6
Tetrahedron
ACCEPTED MANUSCRIPT
Chloroform-d) δ -45.5. FT-IR (cm-1) 3067, 2969, 2942, 2889,
EtOAc (5 mL) and poured into aqueous HCl (12 mL, 1 M
2837, 2541, 2367, 2284, 1895, 1583, 1571, 1489, 1462, 1434,
1406, 1299, 1289, 1249, 1190, 1179, 1104, 1021, 823, 793, 762,
707, 604, 517, 484. HRMS (M-H+) 420.9215.
concentration). The organic layer was decanted, and the crude
product was extracted from the aqueous layer two more times (5
mL EtOAc each time). The organic layers were washed with
brine, dried over MgSO4, filtered, and concentrated. Flash
column chromatography (hexanes) of the crude mixture afforded
2e: 2,2'-((Difluoromethylene)bis(selanediyl))bis(N,N-
dimethylaniline)
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2g in 84% isolated yield (181 mg) as a colorless solid. H NMR
(399 MHz, Chloroform-d) δ 7.64 – 7.57 (m, 1H), 7.38 – 7.30 (m,
1H). 13C NMR (100 MHz, Chloroform-d) δ 138.3 (d, J = 1.1
Hz), 136.7, 129.7, 124.3 (t, J = 1.2 Hz), 118.8 (t, J = 348.2 Hz).
19F NMR (376 MHz, Chloroform-d) δ -44.1. FT-IR (cm-1) 3084,
2923, 2851, 2761, 2645, 2359, 1909, 1645, 1579, 1558, 1470,
1435, 1387, 1350, 1291, 1267, 1084, 1023, 1009, 951, 801, 732,
486.
In an argon glovebox, LiOtBu (0.5 mmol, 1.0 equiv, 40.0 mg),
LiCl (0.6 mmol, 1.2 equiv, 25.4 mg) and 1,2-bis(4-(N,N-
dimethylamino)phenyl) diselenide (0.5 mmol, 199.1 mg) were
weighed into an oven-dried, crimp-top vial equipped with a
magnetic stir bar and sealed. Under N2, DMF (0.63 mL) was
added by syringe, and the solution was stirred for 5 mins,
followed by dropwise addition of TMSCF3 (1.0 mmol, 2 equiv,
148 µL). The solution was stirred for 10 mins, the vial was
opened, the solution was diluted with EtOAc (5 mL) and poured
into saturated K2CO3 (12 mL). The organic layer was decanted,
and the crude product was extracted from the aqueous layer two
more times (5 mL EtOAc each time). The organic layers were
washed with brine, dried over MgSO4, filtered, and concentrated.
Flash column chromatography (gradient of 0% to 10% EtOAc in
hexanes) of the crude mixture afforded 2e in 63% isolated yield
2i: Difluorobis(phenylthio)methane
In an argon glovebox, LiOtBu (1.5 mmol, 3.0 equiv, 120.0
mg), and 1,2-diphenyl disulfide (0.5 mmol, 109.0 mg) were
weighed into an oven-dried, crimp-top vial equipped with a
magnetic stir bar and sealed. Under N2, DMF (0.63 mL) was
added by syringe, and the solution was stirred for 5 mins,
followed by dropwise addition of TMSCF3 (1.0 mmol, 2 equiv,
148 µL). The solution was stirred for 10 mins, the vial was
opened, the solution was diluted with EtOAc (5 mL) and poured
into aqueous HCl (12 mL, 1 M concentration). The organic layer
was decanted, and the crude product was extracted from the
aqueous layer two more times (5 mL EtOAc each time). The
organic layers were washed with brine, dried over MgSO4,
filtered, and concentrated. Flash column chromatography
(hexanes) of the crude mixture afforded 2i in 71% isolated yield
(95 mg) as a pale-yellow oil. 1H NMR (399 MHz, Chloroform-d)
δ 7.66 – 7.56 (m, 4H), 7.49 – 7.43 (m, 2H), 7.43 – 7.36 (m, 4H).
13C NMR (100 MHz, Chloroform-d) δ 136.3, 132.4 (t, J = 312.4
Hz), 130.3, 129.2, 127.4. 19F NMR (376 MHz, Chloroform-d) δ -
49.5. The NMR data matches previous reports.31
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(141 mg) as a pale-yellow oil. H NMR (399 MHz, Chloroform-
d) δ 7.81 (d, J = 7.9 Hz, 2H), 7.30 – 7.25 (m, 2H), 7.16 (dd, J =
8.0, 1.5 Hz, 2H), 7.07 (ddd, J = 7.9, 7.2, 1.4 Hz, 2H), 2.69 (s,
12H). 13C NMR (100 MHz, Chloroform-d) δ 153.4, 133.3 (t, J =
2.2 Hz), 128.7, 128.2, 125.2, 120.9, 120.6 (t, J = 346.5 Hz), 45.3.
19F NMR (376 MHz, Chloroform-d) δ -46.6. FT-IR (cm-1) 2940,
2824, 2785, 1570, 1491, 1473, 1291, 1250, 1173, 1018, 1013,
940, 794, 760, 731, 651, 518, 491. HRMS (M-H+) 447.2703.
2f: Difluorobis((3-methoxyphenyl)selanyl)methane
In an argon glovebox, LiOtBu (0.5 mmol, 1.0 equiv, 40.0 mg),
LiCl (0.6 mmol, 1.2 equiv, 25.4 mg) and 1,2-bis(3-
methoxyphenyl) diselenide (0.5 mmol, 186.1 mg) were weighed
into an oven-dried, crimp-top vial equipped with a magnetic stir
bar and sealed. Under N2, DMF (0.63 mL) was added by syringe,
and the solution was stirred for 5 mins, followed by dropwise
addition of TMSCF3 (1.0 mmol, 2 equiv, 148 µL). The solution
was stirred for 10 mins, the vial was opened, the solution was
diluted with EtOAc (5 mL) and poured into aqueous HCl (12 mL,
1 M concentration). The organic layer was decanted, and the
crude product was extracted from the aqueous layer two more
times (5 mL EtOAc each time). The organic layers were washed
with brine, dried over MgSO4, filtered, and concentrated. Flash
column chromatography (gradient of 0% to 10% EtOAc in
hexanes) of the crude mixture afforded 2f in 82% isolated yield
2j: Difluorobis((3-fluorophenyl)thio)methane
In an argon glovebox, LiOtBu (1.5 mmol, 3.0 equiv, 120.0
mg), and bis(3-fluorophenyl) disulfide (0.5 mmol, 127.2 mg)
were weighed into an oven-dried, crimp-top vial equipped with a
magnetic stir bar and sealed. Under N2, DMF (0.63 mL) was
added by syringe, and the solution was stirred for 5 mins,
followed by dropwise addition of TMSCF3 (1.0 mmol, 2 equiv,
148 µL). The solution was stirred for 10 mins, the vial was
opened, the solution was diluted with EtOAc (5 mL) and poured
into aqueous HCl (12 mL, 1 M concentration). The organic layer
was decanted, and the crude product was extracted from the
aqueous layer two more times (5 mL EtOAc each time). The
organic layers were washed with brine, dried over MgSO4,
filtered, and concentrated. Flash column chromatography
(gradient of 0% to 10% EtOAc in hexanes) of the crude mixture
afforded 2j in 62% isolated yield (94 mg) as a pale-yellow oil. 1H
NMR (399 MHz, Chloroform-d) δ 7.4 – 7.3 (m, 6H), 7.2 (m,
2H). 13C NMR (100 MHz, Chloroform-d) δ 162.5 (d, J = 250.2
Hz), 132.1 (t, J = 315.5 Hz), 131.8 (d, J = 3.2 Hz), 130.5 (d, J =
8.3 Hz), 129.0 (dt, J = 7.9, 1.4 Hz), 122.9 (d, J = 22.1 Hz), 117.7
(d, J = 21.0 Hz). 19F NMR (376 MHz, Chloroform-d) δ -49.2, -
110.5 – -113.3 (m). HRMS (M-H+) 303.0011.
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(174 mg) as a pale-yellow oil. H NMR (399 MHz, Chloroform-
d) δ 7.30 – 7.27 (m, 4H), 7.25 – 7.23 (m, 2H), 7.01 – 6.95 (m,
2H), 3.82 (s, 6H). 13C NMR (100 MHz, Chloroform-d) δ 159.8,
130.1, 129.0, 126.9, 121.9, 119.1 (t, J = 347.4 Hz), 115.9, 55.5.
19F NMR (376 MHz, Chloroform-d) δ -43.5. FT-IR (cm-1) 3085,
3053, 3017, 2964, 2938, 2837, 2518, 2059, 1587, 1571, 1477,
1465, 1455, 1440, 1421, 1301, 1286, 1232, 1184, 1169, 1035,
1013, 899, 877, 830, 800, 770, 684, 664, 574, 557, 453. HRMS
(M-H+) 420.9156.
2g: Bis((4-chlorophenyl)selanyl)difluoromethane
In an argon glovebox, LiOtBu (0.5 mmol, 1.0 equiv, 40.0 mg),
LiCl (0.6 mmol, 1.2 equiv, 25.4 mg) and 1,2-bis(4-chlorophenyl)
diselenide (0.5 mmol, 191.0 mg) were weighed into an oven-
dried, crimp-top vial equipped with a magnetic stir bar and
sealed. Under N2, DMF (0.63 mL) was added by syringe, and the
solution was stirred for 5 mins, followed by dropwise addition of
TMSCF3 (1.0 mmol, 2 equiv, 148 µL). The solution was stirred
for 10 mins, the vial was opened, the solution was diluted with
2k: Difluorobis(p-tolylthio)methane
In an argon glovebox, LiOtBu (1.5 mmol, 3.0 equiv, 120.0
mg), and di-p-tolyl disulfide (0.5 mmol, 123.2 mg) were weighed
into an oven-dried, crimp-top vial equipped with a magnetic stir
bar and sealed. Under N2, DMF (0.63 mL) was added by syringe,
and the solution was stirred for 5 mins, followed by dropwise
addition of TMSCF3 (1.0 mmol, 2 equiv, 148 µL). The solution