Cu-Catalyzed photoredox chlorosulfonation of alkenes and alkynes

Article abstract of DOI:10.1021/acs.joc.9b00238

Visible-light photoredox chlorosulfonation of alkenes and alkynes is achieved using a Cu photocatalyst. The reactions occur under mild conditions, have broad scope, and have high functional group tolerance.

Full text of DOI:10.1021/acs.joc.9b00238

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Cu-Catalyzed Photoredox Chlorosulfonation of Alkenes and Alkynes
Murat Alkan-Zambada, and Xile Hu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00238 • Publication Date (Web): 14 Mar 2019
Downloaded from http://pubs.acs.org on March 14, 2019
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Murat Alkan-Zambada and Xile Hu
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Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique
Fédérale de Lausanne (EPFL), ISIC-LSCI, BCH 3305, Lausanne 1015, Switzerland.
Supporting Information Placeholder
ABSTRACT: Visible-light photoredox chlorosulfonation of alkenes and alkynes is achieved using a Cu photocatalyst. The reactions
occur under mild conditions, have broad scope and high functional group tolerance.
Sulfones are widely present in pharmaceutical compounds (Fig-
ure 1A).1 Methods introducing the sulfone functional group into
organic compounds are highly desirable. Traditionally, sulfones
are made in two steps: first thiolation followed by oxidation.2-3
Chlorosulfonation of alkenes and alkynes is an attractive
method to introduce both sulfone and chloro functional groups
into organic molecules using feedstock reagents.4-9 Recently,
photoredox catalysis was developed for efficient sulfonations of
alkenes and heteroarenes using organic sulfonyl chlorides as
sulfonating agents.10-13 However, there were still only a few re-
ports of photocatalytic chlorosulfonation of alkenes and al-
kynes.14-17 Here we describe a broad-scope photoredox
chlorosulfonation of terminal alkenes and alkynes, employing
our recently developed Cu photocatalyst18 1 (Figure 1B).
The chlorosulfonation of methacrylamide 2 using
para-fluorobenzylsulfonyl chloride (3) yielding a Bicalutamide
derivative 4 was the test reaction for the optimization of condi-
tions (Table 1). Cu complex 1, previously developed by us for
chlorotrifluoromethylation of alkenes18, was chosen as the cat-
alyst. After an initial screening, we found that 4 could indeed
be formed, albeit in low yields, when the reaction was con-
ducted at room temperature in dichloromethane (DCM) using a
2 W LED light (Table 1, entries 1-3). A loading of 2.5 mol% of
1 gave the best result (Table 1, entry 2). The optimal ratio of 2:3
was 1:1 (SI, Table S1, entries 1-5). A 40 W light source im-
proved the conversion to 70% and the yield to 59% (Table 1,
entry 4). Various additives did not improve conversions or
yields (SI, Table S1, entries 5-9). While acetonitrile (MeCN)
alone was less effective as the solvent (Table 1, entry 5), a mix-
ture of DCM and MeCN gave better yields (Table 1, entries 6-
7). The reaction could be conducted at a 5 mmol scale (Table 1,
entry 7). Control reactions showed that a high-energy light
source (SI, Table S1, entry 10), PC 1, light and a N2 atmosphere
were all needed for the reaction to proceed smoothly (SI, Table
S2, entries 1-3).
Figure 1. (A) Examples of sulfone-containing pharmaceutical com-
pounds. (B) Cu-catalyzed chlorosulfonation of both alkenes and al-
kynes.
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Table 1. Optimization of reaction conditions for chlorosul-
fonation.
lower yields even when 5 equiv. of styrene was used (Figure 2,
8z-8ab).
1
2
3
4
5
6
7
8
9
Entry
x
y
Solvent
Time Conversiona
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[h]
(yield)b [%]
1
2
3
4
5
6
2
2
2
1
DCM (3 mL)
67.5
24
36 (n.d.)c
45 (33)
20 (n.d.)
70 (59)
55 (47)
90 (71)
2.5 DCM (3 mL)
DCM (3 mL)
5
24
40 2.5 DCM (3 mL)
40 2.5 MeCN (3 mL)
24
24
40 2.5 DCM+MeCN
(1.5+1.5 mL)
24
7
40 2.5 DCM+MeCN
(2.5+2.5 mL)
66
93 (86, 64d)
aDetermined by 1H NMR. bIsolated yields. cn.r. = no reaction,
n.d. = not determined. dReaction performed in 5 mmol scale.
We further tested common Ru and Ir based PCs as
well as organic PCs (SI, Table S3) in place of catalyst 1. Or-
ganic PC 5,10-di(4-trifluoromethylphenyl)-5,10-dihydro-
phenazine gave 43% yield at 50% conversion of starting mate-
rial (SI, Table S2, entry 10). [Ir(dtbbpy)(ppy)2][PF6] gave 42%
yield at full conversion of starting material (SI, Table S2, entry
13). All other tested Ru, Ir, and organic PCs gave no or only a
trace amount of product. No reaction occurred when the radical
initiator AIBN was used instead of a catalyst. The commonly
used Cu PC [Cu(dap)2]Cl (5, dap = 2,9-bis(4-anisyl)-1,10-phe-
nanthroline) was a good catalyst, giving 89% yield at full con-
version of starting material (SI, Table S2, entry 5). This result
prompted us to compare the efficiencies of catalysts 1 and 5 for
the reactions of several other substrates (SI, Figure S2). For all
substrates examined, catalyst 1 was more efficient than 5. Thus,
catalyst 1 was used for the study of scope.
Figure 2. Substrate scope of sulfonyl chlorides. a2 W LED450, 1
(1.0 mol%), DCM (3 mL), 24 h, rt, N2 atm., 1 mmol scale.
b5 equiv. of styrene.
We then probed the substrate scope of the alkenes us-
ing the arylsulfonyl chloride 3 as the reaction partner (Figure 3).
Both electron-donating and electron-withdrawing substituents
at the 4-position of styrenes reacted in good yields (Figure 3,
10a-10h). The product from 4-methoxy styrene was unstable
with respect to elimination of HCl, and an (E)-vinylsulfone
(10e) was obtained after purification. Styrenes with a halogen
group in 4-, 3- or 2-position all reacted in excellent yields (Fig-
ure 3, 10f-10n). The reaction tolerated a 2,4,6-trisubstituted sty-
rene (Figure 3, 10o). Pyridyl- or naphtyl substrates also reacted
well (Figure 3, 10p-10r). A styrene substituted at the α-position
was a viable substrate (Figure 3, 10s). Internal styrenes also
worked (Figure 3, 10t-10u), but cinnamaldehyde was unreac-
tive. Alkenes substituted by an electron-withdrawing group
were reactive only when there was an additional Me-group at
the 2-position of the alkenes (Table 1, 4; Figure 3, 10v). Un-
branched, terminal alkenes substituted by an electron-with-
drawing group underwent no reaction. Unactivated terminal al-
kyl alkenes gave low yields while internal alkyl alkenes gave
no reaction (Figure 3, 10w-10y). To our delight, a complex, Es-
trone-derived substrate reacted to give 10z in 66% yield.
The scope of sulfonyl chlorides was first probed using
styrene as the alkene partner (Figure 2). A large number of ar-
ylsulfonyl chlorides with various substituents at 4-, 3-, or 2-po-
sition of the aryl groups reacted in good yields (Figure 2, 8a-
8p). Both electron donating and withdrawing substituents were
tolerated. For some unknown reason 2-fluorobenzylsulfonyl
chloride did not react. For a very bulky aryl sulfonyl chloride
with an isopropyl group at 2,4,6-positions of the aryl group, the
yield was still 50% (Figure 2, 8q). A heteroaryl suflonyl chlo-
ride was also successfully employed (Figure 2, 8r). Interest-
ingly, when trichloromethylsulfonyl chloride was used, extru-
sion of SO2 was observed (Figure 2, 8s). Alkylsulfonyl chlo-
rides were suitable substrates as well (Figure 2, 8t-8y). In some
cases (8b, 8d, 8f, 8g and 8s), the catalyst loading could be low-
ered to 1.0 mol% under slightly modified conditions. Sulfamoyl
chlorides were more challenging substrates, generally giving
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Figure 3. Substrate scope of alkenes.
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Figure 4. Substrate scope of alkynes. The single crystal X-ray
structure of 12d is displayed with ellipsoids at 50% probability
level; hydrogen atoms are omitted for clarity.
Phenylacetylenes were also tested as substrates using
the same optimized conditions (Figure 4). In contrast to the re-
cently reported Ir-catalyzed chlorosulfonation of alkynes,
which gave a mixture of (E)- and (Z)-alkenes17, we obtained ex-
clusively (E)-chlorosulfonylvinylbenzenes. The excellent E-se-
lectivity might originate from an outer-sphere reaction mecha-
nism where the radical termination step proceeds through the
thermodynamically favored configuration. The yields were typ-
ically modest. Substituents at 4, 3-, or 2-positions were tolerated
(Figure 4, 12a-12m). A single crystal X-ray structure of 12d
was determined, confirming the connectivity and stereochemis-
try (Figure 4). Unactivated alkyl alkynes or internal aryl alkynes
were not reactive.
Overall, the chlorosulfonation of alkenes and alkynes
tolerated various functional groups such as ester (8j), nitrile
(8i), halogens (8e-8h and 8k-8o), thiophene (8r) and amine (8z-
8ab) in the sulfonyl chloride reagents, as well as ester (10b,
10v, 12c), F (10f, 10i, 10l, 12f, 12j, 12m), Cl (10g, 10j, 10m,
12g, 12k) and Br (10h, 10k, 10n, 12h) functional groups in the
alkene and alkyne substrates.
In summary, a Cu-catalyzed photoredox chlorosul-
fonation of alkenes and alkynes has been developed. The
method has broad substrate scope and high functional group tol-
erance. It can be used to prepare a wide range of organic sul-
fones from feedstock reagents under mild conditions.
All chemicals were purchased from
commercial suppliers and used without further purification.
Complex 118 and (8R,9S,13S,14S)-13-methyl-3-vinyl-
6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phe-
nanthren-17-one19 were prepared according to literature proce-
dure. All photoredox reactions were carried out under an N2 at-
mosphere using standard glovebox techniques and NMR spec-
tra of known compounds agree with reports. The light sources
were either a homemade device (700 mA or ca. 2 W as previ-
ously reported18 from the mechanical and electrical workshop
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of EPFL or LEDs purchased from Kessil Co., Ltd. (40 W max.,
m/z: [M+Na]+ Calcd for C18H13ClF4N2NaO3S 471.0164; Found
471.0173.
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product No. A160WE) cooled by table fans purchased from
Galaxus Co., Ltd. (35 W max.). Solvents were purified using a
two-column solid-state purification system (Innovative Tech-
nology, NJ, USA) and transferred to the glovebox without ex-
posure to air. NMR spectra were recorded on a Bruker Avance
GP B was applied (298 mg = 98%, white solid). 1H NMR
2
(400 MHz, CDCl3, ppm): δ = 2.41 (s, 3H), 3.86 (dd, JH,H
=
1
14.75 Hz, 3JH,H = 7.18 Hz, 1H), 3.95 (dd, 2JH,H = 14.75 Hz, 3JH,H
= 6.74 Hz, 1H), 5.32 (t, 3JH,H = 6.94 Hz, 1H), 7.26-7.32 (m, 7H),
400 Spectrometer. H and 13C{1H} chemical shifts were refer-
enced internally to residual solvent peaks relative to TMS (δ =
0 ppm) and 19F chemical shifts were externally referenced to
CFCl3 (δ = 0 ppm). High resolution mass spectra, X-ray struc-
tures and elemental analyses were determined by the respective
EPFL facilities. X-ray quality crystals were grown by slow dif-
fusion of Et2O in DCM. The stereochemistry of compounds
12a-12m were confirmed by one dimensional NOESY experi-
ments which showed no NOE signal to the aryl moieties.
7.61 (d, JH,H = 8.40 Hz, 2H). 13C{1H} NMR (100.6 MHz,
3
CDCl3, ppm): δ = 21.7, 55.7, 64.2, 127.6, 128.5, 129.3, 129.5,
130.2, 136.7, 139.1, 145.6. HRMS (ESI/QTOF) m/z: [M+Na]+
Calcd for C15H15ClNaO2S 317.0373; Found 317.0383.
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GP A was
1
applied (267 mg = 95%, white solid). H NMR (400 MHz,
CDCl3, ppm): δ = 3.82-3.90 (m, 4H), 3.96 (dd, 2JH,H = 14.75 Hz,
3JH,H = 6.90 Hz, 1H), 5.34 (t, 3JH,H = 6.88 Hz, 1H), 6.91 (d, 3JH,H
A Schlenk flask (10 mL) was
charged with a magnetic stirring bar and catalyst 1 (10.8 mg,
1.0 mol%). The Schlenk flask was then transferred into a glove-
box where DCM (3 mL), sulfonyl chloride (1.0 mmol) and al-
kene (1.0 mmol) were added. The reaction mixture was then ir-
radiated with a blue LED (λmax = 450 nm, 700 mA, ca. 2 W as
previously reported18) from a distance of ca. 1 cm and stirred at
rt for 24 hours. After completion of the reaction, the flask was
transferred out of the glovebox, the solvent was removed under
reduced pressure and the crude mixture was purified by column
chromatography. NMR spectra of known compounds agree
with literature values and new compounds were further charac-
terized by HRMS and/or elemental analysis.
3
= 8.72 Hz, 2H), 7.25-7.32 (m, 5H), 7.69 (d, JH,H = 8.72 Hz,
2H). 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 55.4, 55.8,
64.4, 114.5, 127.3, 129.0, 129.2, 130.5, 130.7, 138.8, 163.3.
HRMS (ESI/QTOF) m/z: [M+Na]+ Calcd for C14H13ClO2SNa
303.0222; Found 303.0226.
GP B was applied (292 mg = 94%, white solid). 1H NMR
(400 MHz, CDCl3, ppm): δ = 3.82-3.90 (m, 4H), 3.96 (dd, 2JH,H
= 14.75 Hz, 3JH,H = 6.90 Hz, 1H), 5.34 (t, 3JH,H = 6.88 Hz, 1H),
3
6.91 (d, 3JH,H = 8.72 Hz, 2H), 7.25-7.32 (m, 5H), 7.69 (d, JH,H
= 8.72 Hz, 2H). 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ =
55.4, 55.8, 64.4, 114.5, 127.3, 129.0, 129.2, 130.5, 130.7, 138.8,
163.3. HRMS (ESI/QTOF) m/z: [M-Cl]+ Calcd for C15H15O3S
275.0736; Found 275.0737.
A screw-cap reaction vial
(10 mL) was charged with a magnetic stirring bar and catalyst
1 (27 mg, 2.5 mol%) and transferred into a glovebox. Solvents
(DCM:MeCN, 2.5:2.5 mL), sulfonyl chloride (1.0 mmol) and
alkene/alkyne (1.0 mmol) were added and the screw-cap vial
was closed and further sealed with electrical tape. The reaction
vial was moved outside the glovebox, placed ca. 10 cm under a
40 W blue LED from Kessil Co., Ltd. and cooled with a fan.
The reaction mixture was then stirred under irradiation for 24
hours. Afterwards the solvent mixture was removed under re-
duced pressure and the crude mixture was purified by column
chromatography. NMR spectra of known compounds agree
with literature values and new compounds were further charac-
terized by HRMS and/or elemental analysis. One LED/fan
setup was used for a maximum of three reactions at once to as-
sure sufficient light-irradiation per reaction vial. A temperature
increase from rt to ca. 30 °C could be measured with a regular
thermometer over the course of 24 hours irradiation.
1
GP A was applied (195 mg = 60%, yellow solid). H NMR
(400 MHz, CDCl3, ppm): δ = 3.87 (dd, 2JH,H = 15.09 Hz, 3JH,H
=
7.20 Hz, 1H), 3.98 (dd, 2JH,H = 15.09 Hz, 3JH,H = 6.88 Hz, 1H),
5.30 (t, 3JH,H = 7.04 Hz, 1H), 7.15-7.22 (m, 5H), 7.81 (d, 3JH,H
=
3
8.88 Hz, 2H), 8.16 (d, JH,H = 8.85 Hz, 1H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 55.0, 64.2, 124.3, 127.4, 129.0,
129.2, 129.6, 129.8, 137.9, 144.8, 150.8. HRMS (APPI/LTQ-
Orbitrap) m/z: [M+OH]- Calcd for C14H15ClNO5S 342.0208;
Found 342.0209.
1
GP B was applied (263 mg = 88%, white solid). H NMR
(400 MHz, CDCl3, ppm): δ = 3.87 (dd, 2JH,H = 14.89 Hz, 3JH,H
=
7.12 Hz, 1H), 3.97 (dd, 2JH,H = 14.89 Hz, 3JH,H = 6.84 Hz, 1H),
5.34 (t, 3JH,H = 6.96 Hz, 1H), 7.05-7.13 (m, 2H), 7.23-7.7.32 (m,
5H), 7.69-7.77 (m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3,
ppm): δ = -102.99. 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ
= 55.2, 64.3, 116.5 (d, 2JC,F = 22.74 Hz), 129.1, 129.4, 131.2 (d,
3JC,F = 9.69 Hz), 135.4 (d, 4JC,F = 3.08 Hz), 138.4, 165.9 (d, 1JC,F
= 257.01 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd
for C14H12FO2S 263.0537; Found 263.0535.
GP B
was applied (385 mg = 86%, white solid). 1H NMR (400 MHz,
CD2Cl2, ppm): δ = 1.93 (s, 3H), 3.79 (d, 2JH,H = 14.73 Hz, 1H),
4.27 (d, 2JH,H = 14.69 Hz, 1H), 7.20-7.30 (m, 2H), 7.82-7.89 (m,
1H), 7.89-8.00 (m, 3H), 8.12 (s, 1H), 8.97 (s, 1H). 19F{1H}
NMR (376.3 MHz, CD2Cl2, ppm): δ = -62.49, -103.48. 13C{1H}
NMR (100.6 MHz, CD2Cl2, ppm): δ = 31.2, 65.9, 66.5, 105.8,
2
3
115.4, 117.1 (d, JC,F = 22.89 Hz), 118.4 (q, JC,F = 4.98 Hz),
1
122.7 (q, JC,F = 270.17 Hz), 123.2, 131.5 (d, 3JC,F = 9.85 Hz),
1
GP B was applied (306 mg = 97%, white solid). H NMR
(400 MHz, CDCl3, ppm): δ = 3.87 (dd, 2JH,H = 14.89 Hz, 3JH,H
=
2
4
134.1 (q, JC,F = 32.76 Hz), 136.4, 137.0 (d, JC,F = 2.86 Hz),
7.12 Hz, 1H), 3.97 (dd, 2JH,H = 14.89 Hz, 3JH,H = 6.84 Hz, 1H),
5.33 (t, 3JH,H = 6.98 Hz, 1H), 7.22-7.30 (m, 5H), 7.39 (d, 3JH,H
141.6, 166.2 (d, 1JC,F = 256.34 Hz), 168.5. HRMS (ESI/QTOF)
=
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8.56 Hz, 2H), 7.64 (d, JH,H = 8.56 Hz, 2H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 55.2, 64.3, 127.3, 129.1, 129.4,
129.5, 129.8, 137.8, 138.3, 140.8. HRMS (ESI/QTOF) m/z:
[M+Na]+ Calcd for C14H12Cl2NaO2S 336.9827; Found
336.9830.
5.34 (t, 3JH,H = 7.06 Hz, 1H), 7.23-7.30 (m, 5H), 7.33-7.40 (m,
1H), 7.48-7.54 (m, 1H), 7.58-7.64 (m, 2H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 55.1, 64.2, 126.3, 127.3, 128.5,
129.1, 129.6, 130.2, 134.0, 135.5, 138.1, 141.0. HRMS
(APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for C14H12ClO2S
279.0241; Found 279.0241.
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2
3
4
5
6
7
8
GP B was applied (356 mg = 99%, white solid). 1H NMR
(400 MHz, CDCl3, ppm): δ = 3.87 (dd, 2JH,H = 14.89 Hz, 3JH,H
=
GP B was applied (281 mg = 78%, white solid). 1H NMR
7.16 Hz, 1H), 3.97 (dd, 2JH,H = 14.89 Hz, 3JH,H = 6.80 Hz, 1H),
(400 MHz, CDCl3, ppm): δ = 3.91 (dd, 2JH,H = 14.71 Hz, 3JH,H
=
3
5.33 (t, JH,H = 6.98 Hz, 1H), 7.20-7.31 (m, 5H), 7.55 (s, 4H).
7.58 Hz, 1H), 3.99 (dd, 2JH,H = 14.75 Hz, 3JH,H = 6.42 Hz, 1H),
5.34 (t, 3JH,H = 6.80 Hz, 1H), 7.10-7.33 (m, 5H), 7.61-7.69 (m,
2H), 7.75 (s, 1H). 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ
= 55.1, 64.1, 123.2, 126.7, 127.3, 129.0, 129.6, 130.7, 131.2,
136.9, 138.0, 141.1. HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+
Calcd for C14H12BrO2S 322.9736; Found 322.9734.
9
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 55.1, 64.2, 127.3,
129.1, 129.3, 129.4, 129.8, 132.5, 138.2, 138.3. HRMS (LTQ-
Orbitrap) m/z: [M-Cl]+ Calcd for C14H12BrO2S 322.9736; Found
322.9739.
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1
GP B was applied (390 mg = 96%, off-white solid). H NMR
(400 MHz, CDCl3, ppm): δ = 3.86 (dd, 2JH,H = 14.81 Hz, 3JH,H
=
GP B was applied (271 mg = 86%, white solid). 1H NMR
7.20 Hz, 1H), 3.96 (dd, 2JH,H = 14.73 Hz, 3JH,H = 6.52 Hz, 1H),
(400 MHz, CDCl3, ppm): δ = 4.22 (dd, 2JH,H = 15.05 Hz, 3JH,H
=
5.32 (t, 3JH,H = 6.62 Hz, 1H), 7.16-7.27 (m, 5H), 7.39 (d, 3JH,H
=
6.96 Hz, 1H), 4.27 (dd, 2JH,H = 15.05 Hz, 3JH,H = 7.20 Hz), 5.34
(t, 3JH,H = 7.08 Hz, 1H), 7.16-7.22 (m, 3H), 7.23-7.31 (m, 3H),
7.40-7.48 (m, 2H), 7.78-7.85 (m, 1H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 55.4, 61.8, 127.2, 127.4, 129.0,
129.4, 131.7, 131.8, 132.5, 134.8, 136.8, 138.1. HRMS
(APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for C14H12ClO2S
279.0241; Found 279.0237.
3
7.76 Hz, 2H), 7.76 (d, JH,H = 7.88 Hz, 2H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 55.1, 64.1, 102.0, 127.3, 129.1,
129.3, 129.5, 138.5. HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+
Calcd for C14H12IO2S 370.9597; Found 370.9598.
GP
B was applied (214 mg = 70%, white solid). 1H NMR
(400 MHz, CDCl3, ppm): δ = 3.91 (dd, 2JH,H = 15.05 Hz, 3JH,H
=
7.24 Hz, 1H), 4.02 (dd, 2JH,H = 15.05 Hz, 3JH,H = 6.84 Hz), 5.35
GP B was applied (313 mg = 87%, white solid). 1H NMR
3
3
(400 MHz, CDCl3, ppm): δ = 4.25 (dd, 2JH,H = 15.02 Hz, 3JH,H
=
(t, JH,H = 7.02 Hz, 1H), 7.20-7.32 (m, 5H), 7.70 (d, JH,H
=
3
8.32 Hz, 2H), 7.80 (d, JH,H = 8.32 Hz, 2H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 55.0, 64.0, 117.1, 117.6, 127.4,
129.0, 129.2, 129.6, 132.9, 137.9, 143.4. HRMS (APPI/LTQ-
Orbitrap) m/z: [M-Cl]+ Calcd for C15H12NO2S 270.0583; Found
270.0583.
6.84 Hz, 1H), 4.32 (dd, 2JH,H = 15.01 Hz, 3JH,H = 7.34 Hz, 1H),
5.35 (t, 3JH,H = 7.09 Hz, 1H), 7.16-7.22 (m, 3H), 7.24-7.30 (m,
2H), 7.30-7.39 (m, 2H), 7.62-7.68 (m, 1H), 7.82-7.87 (m, 1H).
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 55.4, 61.4, 120.9,
127.3, 128.0, 129.0, 129.4, 132.3, 134.8, 135.3, 138.1, 138.5.
HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for
C14H12BrO2S 322.9736; Found 322.9740.
1
GP B was applied (295 mg = 87%, white solid). H NMR
(400 MHz, CDCl3, ppm): δ = 3.81-4.11 (m, 5H), 5.35 (t, 3JH,H
=
6.80 Hz, 1H), 7.14-7.33 (m, 5H), 7.79 (d, 3JH,H = 8.08 Hz, 2H),
1
GP B was applied (259 mg = 88%, red solid). H NMR
3
8.07 (d, JH,H = 8.08 Hz, 2H). 13C{1H} NMR (100.6 MHz,
2
(400 MHz, CDCl3, ppm): δ = 2.34 (s, 3H), 3.87 (dd, JH,H
=
14.75 Hz, 3JH,H = 7.34 Hz, 1H), 3.96 (dd, 2JH,H = 14.73 Hz, 3JH,H
= 6.64 Hz, 1H), 5.34 (t, 3JH,H = 6.98 Hz, 1H), 7.22-7.29 (m, 5H),
7.29-7.38 (m, 2H), 7.44-7.49 (m, 1H), 7.52-7.59 (m, 1H).
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 21.3, 55.2, 64.1,
125.3, 127.3 128.6, 128.9, 129.1, 129.3, 134.7, 138.52, 139.1,
139.5. HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for
C15H15O2S 259.0787; Found 259.0784.
CDCl3, ppm): δ = 52.9, 55.1, 64.1, 127.3, 128.3, 129.1, 129.4,
130.3, 143.9, 138.2, 143.1, 165.5. HRMS (ESI/QTOF) m/z:
[M+Na]+ Calcd for C16H15ClNaO4S 361.0272; Found 361.0275.
1
GP B was applied (293 mg = 98%, white solid). H NMR
(400 MHz, CDCl3, ppm): δ = 3.89 (dd, 2JH,H = 14.87 Hz, 3JH,H
=
7.30 Hz, 1H), 3.99 (dd, 2JH,H = 14.89 Hz, 3JH,H = 6.72 Hz, 1H),
5.34 (t, 3JH,H = 7.00 Hz, 1H), 7.21-7.29 (m, 6H), 7.35-7.47 (m,
2H), 7.50-7.57 (m, 1H). 19F NMR{1H} (376.3 MHz, CDCl3,
ppm): δ = 109.13. 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ
GP B was applied (204 mg = 50%, white solid).
1H NMR (400 MHz, CDCl3, ppm): δ = 1.25 (d, 3JH,H = 6.92 Hz,
6H), 1.27 (d, 3JH,H = 6.72 Hz, 6H), 1.28 (d, 3JH,H = 6.68 Hz, 6H),
2
2
= 55.1, 64.2, 115.7 (d, JC,F = 24.53 Hz), 121.2 (d, JC,F
=
21.18 Hz), 124.0 (d, 4JC,F = 3.39 Hz), 127.3, 129.1, 129.5, 131.1
(d, 3JC,F = 7.56 Hz), 138.2, 141.3 (d, 3JC,F = 6.53 Hz), 162.3 (d,
1JC,F = 252.52 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+
Calcd for C14H12FO2S 263.0537; Found 263.0534.
3
2
2.90 (sept., JH,H = 6.93 Hz, 1H), 3.86 (dd, JH,H = 14.61 Hz,
3JH,H = 5.68 Hz, 1H), 4.01 (dd, 2JH,H = 14.61 Hz, 3JH,H = 7.52 Hz,
1H), 4.10 (sept., 3JH,H = 6.76 Hz, 2H), 5.49 (dd, 2JH,H = 7.48 Hz,
3JH,H = 5.72 Hz, 1H), 7.15 (s, 2H), 7.27-7.37 (m, 5H). 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 23.67, 23.70, 25.0, 25.2,
29.8, 34.4, 55.3, 66.2, 124.2, 129.1, 129.2, 132.9, 139.4, 151.1,
154.2. HRMS (ESI/QTOF) m/z: [M+Na]+ Calcd for
C23H31ClNaO2S 429.1625; Found 429.1627.
1
GP B was applied (296 mg = 94%, white solid). H NMR
(400 MHz, CDCl3, ppm): δ = 3.90 (dd, 2JH,H = 14.89 Hz, 3JH,H
=
7.56 Hz, 1H), 3.99 (dd, 2JH,H = 14.89 Hz, 3JH,H = 6.56 Hz, 1H),
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1.71 (m, 1H), 1.80-1.90 (m, 2H), 1.93-2.05 (m, 1H), 2.05-2.16
(m, 1H), 2.50 (tt, 3JH,H = 12.12 Hz, 3.35 Hz, 1H), 3.59 (dd, 2JH,H
GP B
was applied (267 mg = 93%, white solid). 1H NMR (400 MHz,
1
2
3
4
5
6
7
8
3
2
2
3
= 14.97 Hz, JH,H = 6.60 Hz, 1H), 3.78 (dd, JH,H = 14.95 Hz,
3JH,H = 7.06 Hz, 1H), 5.40 (t, 3JH,H = 6.82 Hz, 1H), 7.31-7.51 (m,
5H). 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 24.7, 24.8,
25.0, 25.07, 25.08, 55.5, 58.3, 61.8, 127.3, 129.2, 129.5, 139.2.
HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for
C14H19O2S 251.1100; Found 251.1100.
CDCl3, ppm): δ = 3.97 (dd, JH,H = 14.83 Hz, JH,H = 6.98 Hz,
2
3
1H), 4.06 (dd, JH,H = 14.81 Hz, JH,H = 6.80 Hz, 1H), 5.37 (t,
3JH,H = 6.86 Hz, 1H), 7.02 (dd, JH,H = 4.86 Hz, 3.90 Hz, 1H),
3
3
4
7.29-7.33 (m, 5H), 7.48 (dd, JH,H = 3.80 Hz, JH,H = 1.24 Hz,
1H), 7.66 (dd, JH,H = 4.95 Hz, JH,H = 1.22 Hz, 1H). 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 55.2, 65.5, 127.3, 128.0,
129.1, 129.4, 134.7, 135.1, 138.6, 140.5. HRMS (APPI/LTQ-
Orbitrap) m/z: [M-Cl]+ Calcd for C12H11O2S2 251.0195; Found
251.0191.
3
4
GP B was
1
9
applied (40 mg = 13%, white solid). H NMR (400 MHz,
CDCl3, ppm): δ = 3.45 (dd, JH,H = 15.21 Hz, JH,H = 5.80 Hz,
2
3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
GP A was applied
2
3
1H), 3.76 (dd, JH,H = 15.19 Hz, JH,H = 7.82 Hz, 1H), 4.07 (d,
1
2JH,H = 13.97 Hz, 1H), 4.20 (d, JH,H = 13.97 Hz, 1H), 5.44 (d,
(163 mg = 63%, colorless oil). H NMR (400 MHz, CDCl3,
2
ppm): δ = 3.55 (dd, 2JH,H = 15.33 Hz, 3JH,H = 6.44 Hz, 1H), 3.63
3JH,H = 7.82 Hz, 5.86 Hz, 1H), 7.29-7.50 (m, 10H). 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 55.8, 59.9, 60.9, 127.35,
127.36, 129.2, 129.32, 129.34, 129.7, 131.1, 138.8. HRMS
(APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for C15H15O2S
259.0787; Found 259.0786.
2
3
3
(dd, JH,H = 15.33 Hz, JH,H = 5.44 Hz, 1H), 5.31 (t, JH,H
=
5.92 Hz), 7.31-7.49 (m, 5H). 13C{1H} NMR (100.6 MHz,
CDCl3, ppm): δ = 58.4, 62.9, 96.343 127.5, 129.1, 140.6.
GP B was
1
applied (138 mg = 63%, white solid). H NMR (400 MHz,
GP B
CDCl3, ppm): δ = 2.76 (s, 3H), 3.64 (dd, 2JH,H = 15.15 Hz, 3JH,H
2
3
with 5 equiv. of Styrene was applied (122 mg = 42%, white
= 5.86 Hz, 1H), 3.85 (dd, JH,H = 15.17 Hz, JH,H = 7.76 Hz,
1H), 5.39 (t, 3JH,H = 6.78 Hz), 7.34-7.48 (m, 5H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 42.8, 55.7, 63.7, 127.3, 129.4,
129.7, 138.7. HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd
for C9H11O2S 183.0474; Found 183.0472.
1
solid). H NMR (400 MHz, CDCl3, ppm): δ = 3.07-3.15 (m,
2
2H), 3.15-3.22 (m, 2H), 3.58-3.70 (m, 5H), 3.74 (dd, JH,H
=
3
3
14.61 Hz, JH,H = 6.72 Hz, 1H), 5.31 (t, JH,H = 6.72 Hz, 1H),
7.35-7.45 (m, 5H). 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ
= 45.5, 55.7, 58.1, 64.7, 66.6, 127.2, 129.2, 129.5, 139.3.
HRMS (APCI/QTOF) m/z: [M+H]+ Calcd for C12H17ClNO3S
290.0612; Found 290.0614.
GP B was
1
applied (121 mg = 52%, white solid). H NMR (400 MHz,
CDCl3, ppm): δ = 1.33 (t, JH,H = 7.44 Hz, 3H), 2.74-2.95 (m,
3
2H), 3.59 (dd, 2JH,H = 15.17 Hz, 3JH,H = 5.88 Hz, 1H), 3.82 (dd,
2JH,H = 15.19 Hz, 3JH,H = 7.70 Hz, 1H), 5.40 (dd, 3JH,H = 7.64 Hz,
5.96 Hz, 1H), 7.34-7.47 (m, 5H). 13C{1H} NMR (100.6 MHz,
CDCl3, ppm): δ = 6.7, 49.0, 55.6, 60.9, 127.2, 129.4, 129.7,
138.9. HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for
C10H13O2S 197.0631; Found 197.0628.
GP B
with 5 equiv. of Styrene was applied (58 mg = 20%, white
1
solid). H NMR (400 MHz, CDCl3, ppm): δ = 1.44-1.64 (m,
2
3
6H), 3.03-3.20 (m, 4H), 3.63 (dd, JH,H = 14.53 Hz, JH,H
=
6.80 Hz, 1H), 3.70 (dd, 2JH,H = 14.53 Hz, 3JH,H = 6.72 Hz, 1H),
5.31 (t, 3JH,H = 6.74 Hz, 1H), 7.32-7.45 (m, 5H). 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 23.8, 25.7, 46.4, 56.0, 58.2,
127.2, 129.1, 129.3, 139.6. HRMS (APPI/LTQ-Orbitrap) m/z:
[M+H]+ Calcd for C13H19ClNO2S 288.0820; Found 288.0814.
GP B was ap-
1
plied (181 mg = 57%, colorless oil). H NMR (400 MHz,
3
CDCl3, ppm): δ = 0.88 (t, JH,H = 6.90 Hz, 3H), 1.14-1.35 (m,
2
10H), 1.61-1.85 (m, 2H), 2.65-2.83 (m, 2H), 3.60 (dd, JH,H
=
GP
15.11 Hz, 3JH,H = 6.26 Hz, 1H), 3.79 (dd, 2JH,H = 15.13 Hz, 3JH,H
= 7.44 Hz, 1H), 5.39 (t, 3JH,H = 6.84 Hz, 1H), 7.34-7.48 (m, 5H).
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 14.2, 21.9, 22.7,
28.4, 29.0, 31.8, 54.5, 55.6, 61.4, 127.3, 129.3, 129.6, 138.9.
HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for
C16H25O2S 281.1570; Found 281.1565.
B with 5 equiv. of Styrene was applied (55 mg = 20%, white
1
solid). H NMR (400 MHz, CDCl3, ppm): δ = 1.73-1.85 (m,
2
4H), 3.12-3.23 (m, 2H), 3.23-3.33 (m, 2H), 3.70 (dd, JH,H
=
14.74 Hz, 3JH,H = 6.70 Hz, 1H), 3.80 (dd, 2JH,H = 14.74 Hz, 3JH,H
= 6.79 Hz, 1H), 5.34 (t, 3JH,H = 6.74 Hz, 1H), 7.31-7.46 (m, 5H).
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 25.9, 47.6, 56.2,
58.5, 127.2, 129.2, 129.3, 139.6. HRMS (ESI/QTOF) m/z:
[M+Na]+ Calcd for C12H16ClNNaO2S 296.0482; Found
296.0488.
GP B
was applied (86 mg = 35%, colorless oil). 1H NMR (400 MHz,
CDCl3, ppm): δ = 1.32 (d, 3JH,H = 6.86 Hz, 3H), 1.36 (d, 3JH,H
6.76 Hz, 3H), 2.99 (sept., 3JH,H = 6.83 Hz, 1H), 3.57 (dd, 2JH,H
=
=
14.95 Hz, 3JH,H = 5.90 Hz, 1H), 3.84 (dd, 2JH,H = 14.97 Hz, 3JH,H
= 7.60 Hz, 1H), 5.43 (t, 3JH,H = 6.72 Hz, 1H), 7.35-7.48 (m, 5H).
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 14.8. 15.4. 54.2.
55.5. 58.4. 127.2. 129.3. 129.6. 139.2. HRMS (APPI/LTQ-
Orbitrap) m/z: [M-Cl]+ Calcd for C11H15O2S 211.0787; Found
211.0782.
GP B was applied (307 mg = 98%,
white solid). H NMR (400 MHz, CDCl3, ppm): δ = 2.31 (s,
1
3H), 3.87 (dd, 2JH,H = 14.83 Hz, 3JH,H = 7.30 Hz, 1H), 3.96 (dd,
2JH,H = 14.81 Hz, 3JH,H = 6.68 Hz, 1H), 5.31 (t, 3JH,H = 6.94 Hz,
1H), 6.98-7.18 (m, 6H), 7.64-7.77 (m, 2H). 19F{1H} NMR
(376.3 MHz, CDCl3, ppm): δ = -103.19. 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 21.2, 55.2, 64.3, 116.4 (d, 2JC,F
= 22.85 Hz), 127.2, 129.7, 131.2 (d, 3JC,F = 9.69 Hz), 135.4 (d,
GP B
was applied (141 mg = 49%, white solid). 1H NMR (400 MHz,
CDCl3, ppm): δ = 0.98-1.27 (m, 3H), 1.42-1.56 (m, 2H), 1.60-
1
4JC,F = 5.44 Hz), 139.5, 165.9 (d, JC,F = 256.57 Hz). HRMS
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The Journal of Organic Chemistry
(ESI/QTOF) m/z: [M+Na]+ Calcd for C15H14ClFNaO2S
335.0279; Found 335.0278.
NMR (100.6 MHz, CDCl3, ppm): δ = 54.4, 64.4, 116.1 (d, 2JC,F
= 21.97 Hz), 116.6 (d, 2JC,F = 22.74 Hz), 129.3 (d, 3JC,F = 8.57
Hz), 131.2 (d, 3JC,F = 9.63 Hz), 134.4 (d, 4JC,F = 3.52 Hz), 135.3
(d, 4JC,F = 3.32 Hz), 163.1 (d, 1JC,F = 249.90 Hz), 166.0 (d, 1JC,F
= 257.39 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd
for C14H11F2O2S 281.0442; Found 281.0440.
1
2
3
4
1
GP B was applied (178 mg = 50%, grey solid). H
NMR (400 MHz, CDCl3, ppm): δ = 2.30 (s, 3H), 3.86 (dd, 2JH,H
5
3
2
= 14.89 Hz, JH,H = 7.32 Hz, 1H), 3.96 (dd, JH,H = 14.89 Hz,
3JH,H = 6.72 Hz, 1H), 5.35 (t, 3JH,H = 7.02 Hz, 1H), 6.96-7.02 (m,
2H), 7.08-7.16 (m, 2H), 7.25-7.30 (m, 2H), 7.66-7.73 (m, 2H).
19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -102.74. 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 21.2, 54.6, 64.4, 116.7 (d,
2JC,F = 22.81 Hz), 122.3, 128.5, 131.2 (d, 3JC,F = 9.67 Hz), 135.3
(d, 4JC,F = 3.10 Hz), 135.8, 151.3, 166.0 (d, 1JC,F = 257.22 Hz),
169.1. HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for
C16H14FO4S 321.0591; Found 321.0591.
6
7
8
9
GP B was applied (320 mg = 96%, white solid).
2
1H NMR (400 MHz, CDCl3, ppm): δ = 3.85 (dd, JH,H
=
14.81 Hz, 3JH,H = 7.40 Hz, 1H), 3.96 (dd, 2JH,H = 14.81 Hz, 3JH,H
= 6.64 Hz, 1H), 5.34 (t, 3JH,H = 7.02 Hz, 1H), 7.11-7.20 (m, 2H),
7.21-7.32 (m, 4H), 7.72-7.80 (m, 2H). 19F{1H} NMR
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(376.3 MHz, CDCl3, ppm): δ = -102.49. 13C{1H} NMR
2
(100.6 MHz, CDCl3, ppm): δ = 54.3, 64.2, 116.7 (d, JC,F
=
3
22.76 Hz), 128.7, 129.3, 131.2 (d, JC,F = 9.87 Hz), 135.3 (d,
4JC,F = 3.04 Hz), 135.4, 136.9, 166.1 (d, 257.45 Hz). HRMS
(ESI/QTOF) m/z: [M+Na]+ Calcd for C14H11Cl2FNaO2S
354.9733; Found 354.9729.
GP B was applied (162 mg = 47%, grey solid). 1H
NMR (400 MHz, CDCl3, ppm): δ = 3.80 (dd, 2JH,H = 14.73 Hz,
3JH,H = 7.20 Hz, 1H), 3.92 (d, 2JH,H = 14.73 Hz, 3JH,H = 6.68 Hz,
3
1H), 5.38 (t, JH,H = 6.92 Hz, 1H), 7.13-7.23 (m, 2H), 7.46 (d,
3
3JH,H = 8.28 Hz, 2H), 7.63 (d, JH,H = 8.24 Hz, 1H), 7.76-7.85
GP B was applied (366 mg = 97%, white solid).
(m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -101.84.
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 53.9, 64.0, 113.4,
1H NMR (400 MHz, CDCl3, ppm): δ = 3.82 (dd, JH,H
=
2
14.81 Hz, 3JH,H = 7.48 Hz, 1H), 3.93 (dd, 2JH,H = 14.81 Hz, 3JH,H
= 6.60 Hz, 1H), 5.30 (t, 3JH,H = 7.04 Hz, 1H), 7.09-7.18 (m, 4H),
7.38-7.45 (m, 2H), 7.69-7.77 (m, 2H). 19F{1H} NMR
2
3
116.9 (d, JC,F = 22.69 Hz), 128.2, 131.2 (d, JC,F = 9.70 Hz),
132.9, 135.2 (d, 4JC,F = 2.73 Hz), 143.4, 166.2 (d, 1JC,F = 257.99
Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for
C14H11FNO4S 308.0387; Found 308.0383.
(376.3 MHz, CDCl3, ppm): δ = -102.44. 13C{1H} NMR
2
(100.6 MHz, CDCl3, ppm): δ = 54.4, 64.2, 116.7 (d, JC,F
=
22.74 Hz), 123.6, 129.0, 131.2 (d, 3JC,F = 9.85 Hz), 132.3, 135.3
(d, 4JC,F = 3.07 Hz), 137.4, 166.1 (d, 1JC,F = 257.51 Hz). HRMS
(APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for C14H11BrFO2S
340.9642; Found 340.9640.
GP B was applied (311 mg = 96%, white solid).
2
1H NMR (400 MHz, CDCl3, ppm): δ = 3.80 (dd, JH,H = 14.73
Hz, 3JH,H = 7.16 Hz, 1H), 3.93 (dd, 2JH,H = 14.71 Hz, 3JH,H = 6.70
Hz, 1H), 5.38 (t, 3JH,H = 6.92 Hz, 1H), 7.14-7.24 (m, 2H), 7.46
(d, 3JH,H = 8.36 Hz, 2H), 7.63 (d, 3JH,H = 8.40 Hz, 2H), 7.76-7.85
(m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -101.34.
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 53.9, 64.0, 113.4,
116.9 (d, 2JC,F = 22.75 Hz), 118.0, 128.2, 131.2 (d, 3JC,F = 9.65
GP B was applied (304 mg = 96%, white solid).
2
1H NMR (400 MHz, CDCl3, ppm): δ = 3.85 (dd, JH,H = 14.87
Hz, 3JH,H = 7.10 Hz, 1H), 3.96 (dd, 2JH,H = 14.85 Hz, 3JH,H = 6.80
Hz, 1H), 5.35 (t, 3JH,H = 6.94 Hz, 1H), 6.94-7.05 (m, 2H), 7.06-
12 (m, 1H), 7.13-7.21 (m, 2H), 7.24-7.35 (m, 1H), 7.75-7.83
(m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -102.57,
-111.28. 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 54.3,
4
1
Hz), 132.9, 135.2 (d, JC,F = 3.06 Hz), 143.4, 166.2 (d, JC,F
=
258.19 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd
for C15H11FNO2S 288.0489; Found 288.0485.
2
2
64.2, 114.4 (d, JC,F = 22.73 Hz), 116.5 (d, JC,F = 21.47 Hz),
116.7 (d, 2JH,H = 23.06 Hz), 123.1 (d, 4JC,F = 2.98 Hz), 130.8 (d,
3JC,F = 8.46 Hz), 131.2 (d, 3JC,F = 9.82 Hz), 135.3 (d, 4JC,F = 3.20
1
GP B was applied (216 mg = 74%, off-white solid). H NMR
3
3
1
(400 MHz, CDCl3, ppm): δ = 3.84 (s, 3H), 6.69 (d, JH,H
=
Hz), 140.8 (d, JC,F = 7.33 Hz), 162.9 (d, JC,F = 248.06 Hz),
166.1 (d, 1JC,F = 257.32 Hz). HRMS (APPI/LTQ-Orbitrap) m/z:
[M-Cl]+ Calcd for C14H11F2O2S 281.0442; Found 281.0437.
15.33 Hz, 1H), 6.87-6.94 (m, 2H), 7.17-7.24 (m, 2H), 7.39-7.47
3
(m, 2H), 7.63 (d, JH,H = 15.33 Hz, 1H), 7.90-8.00 (m, 2H).
19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -104.41. 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 55.6, 114.7, 116.7 (d, 2JC,F
3
= 22.62 Hz), 124.4, 125.0, 130.5 (d, JC,F = 9.45 Hz), 130.6,
GP B was applied (317 mg = 95%, white solid).
4
1
2
1H NMR (400 MHz, CDCl3, ppm): δ = 3.84 (dd JH,H
=
137.4 (d, JC,F = 3.37 Hz), 142.6, 162.3, 165.6 (d, JC,F
=
255.14 Hz). HRMS (APCI/QTOF) m/z: [M+H]+ Calcd for
14.86 Hz, 3JH,H = 7.42 Hz, 1H), 3.94 (dd, 2JH,H = 14.86 Hz, 3JH,H
3
C15H14FO3S 293.0642; Found 293.0647.
= 6.60 Hz), 5.29 (t, JH,H = 7.00 Hz, 1H), 7.08-7.15 (m, 2H),
7.15-7.28 (m, 4H), 7.68-7.78 (m, 2H). 19F{1H} NMR
(376.3 MHz, CDCl3, ppm): δ = -102.55. 13C{1H} NMR
2
GP B was applied (301 mg = 95%, white solid).
(100.6 MHz, CDCl3, ppm): δ = 54.3, 64.1, 116.7 (d, JC,F
=
2
1H NMR (400 MHz, CDCl3, ppm): δ = 3.86 (dd, JH,H = 14.81
22.69 Hz), 125.6, 127.6, 129.6, 130.4, 131.2 (d, 3JC,F = 9.73 Hz),
Hz, 3JH,H = 7.40 Hz, 1H), 3.97 (dd, 2JH,H = 14.81 Hz, 3JH,H = 6.64
Hz, 1H), 5.37 (t, 3JH,H = 7.02 Hz, 1H), 6.96-7.05 (m, 2H), 7.12-
7.20 (m, 2H), 7.25-7.33 (m, 2H), 7.72-7.81 (m, 2H). 19F{1H}
NMR (376.3 MHz, CDCl3, ppm): δ = -102.59, -111.32. 13C{1H}
135.0, 135.2 (d, JC,F = 3.37 Hz), 140.2, 166.1 (d, JC,F
=
4
1
257.83 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd
for C14H11ClFO2S 297.0147; Found 297.0142.
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The Journal of Organic Chemistry
Page 8 of 11
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 20.60, 20.64,
2
1
2
3
4
20.9, 50.8, 62.4, 116.3 (d, JC,F = 22.85 Hz), 129.5, 131.0 (d,
GP B was applied (298 mg = 79%, white solid).
3JC,F = 9.90 Hz), 131.1, 131.6, 134.8 (d, 4JC,F = 3.25 Hz), 136.7,
137.4, 139.2, 165.9 (d, 1JC,F = 256.95 Hz). HRMS (ESI/QTOF)
m/z: [M-Cl]+ Calcd for C17H18FO2S 305.1012; Found 305.1014.
2
1H NMR (400 MHz, CDCl3, ppm): δ = 3.84 (dd, JH,H
=
14.89 Hz, 3JH,H = 7.52 Hz, 1H), 3.94 (dd, 2JH,H = 14.87 Hz. 3JH,H
3
= 6.54 Hz, 1H), 5.28 (t, JH,H = 7.02 Hz), 7.08-7.19 (m, 3H),
7.19-7.25 (m, 1H), 7.36 (s, 1H), 7.38-7.43 (m, 1H), 7.68-7.77
(m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -102.51.
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 54.2, 64.0, 116.7
(d, 2JC,F = 22.90 Hz), 123.0, 126.1, 130.4, 130.6, 131.2 (d, 3JC,F
= 10.07 Hz), 132.5, 135.1 (d, 4JC,F = 2.97 Hz), 140.4, 166.0 (d,
1JC,F = 257.16 Hz). HRMS (LTQ-Orbitrap) m/z: [M-Cl]+ Calcd
for C14H11BrFO2S 340.9642; Found 340.9641.
5
6
7
8
GP B was applied (114 mg = 38%, white solid). 1H NMR
(400 MHz, CDCl3, ppm): δ = 3.98 (dd, 2JH,H = 14.69 Hz, 3JH,H
=
5.80 Hz, 1H), 4.46 (dd, 2JH,H = 14.67 Hz, 3JH,H = 7.62 Hz, 1H),
5.41 (dd, 3JH,H = 7.58 Hz, 5.82 Hz, 1H), 7.06-7.14 (m, 2H), 7.19
9
3
4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(ddd, JH,H = 7.50 Hz, 4.86 Hz, JH,H = 0.72 Hz, 1H), 7.36 (d,
3JH,H = 7.80 Hz, 1H), 7.67 (td, 3JH,H = 7.70 Hz, 4JH,H = 1.76 Hz,
1H), 7.73-7.79 (m, 2H), 8.40 (d, 3JH,H = 4.12 Hz, 1H). 19F{1H}
NMR (376.3 MHz, CDCl3, ppm): δ = -103.16. 13C{1H} NMR
GP B was applied (282 mg = 89%, white solid).
2
2
1H NMR (400 MHz, CDCl3, ppm): δ = 3.89 (d, JH,H = 14.89
(100.6 MHz, CDCl3, ppm): δ = 54.8, 61.7, 116.5 (d, JC,F
=
3
Hz, 3JH,H = 6.56 Hz, 1H), 3.96 (dd, 2JH,H = 14.89 Hz, 3JH,H = 7.64
Hz, 1H), 5.44 (t, 3JH,H = 7.08 Hz, 1H), 6.81-6.92 (m, 1H), 6.98-
7.08 (m, 3H), 7.16-7.28 (m, 2H), 7.62-7.74 (m, 2H). 19F{1H}
NMR (376.3 MHz, CDCl3, ppm): δ = -102.83, -115.39. 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 49.6 (d, JC,F = 2.90 Hz),
22.72 Hz), 123.2, 123.9, 131.2 (d, JC,F = 9.65 Hz), 135.5 (d,
1
4JC,F = 3.08 Hz), 137.3, 149.8, 156.0, 165.9 (d, JC,F
=
256.91 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd
for C13H12ClFNO2S 300.0256; Found 300.0254.
2
62.7 (d, JC,F = 2.66 Hz), 116.3 (d, JC,F =21.38 Hz), 116.6 (d,
GP B was applied (324 mg = 93%, white solid). 1H NMR
4
3
2JC,F = 22.74 Hz), 124.8 (d, JC,F = 3.61 Hz), 125.5 (d, JC,F
=
(400 MHz, CDCl3, ppm): δ = 3.98 (dd, 2JH,H = 14.89 Hz, 3JH,H
=
11.95 Hz), 129.4 (d, 4JC,F = 3.20 Hz), 131.2 (d, 3JC,F = 9.63 Hz),
131.4 (d, 3JC,F = 8.68 Hz), 135.0 (d, 3JC,F = 3.22 Hz), 160.0 (d,
7.64 Hz, 1H), 4.86 (dd, 2JH,H = 14.89 Hz, 3JH,H = 6.52 Hz), 5.51
(t, 3JH,H = 7.06 Hz), 6.84-6.92 (m, 2H), 7.29 (dd, 3JH,H = 8.56 Hz,
4JH,H = 1.84 Hz), 7.48-7.55 (m, 2H), 7.59-7.66 (m, 2H), 7.67-
7.73 (m, 2H), 7.74-7.81 (m, 2H). 19F{1H} NMR (376.3 MHz,
CDCl3, ppm): δ = -103.09. 13C{1H} NMR (100.6 MHz, CDCl3,
ppm): δ = 55.6, 64.2, 116.3 (d, 2JC,F = 22.77 Hz), 123.9, 127.0,
1JC,F = 250.35 Hz), 166.0 (d, JC,F = 256.99 Hz). HRMS
1
(APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for C14H11F2O2S
281.0442; Found 281.0439.
3
127.1, 127.3, 127.8, 128.2, 128.3, 131.1 (d, JC,F = 9.64 Hz),
GP B was applied (300 mg = 90%, white
4
1
solid). 1H NMR (400 MHz, CDCl3, ppm): δ = 3.82 (dd, 2JH,H
=
132.9, 133.5, 135.1 (d, JC,F = 3.10 Hz), 165.7 (d, JC,F
=
256.99 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M]+ Calcd for
14.99 Hz, 3JH,H = 7.30 Hz, 1H), 3.88 (dd, 2JH,H = 14.99 Hz, 3JH,H
= 6.46 Hz, 1H), 5.71 (t, 3JH,H = 6.86 Hz, 1H), 7.03-7.11 (m, 2H),
7.11-7.21 (m, 2H), 7.22 (m, 1H), 7.29-7.35 (m, 1H), 7.77-7.82
(m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -102.69.
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 51.5, 62.9, 116.7
(d, 2JC,F = 22.73 Hz), 127.7, 129.0, 130.3, 130.5, 131.4 (d, 3JC,F
C18H14ClFO2S 348.0382; Found 348.0381.
GP B was applied (258 mg = 74%, white solid). 1H NMR
(400 MHz, CDCl3, ppm): δ = 3.99-4.24 (m, 2H), 6.14 (br. s,
1H), 1.91-7.04 (m, 2H), 7.35 (t, 3JH,H = 7.74 Hz, 1H), 7.48-7.56
(m, 2H), 7.60 (t, 3JH,H = 7.54 Hz, 1H), 7.63-7.72 (m, 2H), 7.78
(d, 3JH,H = 8.20 Hz, 1H), 7.84 (d, 3JH,H = 8.04 Hz, 1H), 8.10 (d,
3JH,H = 8.52 Hz, 1H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm):
δ = -103.07. 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 52.2
4
= 9.80 Hz), 132.9, 135.7, 135.8 (d, JC,F = 3.05 Hz), 166.1 (d,
257.33 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd
for C14H11ClFO2S 297.0147; Found 297.0145.
2
(br. s, FWHM = 94.59 Hz), 63.7, 116.3 (d, JC,F = 22.75 Hz),
GP B was applied (340 mg = 90%, white solid).
1H NMR (400 MHz, CDCl3, ppm): δ = 3.80-3.96 (m, 2H), 5.77
122.5 (br. s, FWHM = 11.83 Hz), 125.2, 125.9 (br. s, FWHM =
3
3
3
31.52 Hz), 126.4, 127.3, 129.3, 129.8, 130.2, 131.0 (d, JC,F
=
(t, JH,H = 6.80 Hz, 1H), 7.11-7.20 (m, 3H), 7.26 (t, JH,H
=
=
3
3
9.65 Hz), 133.5 (br. s, FWHM = 16.14 Hz), 134.0, 134.9 (br. s,
7.48 Hz, 1H), 7.40 (d, JH,H = 7.80 Hz, 1H), 7.52 (d, JH,H
1
7.96 Hz, 1H), 7.81-7.91 (m, 2H). 19F{1H} NMR (376.3 MHz,
CDCl3, ppm): δ = -102.67. 13C{1H} NMR (100.6 MHz, CDCl3,
ppm): δ = 53.9, 63.1, 116.7 (d, 2JC,F = 22.84 Hz), 123.0, 128.3,
129.1, 130.7, 131.4, 131.5 (d, 3JC,F = 9.85 Hz), 133.5, 135.0 (d,
FWHM = 9.72 Hz), 165.8 (d, JC,F = 256.89 Hz). HRMS
(APPI/LTQ-Orbitrap) m/z: [M]+ Calcd for C18H14ClFO2S
348.0382; Found 348.0387.
4JC,F = 3.37 Hz), 137.3, 166.1 (d, JC,F = 257.83 Hz). HRMS
1
GP B was applied (228 mg = 73%, white solid). 1H NMR
(APPI/LTQ-Orbitrap) m/z: [M-Cl]+ Calcd for C14H11BrFO2S
2
(400 MHz, CDCl3, ppm): δ = 2.38 (s, 3H), 4.01 (d, JH,H
=
340.9642; Found 340.9640.
2
14.84 Hz, 1H), 4.18 (d, JH,H = 14.85 Hz, 1H), 6.93-7.03 (m,
2H), 7.17-7.24 (m, 3H), 7.33-7.40 (m, 2H), 7.46-7.53 (m, 2H).
19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -103.73. 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 29.9, 67.5, 70.0, 116.4 (d,
2JC,F = 22.46 Hz), 126.7, 128.4, 128.7, 130.8 (d, 3JC,F = 9.91 Hz),
GP B was applied (239 mg = 70%, white
solid). 1H NMR (400 MHz, CDCl3, ppm): δ = 2.21 (s, 3H), 2.27
(s, 3H), 2.44 (s, 3H), 3.98-4.11 (m, 2H), 5.88 (t, 3JH,H = 7.01 Hz,
1H), 6.61 (s, 1H), 6.81 (s, 1H), 6.98-7.11 (m, 2H), 7.60-7.72 (m,
2H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -103.18.
4
1
136.1 (d, JC,F = 3.24 Hz), 141.0, 165.6 (d, JC,F = 256.19 Hz).
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The Journal of Organic Chemistry
HRMS (APCI/QTOF) m/z: [M+Na]+ Calcd for C15H14ClF-
NaO2S 335.0279; Found 335.0274.
NMR (376.3 MHz, CDCl3, ppm): δ = -102.61. 13C{1H} NMR
(100.6 MHz, CDCl3, ppm): δ = 44.2, 54.4, 62.6, 116.9 (d, 2JC,F
1
2
3
4
5
6
7
8
3
= 22.72 Hz), 127.6, 128.9, 129.7, 131.3 (d, JC,F = 9.55 Hz),
4
1
135.6 (d, JC,F = 3.37 Hz), 135.8, 166.2 (d, JC,F = 257.06 Hz).
HRMS (APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd for
C15H15ClFO2S 313.0460; Found 313.0453.
GP B was applied (238 mg = 76%, d.r.
1:1, white solid). H NMR (400 MHz, CDCl3, ppm): δ = 1.45
1
(s, 3H), 1.47 (s, 3H), 3.45-3.54 (m, 2H), 5.68 (s, 1H), 5.69 (s,
1H), 7.13-7.23 (m, 4H), 7.27-7.37 (m, 10H), 7.82-7.91 (m, 4H).
19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -103.08. 13C{1H}
NMR (100.6 MHz, CDCl3, ppm): δ = 9.5, 60.0, 67.3, 116.5 (d,
2JC,F = 22.89 Hz), 127.3, 128.9, 128.9, 132.4 (d, 3JC,F = 9.86 Hz),
GP B was applied (14 mg = 5%, colorless oil). 1H NMR
(400 MHz, CDCl3, ppm): δ = 0.97 (t, 3JH,H = 7.32 Hz, 3H), 1.48-
9
2
1.62 (m, 2H), 1.88 (s, 3H), 1.95-2.11 (m, 2H), 3.57 (d, JH,H
=
4
1
2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
133.7 (d, JC,F = 3.19 Hz), 138.5, 166.9 (d, JC,F = 256.87).
HRMS (ESI/QTOF) m/z: [M+Na]+ Calcd for C15H14ClFNaO2S
335.0279; Found 335.0279.
14.29 Hz, 1H), 3.64 (d, JH,H = 14.29 Hz, 1H), 7.21-7.30 (m,
2H), 7.90-7.99 (m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3,
ppm): δ = -102.96. 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ
= 14.0, 18.3, 30.7, 45.7, 67.2, 69.7, 116.8 (d, 2JC,F = 22.70 Hz),
131.0 (d, 3JC,F = 9.62 Hz), 137.0 (d, 4JC,F = 3.34 Hz), 166.1 (d,
1JC,F = 257.04 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M-Cl]+
Calcd for C12H16FO2S 243.0850; Found 243.0854.
GP B was applied (296 mg = 91%,
white solid). H NMR (400 MHz, CDCl3, ppm): δ = 2.17-2.30
1
(m, 1H), 2.54-2.66 (m, 1H), 2.83-2.96 (m, 1H), 2.96-3.08 (m,
1H), 3.81-3.90 (m, 1H), 5.57 (d, 3JH,H = 3.76 Hz, 1H), 7.01-7.13
(m, 1H), 7.17-7.28 (m, 4H), 7.30-7.40 (m, 1H), 7.84-7.97 (m,
2H). 19F{1H} NMR (376.3 MHz, CDCl3, ppm): δ = -102.54.
13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ = 20.1, 25.7, 54.1,
GP B was ap-
plied (314 mg = 66%, white solid). 1H NMR (400 MHz, CDCl3,
ppm): δ = 0.90-0.95 (m, 3H), 1.25 (s, 1H), 1.33-1.45 (m, 1H),
1.47-1.54 (m, 3H), 1.60-1.71 (m, 1H), 1.93-2.10 (m, 3H), 2.14
(dd, 2JH,H = 18.73 Hz, 3JH,H = 8.92 Hz, 1H), 2.19-2.29 (m, 1H),
2
67.9, 116.8 (d, JC,F = 22.62 Hz), 127.1, 128.9, 129.1, 130.2,
3
4
131.8 (d, JC,F = 9.90 Hz), 133.5, 134.2 (d, JC,F = 3.29 Hz),
1
135.9, 166.2 (d, JC,F = 257.52 Hz). HRMS (APPI/LTQ-
Orbitrap) m/z: [M-Cl]+ Calcd for C16H14FO2S 289.0693; Found
2.33-2.43 (m, 1H), 2.52 (dd, 2JH,H = 18.87 Hz, 3JH,H = 8.70 Hz,
2
289.0696.
1H), 2.63-2.78 (m, 1H), 2.78-2.87 (m, 1H), 3.89 (dd, JH,H
=
14.87 Hz, 3JH,H = 7.74 Hz, 1H), 3.96 (dd, 2JH,H = 14.85 Hz, 3JH,H
= 6.44 Hz, 1H), 5.27 (t, 3JH,H = 7.06 Hz, 1H), 6.87 (s, 1H), 7.00-
7.09 (m, 3H), 7.13-7.21 (m, 1H), 7.63-7.72 (m, 2H). 19F{1H}
NMR (376.3 MHz, CDCl3, ppm): δ = -103.29. 13C{1H} NMR
GP B was applied (200 mg = 68%, white solid).
1H NMR (400 MHz, CDCl3, ppm): δ = 2.03 (s, 3H), 3.77 (d,
2
2JH,H = 14.17 Hz, 1H), 3.84 (s, 3H), 4.12 (d, JH,H = 14.17 Hz,
(100.6 MHz, CDCl3, ppm): δ = 13.9, 21.7, 25.9, 26.4, 29.4,
1H), 7.19-7.31 (m, 2H), 7.88-7.99 (m, 2H). 19F{1H} NMR
2
31.7, 35.9, 38.1, 44.5, 48.0, 50.6, 55.1, 64.0, 116.3 (d, JC,F
=
(376.3 MHz, CDCl3, ppm): δ = -102.44. 13C{1H} NMR (100.6
22.56 Hz), 124.9, 126.1, 127.7, 131.2 (d, 3JC,F = 9.55 Hz), 135.3
MHz, CDCl3, ppm): δ = 27.0, 53.9, 62.4, 65.8, 116.9 (d, 2JC,F
=
4
1
(d, JC,F = 3.37 Hz), 135.5, 137.4, 141.4, 165.1 (d, JC,F
=
22.72 Hz). 131.2 (d, 3JC,F = 9.80 Hz), 136.5 (d, 4JC,F = 3.11 Hz),
257.16 Hz). HRMS (ESI/QTOF) m/z: [M+Na]+ Calcd for
C26H28ClFNaO3S 497.1324; Found 497.1322. Elemental analy-
sis: Anal. Calcd for C26H28ClFO3S: C, 65.74; H, 5.94; N, 0.00.
Found: C, 65.97; H, 6.23; N, 0.00.
1
166.2 (d, JC,F = 257.52 Hz), 169.3. HRMS (ESI/QTOF) m/z:
[M+Na]+ Calcd for C11H12ClFNaO4S 317.0021; Found
317.0023.
GP B
was applied (20 mg = 6%, pale yellow oil). 1H NMR (400 MHz,
1
GP B was applied (119 mg = 40%, off-white solid). H
3
CDCl3, ppm): δ = 0.88 (t, JH,H = 6.64 Hz, 3H), 1.27 (br. s.,
NMR (400 MHz, CD2Cl2, ppm): δ = 6.97 (s, 1H), 7.05-7.16 (m,
2H), 7.30-7.41 (m, 4H), 7.41-7.49 (m, 1H), 7.56-7.64 (m, 2H).
19F{1H} NMR (376.3 MHz, CD2Cl2, ppm): δ = -104.33.
10H), 1.36-1.56 (m, 2H), 1.70-1.84 (m, 1H), 1.87-2.00 (m, 1H),
3.47 (dd, 2JH,H = 14.75 Hz, 3JH,H = 5.74 Hz, 1H), 3.57 (dd, 2JH,H
= 14.73 Hz, 3JH,H = 6.72 Hz, 1H), 4.27-4.36 (m, 1H), 7.22-7.30
(m, 2H), 7.91-7.99 (m, 2H). 19F{1H} NMR (376.3 MHz, CDCl3,
ppm): δ = -102.71. 13C{1H} NMR (100.6 MHz, CDCl3, ppm): δ
= 14.2, 22.8, 25.9, 28.9, 29.3, 29.5, 31.9, 38.2, 54.6, 63.9, 116.8
13C{1H} NMR (100.6 MHz, CD2Cl2, ppm): δ = 116.7 (d, 2JC,F
=
22.82 Hz), 128.5, 129.1, 131.0 (d, 3JC,F = 9.78 Hz), 131.2, 131.4,
4
1
134.8, 137.0 (d, JC,F = 3.11 Hz), 148.9, 166.1 (d, JC,F
=
255.87 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd
(d, 2JC,F = 22.75 Hz), 131.3 (d, 3JC,F = 9.85 Hz), 135.7 (d, 4JC,F
=
for C14H12FO2S 263.0537; Found 263.0537.
3.77 Hz), 166.2 (d, 1JC,F = 256.66 Hz). HRMS (ESI/QTOF) m/z:
[M+Na]+ Calcd for C16H24ClFNaO2S 357.1062; Found
357.1059.
(E)-4-(1-Chloro-2-((4-fluorophenyl)sulfonyl)vinyl) benzal-
dehyde (12b). GP B was applied (65 mg = 20%, white solid).
1H NMR (400 MHz, CD2Cl2, ppm): δ = 7.01 (s, 3H), 7.10-7.20
(m, 2H), 7.50-7.60 (m, 2H), 7.61-7.74 (m, 2H), 7.85-8.00 (m,
2H), 10.07 (s, 1H). 19F{1H} NMR (376.3 MHz, CD2Cl2, ppm):
δ = -103.56. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm): δ =
117.0 (d, 2JC,F = 22.96 Hz), 129.5, 129.8, 131.1 (d, 3JC,F = 9.77
Hz), 132.2, 136.8 (d, 4JC,F = 3.08 Hz), 138.0, 140.2, 147.0, 166.3
GP B was applied (16 mg = 5%, colorless oil). 1H NMR
(400 MHz, CDCl3, ppm): δ = 3.13 (dd, 2JH,H = 14.27 Hz, 3JH,H
=
7.38 Hz, 1H), 3.24 (dd, 2JH,H = 14.25 Hz, 3JH,H = 6.04 Hz, 1H),
3
3
3.51 (d, JH,H = 1.68 Hz, 1H), 3.52 (s, 1H), 4.51 (quin., JH,H
=
6.44 Hz, 1H), 7.18-7.36 (m, 8H), 7.87-7.97 (m, 2H). 19F{1H}
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4
1
(d, 1JC,F = 256.6 Hz), 191.6. HRMS (APPI/LTQ-Orbitrap) m/z:
136.8 (d, JC,F = 2.77 Hz), 137.4, 147.4, 166.2 (d, JC,F
=
[M+H]+ Calcd for C15H11ClFO3S 325.0096; Found 325.0096.
256.33 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd
1
2
for C14H10Cl2FO2S 330.9757; Found 330.9762.
3
4
5
6
7
8
9
GP B was applied (117 mg = 33%, white
solid). 1H NMR (400 MHz, CD2Cl2, ppm): δ = 3.93 (s, 3H), 7.00
(s, 1H), 7.07-7.20 (m, 2H), 7.38-7.50 (m, 2H), 7.59-7.70 (m,
2H)-7.98-8.09 (m, 2H). 19F{1H} NMR (376.3 MHz, CD2Cl2,
ppm): δ = -103.76. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm):
δ = 52.7, 116.9 (d, 2JC,F = 22.87 Hz), 129.2, 129.6, 131.1 (d, 3JC,F
GP B was applied (210 mg = 56%, yellow
solid). H NMR (400 MHz, CD2Cl2, ppm): δ = 6.96 (s, 1H),
1
7.12-7.19 (m, 2H), 7.2-7.30 (m, 2H), 7.52-7.58 (m, 2H), 7.62-
7.69 (m, 2H). 19F{1H} NMR (376.3 MHz, CD2Cl2, ppm): δ = -
103.81. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm): δ = 116.9
4
2
3
= 9.83 Hz), 132.1, 132.6, 136.8 (d, JC,F = 3.31 Hz), 138.9,
(d, JC,F = 23.02 Hz), 125.7, 129.1, 130.8, 131.1 (d, JC,F =
147.4, 166.3 (d, 1JC,F = 255.95 Hz), 166.3. HRMS (ESI/QTOF)
m/z: [M+H]+ Calcd for C16H13ClFO4S 355.0202; Found
355.0199.
9.79 Hz), 131.8 (d, 4JC,F = 3.62 Hz), 132.5, 133.7, 147.4, 166.2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
(d, JC,F = 256.49 Hz). HRMS (APPI/LTQ-Orbitrap) m/z:
[M+H]+ Calcd for C14H10BrClFO2S 374.9252; Found 374.9262.
GP B was applied (116 mg = 31%, white solid).
1H NMR (400 MHz, CD2Cl2, ppm): δ = 6.99 (s, 1H), 7.05-7.14
(m, 2H), 7.38-7.52 (m, 5H), 7.58-7.69 (m, 6H). 19F{1H} NMR
(376.3 MHz, CD2Cl2, ppm): δ = -104.23. 13C{1H} NMR
GP B was applied (131 mg = 42%, yel-
low solid). 1H NMR (400 MHz, CD2Cl2, ppm): δ = 2.33 (s, 3H),
6.95 (s, 1H), 7.03-7.12 (m, 3H), 7.12-7.17 (m, 1H), 7.22-7.29
(m, 2H), 7.52-7.63 (m, 2H). 19F{1H} NMR (376.3 MHz,
CD2Cl2, ppm): δ = -104.57. 13C{1H} NMR (100.6 MHz,
2
(100.6 MHz, CD2Cl2, ppm): δ = 116.7 (d, JC,F = 22.96 Hz),
3
2
127.1, 127.6, 128.6, 129.4, 129.8, 131.1 (d, JC,F = 9.76 Hz),
CD2Cl2, ppm): δ = 21.4, 116.6 (d, JC,F = 22.79 Hz), 126.3,
4
3
131.4, 133.6, 137.0 (d, JC,F = 3.59 Hz), 140.2, 144.1, 148.6,
128.4, 129.4, 131.1 (d, JC,F = 9.85 Hz), 131.4, 131.9, 134.7,
166.1 (d, 1JC,F = 255.66 Hz). HRMS (APPI/LTQ-Orbitrap) m/z:
[M]+ Calcd for C20H14ClFO2S 372.0382; Found 372.0390.
CCDC 1889527 contains the supplementary crystallographic
data for 12d. This data can be obtained free of charge from The
137.0 (d, JC,F = 3.08 Hz), 138.6, 149.2, 166.1 (d, JC,F =
4
1
255.54 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd
for C15H13ClFO2S 311.0303; Found 311.0307.
Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
GP B was applied (126 mg = 40%, white solid).
1H NMR (400 MHz, CD2Cl2, ppm): δ = 6.98 (s, 1H), 7.02-7.09
(m, 1H), 7.09-7.22 (m, 4H), 7.31-7.43 (m, 1H), 7.61-7.70 (m,
2H). 19F{1H} NMR (376.3 MHz, CD2Cl2, ppm): δ = -103.86, -
112.75. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm): δ = 116.2
(d, 2JC,F = 23.68 Hz), 116.8 (d, 2JC,F = 22.84 Hz), 118.1 (d, 2JC,F
GP B was applied (167 mg = 51%,
1
white solid). H NMR (400 MHz, CDCl3, ppm): δ = 3.85 (s,
3H), 6.79-6.87 (m, 2H), 6.88 (s, 1H), 7.02-7.14 (m, 2H), 7.32-
7.43 (m, 2H), 7.60-7.70 (m, 2H). 19F{1H} NMR (376.3 MHz,
CDCl3, ppm): δ = -103.52 13C{1H} NMR (100.6 MHz, CDCl3,
ppm): δ = 55.6, 113.6, 116.4 (d, 2JC,F = 22.70 Hz), 126.4, 129.6,
4
3
= 21.07 Hz), 125.2 (d, JC,F = 3.24 Hz), 130.4 (d, JC,F = 8.24
Hz), 131.1 (d, 3JC,F = 9.80 Hz), 132.1, 136.5 (d, 3JC,F = 8.35 Hz),
136.8 (d, JC,F = 3.11 Hz), 146.8, 162.4 (d, JC,F = 247.69 Hz),
166.2 (d, 1JC,F = 256.13 Hz). HRMS (APPI/LTQ-Orbitrap) m/z:
[M+H]+ Calcd for C14H10ClF2O2S 315.0053; Found 315.0058.
4
1
3
4
130.7 (d, JC,F = 9.51 Hz), 131.1, 136.8 (d, JC,F = 3.13 Hz),
149.0, 161.9, 165.7 (d, 1JC,F = 256.21 Hz). HRMS (APPI/LTQ-
Orbitrap) m/z: [M+H]+ Calcd for C15H13ClFO3S 327.0252;
Found 327.0255.
GP B was applied (109 mg = 33%, white solid).
1H NMR (400 MHz, CD2Cl2, ppm): δ = 6.99 (s, 1H), 7.11-7.19
(m, 2H), 7.25-7.30 (m, 2H), 7.32-7.39 (m, 1H), 7.41-7.48 (m,
1H), 7.60-7.68 (m, 2H). 19F{1H} NMR (376.3 MHz, CD2Cl2,
ppm): δ = -103.82. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm):
GP B was applied (135 mg = 43%, off-white
solid). H NMR (400 MHz, CD2Cl2, ppm): δ = 6.97 (s, 1H),
1
7.03-7.19 (m, 4H), 7.34-7.45 (m, 2H), 7.58-7.69 (m, 2H).
19F{1H} NMR (376.3 MHz, CD2Cl2, ppm): δ = -103.95, -
108.98. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm): δ = 115.7
(d, 2JC,F = 22.27 Hz), 116.8 (d, 2JC,F = 23.02 Hz), 130.8 (d, 4JC,F
= 3.61 Hz), 131.0 (d, 3JC,F = 9.68 Hz), 131.6 (d, 3JC,F = 8.56 Hz),
δ = 116.9 (d, 2JC,F = 23.03 Hz), 127.5, 128.9, 130.0, 131.12 (d,
4
3JC,F = 9.84 Hz), 131.13, 132.3, 134.4, 136.3, 136.7 (d, JC,F
=
1
3.08 Hz), 146.8, 166.3 (d, JC,F = 256.56 Hz). HRMS
(APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd for C14H10Cl2FO2S
330.9757; Found 330.9758.
4
1
136.9 (d, JC,F = 3.11 Hz), 147.7, 164.4 (d, JC,F = 251.65 Hz),
166.2 (d, 1JC,F = 255.95 Hz). HRMS (APPI/LTQ-Orbitrap) m/z:
[M+H]+ Calcd for C14H10ClF2O2S 315.0053; Found 315.0053.
GP B was applied (140 mg = 45%, white
solid). 1H NMR (400 MHz, CD2Cl2, ppm): δ = 2.08 (s, 3H), 7.04
(s, 1H), 7.06-7.12 (m, 3H), 7.14-7.23 (m, 2H), 7.31-7.38 (m,
1H), 7.45-7.53 (m, 2H). 19F{1H} NMR (376.3 MHz, CD2Cl2,
ppm): δ = -104.26. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm):
δ = 19.2, 116.6 (d, 2JC,F = 22.78 Hz), 125.6, 129.0, 130.7, 130.8,
GP B was applied (169 mg = 51%, yellow
solid). H NMR (400 MHz, CD2Cl2, ppm): δ = 6.96 (s, 1H),
1
7.08-7.20 (m, 2H), 7.24-7.46 (m, 4H), 7.56-7.72 (m, 2H).
19F{1H} NMR (376.3 MHz, CD2Cl2, ppm): δ = -103.83.
13C{1H} NMR (100.6 MHz, CD2Cl2, ppm): δ = 116.8 (d, 2JC,F
=
131.2 (d, 3JC,F = 9.83 Hz), 132.9, 134.2, 136.4, 136.7 (d, 4JC,F
3.69 Hz), 149.3, 166.2 (d, JC,F = 255.96 Hz). HRMS
=
22.83 Hz), 128.8, 130.7, 131.1 (d, 3JC,F = 9.79 Hz), 131.8, 133.2,
1
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The Journal of Organic Chemistry
(APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd for C15H13ClFO2S
311.0303; Found 311.0310.
Catalyzed by a Mixture of [RuCl2Cp*(PPh3)] and Magnesium. Chemistry
- A European Journal 2007, 13 (24), 6899-6907.
5. Muñoz-Molina, J. M.; Belderraín, T. R.; Pérez, P. J., An
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Inorganic Chemistry 2010, 49 (2), 642-645.
1
2
3
4
5
6
7
8
GP B was applied (110 mg = 33%,
off-white solid). 1H NMR (400 MHz, CD2Cl2, ppm): δ = 6.90-
6.97 (m, 3H), 6.97-7.02 (m, 1H), 7.15-7.23 (m, 2H), 7.67-7.75
(m, 2H). 19F{1H} NMR (376.3 MHz, CD2Cl2, ppm): δ = -
103.40, -108.92. 13C{1H} NMR (100.6 MHz, CD2Cl2, ppm): δ
= 106.5 (t, 2JC,F = 25.18 Hz), 112.5 (d, 2JC,F = 27.28 Hz), 117.0
(d, 2JC,F = 23.00 Hz), 131.1 (d, 3JC,F = 9.82 Hz), 132.7, 136.6 (d,
4JC,F = 3.36 Hz), 137.4 (t, 3JC,F = 10.15 Hz), 146.2, 162.7 (d, 1JC,F
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Zeng, K.; Chen, L.; Chen, Y.; Liu, Y.; Zhou, Y.; Au, C. T.; Yin,
S. F., Iron(III) Chloride‐ Mediated Regio‐ and Stereoselective
Chlorosulfonylation of Alkynes and Alkenes with Sodium Sulfinates.
Advanced Synthesis & Catalysis 2017, 359 (5), 841-847.
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reactions—IV: The reaction of methanesulphonyl and methanedisulphonyl
chlorides with alkenes. Tetrahedron 1965, 21 (10), 2743-2747.
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10
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12
13
14
15
16
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18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
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= 250.20 Hz), 162.8 (d, JC,F = 250.42 Hz), 166.4 (d, JC,F
=
256.56 Hz). HRMS (APPI/LTQ-Orbitrap) m/z: [M+H]+ Calcd
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Li, X.; Shi, X.; Fang, M.; Xu, X., Iron Halide-Mediated Regio-
for C14H9ClF3O2S 332.9958; Found 332.9962.
and Stereoselective Halosulfonylation of Terminal Alkynes with
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The Supporting Information (experimental procedure for photore-
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thesized compounds as PDF) is available free of charge on the ACS
Publications website.
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Jiang, H.; Cheng, Y.; Zhang, Y.; Yu, S., Sulfonation and
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Dr. Rosario Scopelliti (EPFL) and Dr. Farzaneh Fadaei Tirani
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