43.1, 32.5, 7.9.
N-(4-methoxy-4-methylcyclohexa-2,5-dien-1-ylidene)ethanesulfonamide (21d): was obtained by
silica gel chromatography with a mixture of EtOAc/Hexane (1:9) as a white solid: 0.86 mmol, 197 mg,
86% yield; Mp: 79ꢀ80 °C; 1H NMR (300 MHz, CDCl3) δ 7.40 (dd, J = 10.5, 2.0 Hz, 1H), 6.74 – 6.61
(m, 2H), 6.36 (dd, J = 10.2, 2.0 Hz, 1H), 3.20 (q, J = 7.4 Hz, 2H), 3.13 (s, 3H), 1.44 (t, J = 7.4 Hz, 3H),
1.37 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 164.4, 152.2, 150.8, 130.3, 124.2, 72.7, 53.6, 49.3, 26.0, 8.1;
LRMS Calc. for C10H16NO3S (M+H)+: 230; found: 230.
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N-(4-methoxy-4-methylcyclohexa-2,5-dien-1-ylidene)-2-nitrobenzenesulfonamide
(21e):
was
obtained by silica gel chromatography with a mixture of EtOAc/Hexane (15:85) as a white solid: 0.71
mmol, 228 mg, 71% yield; Mp: 151ꢀ152 °C; 1H NMR (300 MHz, CDCl3) δ 8.33 – 8.27 (m, 1H), 7.89 –
7.82 (m, 1H), 7.79 – 7.73 (m, 2H), 7.55 (d, J = 9.9 Hz, 1H), 6.86 – 6.75 (m, 2H), 6.41 (d, J = 9.3 Hz,
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1H), 3.20 (s, 3H), 1.43 (s, 3H); C NMR (75 MHz, CDCl3) δ 164.6, 154.0, 152.5, 148.0, 134.5, 134.0,
132.7, 130.1, 124.9, 124.2, 73.0, 53.8, 26.0; LRMS Calc. for C14H15N2O5S (M+H)+: 323; found: 323.
N-(4-methoxy-4-methylcyclohexa-2,5-dien-1-ylidene)methanesulfonamide (21f)8: was obtained by
silica gel chromatography with a mixture of EtOAc/Hexane (15:85) as a colorless oil: 0.95 mmol, 204
mg, 95% yield; 1H NMR (300 MHz, CDCl3) δ 7.40 (d, J = 9.5 Hz, 1H), 6.76 – 6.64 (m, 2H), 6.44 – 6.31
(m, 1H), 3.17 (s, 3H), 3.16 (s, 3H), 1.39 (s, 3H).
N-(4-methoxy-4-methylcyclohexa-2,5-dien-1-ylidene)-4-methylbenzenesulfonamide (21g): was
obtained by silica gel chromatography with a mixture of EtOAc/Hexane (1:9) as a white solid: 0.89
mmol, 259 mg, 89 % yield; Mp: 123ꢀ124 °C, 1H NMR (300 MHz, CDCl3) δ 7.86 (d, J = 8.1 Hz, 2H),
7.60 (d, J = 10.2 Hz, 1H), 7.30 (d, J = 8.0 Hz, 2H), 6.74 (dd, J = 10.3, 2.2 Hz, 1H), 6.65 (dd, J = 10.0,
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2.2 Hz, 1H), 6.35 (d, J = 10.0 Hz, 1H), 3.13 (s, 3H), 2.40 (s, 3H), 1.37 (s, 3H); C NMR (75 MHz,
CDCl3) δ 163.7, 152.6, 150.9, 143.8, 138.2, 130.5, 129.6, 127.2, 123.9, 72.7, 53.6, 26.0, 21.6; LRMS
Calc. for C15H18NO3S (M+H)+: 292; found: 292.
(E)-N-(4,4-dimethoxynaphthalen-1(4H)-ylidene)methanesulfonamide (21h)2g: was obtained by silica
gel chromatography with a mixture of EtOAc/Hexane (1:9) as an brown oil: 0.95 mmol, 267 mg, 95%
yield; 1H NMR (300 MHz, CDCl3) δ 8.22 (dd, J = 8.0, 0.9 Hz, 1H), 7.75 (dd, J = 7.9, 1.1 Hz, 1H), 7.71
(d, J = 10.7 Hz, 1H), 7.66 (td, J = 7.6, 1.3 Hz, 1H), 7.52 – 7.44 (m, 1H), 6.86 (d, J = 10.7 Hz, 1H), 3.30
(s, 3H), 3.18 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 163.4, 143.9, 139.4, 133.6, 130.9, 129.2, 126.9,
126.4, 94.4, 51.3, 43.3.
Tributyl(2-ethyl-5-(methylsulfonamido)phenyl)phosphonium chloride (22c): was obtained by silica
gel chromatography with a mixture of CH2Cl2/MeOH (95:05) as a brown oil: 0.060 mmol, 24.0 mg,
60% yield; 1H NMR (300 MHz, CDCl3) δ 7.61 (d, J = 8.6 Hz, 1H), 7.43 (dd, J = 15.2, 1.8 Hz, 1H), 7.24
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– 7.18 (m, 1H), 4.51 (br, 1H), 2.92 (s, 3H), 2.62 (q, J = 7.3 Hz, 2H), 2.54 – 2.39 (m, 6H), 1.50 – 1.37
(m, 12H), 1.24 (t, J = 7.5, 3H), 0.90 (t, J = 6.8 Hz, 9H); 13C {1H} NMR (75 MHz, CDCl3) δ 147.5,
135.9, 131.9, 131.8, 126.5, 125.5, 125.4, 113.4, 112.4, 39.8, 29.8, 26.6, 26.6, 24.2, 24.1, 24.0, 23.8,
21.4, 20.7, 16.0, 14.2, 13.6; 31P NMR (122 MHz, CDCl3) δ 29.7 (br); HRMS (ESI): Calc. for
C21H39NO2PS+ (M)+: 400,2434; found: 400.2440.
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Tributyl(5-(ethylsulfonamido)-2-methylphenyl)phosphonium chloride (22d): was obtained by
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recrystallization in diethyl ether as a white solid: 0.072 mmol, 28.8 mg, 72% yield; Mp: 61ꢀ63 °C; H
NMR (300 MHz, CDCl3) δ 7.40 (d, J = 13.8 Hz, 2H), 7.08 (t, J = 7.5 Hz, 1H), 3.04 (q, J = 7.4 Hz, 2H),
2.37 – 2.25 (m, 9H), 1.54 – 1.43 (m, J = 3.6 Hz, 12H), 1.39 (t, J = 7.4 Hz, 3H), 0.96 (t, J = 6.8 Hz, 9H);
13C {1H} NMR (75 MHz, CDCl3) δ 150.8, 150.6, 133.7, 133.5, 126.5, 126.4, 125.9, 125.1, 125.0, 113.2,
112.2, 45.8, 23.9, 23.8, 23.7, 23.5, 20.6, 19.9, 13.3, 9.2; 31P NMR (122 MHz, CDCl3) δ 29.7 (br);
HRMS (ESI): Calc. for C21H39NO2PS+ (M)+: 400,2434; found: 400.2428.
Tributyl(2-methyl-5-(methylsulfonamido)phenyl)phosphonium chloride (22f): was obtained by
silica gel chromatography with a mixture of CH2Cl2/MeOH (9:1) as a yellow solid: 0.059 mmol, 22.8
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mg, 59% yield; Mp: 86ꢀ89 °C; H NMR (300 MHz, CDCl3) δ 7.47 (d, J = 8.8 Hz, 1H), 7.36 – 7.29 (m,
1H), 7.11 (t, J = 7.7 Hz, 1H), 2.96 (s, 3H), 2.39 – 2.26 (m, 9H), 1.54 – 1.41 (m, J = 3.7 Hz, 12H), 0.96
(t, J = 6.7 Hz, 9H); 13C {1H} NMR (75 MHz, CDCl3) δ 150.9, 150.7, 133.8, 133.7, 126.3, 126.2, 125.3,
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125.2, 113.3, 112.3, 39.2, 23.9, 23.8, 23.7, 23.5, 20.6, 19.9, 13.3; P NMR (122 MHz, CDCl3) δ 29.6
(br); HRMS (ESI): Calc. for C20H37NO2PS+ (M)+: 386,2277; found: 386.2271.
Tributyl(2-methyl-5-(4-methylphenylsulfonamido)phenyl)phosphonium chloride (22g): was
obtained by recrystallization in diethyl ether as a white solid: 0.056 mmol, 25.9 mg, 56% yield; Mp:
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114ꢀ117 °C; H NMR (300 MHz, CDCl3) δ 7.82 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.4 Hz, 1H), 7.18 (d, J
= 15.7 Hz, 1H), 7.10 (d, J = 7.9 Hz, 2H), 7.04 – 6.95 (m, 1H), 2.41 – 2.26 (m, 12H), 1.44 – 1.25 (m,
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12H), 0.87 (t, J = 7.0 Hz, 9H); C {1H} NMR (75 MHz, CDCl3) δ 150.1, 149.9, 143.5, 139.6, 133.7,
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133.5, 128.8, 127.1, 127.0, 125.2, 125.1, 113.1, 112.1, 23.9, 23.7, 21.4, 20.6, 20.0, 13.5; P NMR (122
MHz, CDCl3) δ 30.0 (br); HRMS (ESI): Calc. for C26H41NO2PS+ (M)+: 462,2590; found: 462.2598.
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Tributyl(1-methoxy-4-(methylsulfonamido)naphthalen-2-yl)phosphonium chloride (22h): was
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obtained by recrystallization in diethyl ether as a brown solid: 0.080 mmol, 36.2 mg, 80% yield; Mp:
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157ꢀ159 °C; H NMR (300 MHz, CDCl3) δ 8.85 – 8.78 (m, 1H), 7.89 – 7.82 (m, 1H), 7.57 – 7.49 (m,
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2H), 7.37 (d, J = 14.1 Hz, 1H), 4.01 (s, 3H), 3.01 (s, 3H), 2.45 – 2.33 (m, 6H), 1.56 – 1.47 (m, 12H),
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0.96 (t, J = 6.7 Hz, 9H); C {1H} NMR (75 MHz, CDCl3) δ 152.4, 144.8, 144.7, 144.6, 134.8, 134.8,
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127.5, 127.4, 127.4, 127.2, 126.9, 126.79, 126.8, 121.8, 110.7, 63.8, 63.8, 39.3, 24.1, 24.0, 23.9, 23.7,
20.7, 20.1, 13.4; 31P NMR (122 MHz, CDCl3) δ 29.6 (br); HRMS (ESI): Calc. for C24H39NO3PS+ (M)+:
452.2383; found: 452.2393.
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Acknowledgment: We are very grateful to the Natural Sciences and Engineering Research Council of
Canada (NSERC), the Canada Foundation for Innovation (CFI), and the provincial government of
Quebec (FQRNT and CCVC) for their precious financial support in this research. We thank Dr. D.
Warschawski for helpful discussion in NMR. S. Coulibali thanks the “Programme Canadien de Bourses
de la Francophonie" for a scholarship.
Supporting Information Available: The Supporting Information is available free of charge on the
ACS Publications website 1H and 13C NMR spectral data of all compounds.
References and Footnotes:
1 Davies, H. M. L.; Morton, D. J. Org. Chem. 2016, 81, 343.
2 (a) Tamura, Y.; Yakura, T.; Haruta, J.; Kita, Y. J. Org. Chem. 1987, 52, 3927. (b) Farid, U.; Malmedy,
F.; Claveau, R.; Albers, L.; Wirth, T. Angew. Chem. Int. Ed. 2013, 52, 7018. (c) Zhdankin, V. V.
Hypervalent Iodine Chemistry: Preparation, Structure, and Synthetic Applications of Polyvalent Iodine
Compounds; John Wiley & Sons: Chichester, UK, 2013. (d) Coffinier, R.; El Assal, M.; Peixoto, P. A.;
Bosset, C.; Miqueu, K.; Sotiropoulos, J.ꢀM.; Pouységu, L.; Quideau, S. Org. Lett. 2016, 18, 1120. (e)
Jacquemot, G.; Maertens, G.; Canesi, S. Chem. Eur. J. 2015, 21 ,7713. (f) Coulibali, S.; Godou, T.;
Canesi, S. Org. Lett. 2016, 18, 4348. (g) Coulibali, S.; Deruer, E.; Godin, E.; Canesi, S. Org. Lett. 2017,
19, 1188. (h) Martínez, C.; Muñiz, K. Angew. Chem. Int. Ed., 2015, 54, 8287. (h) Antien, K.; Viault, G.;
Pouysegu, L.; Peixoto, P. A.; Quideau, S. Tetrahedron 2017, 73, 3684. (i) Uyanik, M.; Sasakura, N.;
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