Shen et al.
FULL PAPER
General procedure for nucleophilic difluoromethyla-
tion of alkyl halides with PhSO(NTBS)CF2H (5)
688, 592 cm−1; MS (ESI) m/z: 348.1 (M+H+); HRMS
(ESI) m/z calcd for C16H27F2NNaOSSi (M + Na + )
370.1443, found 370.1450.
N-tert-Butyldimethylsilyl-S-1,1-difluoropentyl-S-
phenylsulfoximine (7d) Colorless oil. H NMR (400
MHz, CDCl3) δ: 7.96 (d, J=7.5 Hz, 2H), 7.63 (t, J=7.4
Hz, 1H), 7.54 (t, J=7.6 Hz, 2H), 2.40-1.99 (m, 2H),
1.69-1.48 (m, 2H), 1.47-1.28 (m, 2H), 0.99-0.88
(m, 12H), 0.11 (s, 6H); 19F NMR (376 MHz, CDCl3) δ:
−104.45 (ddd, J=219.1, 23.3, 13.4 Hz), −106.39 (ddd,
J=219.2, 23.9, 13.9 Hz); 13C NMR (101 MHz, CDCl3)
δ: 137.62, 133.42, 130.15, 128.66, 125.01 (t, J=286.9
Hz), 28.67 (t, J=20.9 Hz), 25.81, 23.05 (t, J=3.1 Hz),
22.37, 18.02, 13.68, −2.48, −2.58; IR (film) ν: 3069,
2958, 2931, 2858, 1584, 1471, 1345, 1252, 1172, 1087,
829, 777, 688, 592 cm−1; MS (ESI) m/z: 362.1 (M+H+);
HRMS (ESI) m/z calcd for C17H29F2NNaOSSi (M+
Na+) 384.1599, found 384.1608.
Under N2, to a solution of difluoromethyl sulfoxi-
mine (5, 122 mg) and 1-bromoheptane (6a, 94 µL, 0.6
mmol) in dried THF (4 mL) and dried HMPA (0.8 mL),
was added LiHMDS (1 mol/L in THF, 0.52 mL, 0.52
mmol) at −78 ℃. After 30 min, the reaction was
quenched by adding an excess of saturated NH4Cl (aq.),
followed by extraction with ethyl acetate. The organic
phase was washed with brine and then dried over
anhydrous MgSO4. After the solution was filtered and
the solvent was evaporated under vacuum, the residue
was subjected to silica gel column chromatography us-
ing petroleum ether as eluent to give product 7a (145
mg, 90%).
1
N-tert-Butyldimethylsilyl-S-1,1-difluorooctyl-S-
phenylsulfoximine (7a) Colorless oil. H NMR (300
1
MHz, CDCl3) δ: 7.97 (d, J=7.7 Hz, 2H), 7.64 (t, J=7.3
Hz, 1H), 7.52 (dd, J=7.4 Hz, 2H), 2.19 (ddd, J=22.4,
15.6, 7.9 Hz, 2H), 1.73-1.47 (m, 2H), 1.45-1.17 (m,
8H), 0.99-0.80 (m, 12H), 0.12 (s, 6H); 19F NMR (282
MHz, CDCl3) δ: −104.78 (ddd, J=219.4, 23.4, 14.8 Hz,
1F), −106.79 (ddd, J=219.5, 24.7, 13.5 Hz, 1F); 13C
NMR (101 MHz, CDCl3) δ: 137.64, 133.41, 130.14,
128.65, 125.00 (t, J=287.0 Hz), 31.53, 29.17, 28.98 (t,
J=21.0 Hz), 28.87, 25.82, 22.54, 21.01 (t, J=3.1 Hz),
18.02, 14.01, −2.49, −2.58; IR (film) ν: 3069, 2955,
2929, 2857, 1584, 1471, 1347, 1252, 1171, 1089, 829,
777, 688, 593 cm−1; MS (ESI) m/z: 404.1 (M+H+);
HRMS (ESI) m/z calcd for C20H35F2NNaOSSi (M+
Na+) 426.2069, found 426.2066.
N-tert-Butyldimethylsilyl-S-1,1-difluoroheptyl-S-
phenylsulfoximine (7e) Colorless oil. H NMR (400
1
MHz, CDCl3) δ: 7.96 (d, J=7.5 Hz, 2H), 7.63 (t, J=7.4
Hz, 1H), 7.53 (t, J=7.6 Hz, 2H), 2.30-2.07 (m, 2H),
1.66-1.51 (m, 2H), 1.41-1.20 (m, 6H), 0.93 (s, 9H),
0.88 (t, J=6.8 Hz, 3H), 0.12 (s, 6H); 19F NMR (376
MHz, CDCl3) δ: −104.42 (ddd, J=219.1, 23.2, 13.4 Hz),
−106.35 (ddd, J=219.2, 23.9, 13.9 Hz); 13C NMR (101
MHz, CDCl3) δ: 137.65, 133.42, 130.15, 128.69, 125.01
(t, J=287.0 Hz), 31.39, 29.00 (t, J=21.0 Hz), 28.89,
25.83, 22.38, 20.99 (t, J=3.1 Hz), 18.03, 13.97, −2.47,
−2.57; IR (film) ν: 3069, 2956, 2857, 1584, 1471, 1346,
1252, 1171, 829, 777, 688, 593 cm−1; MS (ESI) m/z:
348.1 (M+H+); HRMS (ESI) m/z calcd for C19H33F2N-
NaOSSi (M+Na+) 412.1912, found 412.1917.
N-tert-Butyldimethylsilyl-S-1,1-difluoropropyl-S-
phenylsulfoximine (7b) Colorless oil. H NMR (300
1
N-tert-Butyldimethylsilyl-S-1,1-difluorotridecyl-
S-phenylsulfoximine (7f) Colorless oil. 1H NMR
(300 MHz, CDCl3) δ: 7.96 (d, J=7.5 Hz, 2H), 7.63 (t,
J=7.3 Hz, 1H), 7.53 (t, J=7.5 Hz, 2H), 2.37-1.95 (m,
2H), 1.72-1.47 (m, 2H), 1.43-1.19 (m, 18H), 0.93 (s,
9H), 0.88 (t, J=6.6 Hz, 3H), 0.11 (s, 6H); 19F NMR
(282 MHz, CDCl3) δ: −104.37 (ddd, J=219.2, 23.1,
13.6 Hz), −106.38 (ddd, J=219.0, 23.7, 14.0 Hz); 13C
NMR (101 MHz, CDCl3) δ: 137.65, 133.40, 130.14,
128.65, 125.00 (t, J=287.1 Hz), 31.89, 29.59, 29.53,
29.35, 29.32, 29.22, 29.20, 28.99 (t, J=20.9 Hz), 28.78,
25.82, 22.66, 21.02 (t, J=3.0 Hz), 18.01, 14.10, −2.48,
−2.58; IR (film) ν: 3069, 2927, 2855, 1470, 1447, 1346,
1170, 1024, 828, 688, 592 cm−1; MS (ESI) m/z: 474.2
(M+H+); HRMS (ESI) m/z calcd for C25H45F2NnaOSSi
(M+Na+) 496.2857, found 496.2869.
N-tert-Butyldimethylsilyl-S-1,1-difluoro-4-methyl-
pentyl-S-phenylsulfoximine (7g) Colorless oil. 1H
NMR (400 MHz, CDCl3) δ: 7.96 (d, J=7.5 Hz, 2H),
7.63 (t, J=7.4 Hz, 1H), 7.53 (t, J=7.6 Hz, 2H), 2.30-
2.06 (m, 2H), 1.70-1.54 (m, 1H), 1.53-1.36 (m, 2H),
0.94 (s, 9H), 0.91 (d, J=6.6 Hz, 6H), 0.12 (s, 6H); 19F
NMR (376 MHz, CDCl3) δ: −104.45 (ddd, J=218.6,
23.0, 13.2 Hz), −106.50 (ddd, J=218.6, 23.7, 13.8 Hz);
13C NMR (101 MHz, CDCl3) δ: 137.63, 133.41, 130.14,
MHz, CDCl3) δ: 7.96 (d, J=7.6 Hz, 2H), 7.64 (t, J=7.4
Hz, 1H), 7.54 (t, J=7.5 Hz, 2H), 2.46-1.90 (m, 2H),
1.10 (t, J=7.5 Hz, 3H), 0.93 (s, 9H), 0.11 (s, 6H); 19F
NMR (282 MHz, CDCl3) δ: −106.56 (ddd, J=219.3,
22.6, 13.5 Hz), −108.69 (ddd, J=219.4, 23.0, 13.9 Hz);
13C NMR (101 MHz, CDCl3) δ: 137.69, 133.43, 130.12,
128.67, 125.01 (t, J=286.9 Hz), 25.81, 22.82 (t, J=
21.7 Hz), 18.00, 5.35 (t, J=4.5 Hz), −2.50, −2.61; IR
(film) ν: 3069, 2954, 2929, 2857, 1584, 1464, 1347,
1253, 1172, 1080, 829, 778, 688, 564 cm−1; MS (ESI)
m/z: 334.0 (M+H+ ); HRMS (ESI) m/z calcd for
+
C15H25F2NNaOSSi (M + Na
) 356.1286, found
356.1295.
N-tert-Butyldimethylsilyl-S-1,1-difluorobutyl-S-
1
phenylsulfoximine (7c) Colorless oil. H NMR (400
MHz, CDCl3) δ: 7.96 (d, J=7.3 Hz, 2H), 7.63 (t, J=7.4
Hz, 1H), 7.53 (t, J=7.6 Hz, 2H), 2.28-2.00 (m, 2H),
1.68-1.49 (m, 2H), 0.99 (t, J=7.4 Hz, 3H), 0.93 (s,
9H), 0.11 (d, J=0.8 Hz, 6H); 19F NMR (376 MHz,
CDCl3) δ: −104.00-−104.85 (m), −106.33 (ddd, J=
219.7, 23.2, 14.5 Hz); 13C NMR (101 MHz, CDCl3) δ:
137.64, 133.41, 130.14, 128.66, 124.91 (t, J=287.1 Hz),
30.94 (t, J=20.9 Hz), 25.81, 18.01, 14.75 (t, J=3.6 Hz),
13.83, −2.49, −2.59; IR (film) ν: 3070, 2956, 2930,
2857, 1645, 1471, 1347, 1252, 1171, 1087, 828, 777,
706
© 2014 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2014, 32, 703—708