10.1002/adsc.201700492
Advanced Synthesis & Catalysis
146.0 (C=C-S), 141.0 (CAr-q), 134.1 (CHAr), 132.3 (C=C-S), 70.57 (s, 6F, 2CF3); 31P NMR (121 MHz, CDCl3, 25 oC):
132.2 (CHAr), 131.9 (CHAr), 129.7 (2CHAr), 128.7 (CHAr),
127.6 (CAr-q), 124.1 (2CHAr), 120.2 (q, JCF = 331.8 Hz,
CF3), 119.9 (q, JCF = 331.6 Hz, CF3), 84.4 (CTf2), 33.7
= 4.48 [s, P, P=O(OiPr)2]; IR (CHCl3): = 1605 (C=C),
1387, 1103 (O=S=O), 1206 (C–F), 988 (P=O) cm–1;
HRMS (ES): calcd for C19H23F6O8PS2Na [M + Na]+:
611.0368; found: 611.0353.
o
(CH2); 19F NMR (282 MHz, C6D6, 25 C): = –70.74 (s,
3F, CF3), –71.63 (s, 3F, CF3); IR (CH2Cl2): = 1386, 1105
(O=S=O), 1212 (C–F) cm–1; HRMS (ES): calcd for
C16H11F6O5S4 [M + H]+: 524.9388; found: 524.9400.
Bis(trifluoromethylsulfonyl)silacyclobutene 21b. From
50 mg (0.17 mmol) of alkyne 20b, and after flash
chromatography of the residue using hexanes/ethyl acetate
(99:1) as eluent gave compound 21b (80 mg, 81%) as a
Bis(trifluoromethylsulfonyl)sulfonylcyclobutene
9i.
1
From 44 mg (0.16 mmol) of alkyne 8i, and after flash
chromatography of the residue using hexanes/ethyl acetate
(97:3) as eluent gave compound 9i (90 mg, quantitative
colorless oil; H NMR (300 MHz, CDCl3, 25 oC): = 7.42
(m, 2H, 2CHAr), 6.89 (m, 2H, 2CHAr), 3.84 (s, 3H, OCH3),
3.32 (s, 2H, CH2), 1.10 (m, 21H, 3CH + 6CH3); 13C NMR
1
yield) as a colorless solid; mp 103–105 ºC; H NMR (300
(75 MHz, CDCl3, 25 oC): = 162.3 (C=C-Si), 160.7 (CAr-q
-
o
MHz, CDCl3, 25 C): = 8.07 (m, 2H, 2CHAr), 7.93 (m,
OCH3), 149.0 (C=C-Si), 129.9 (2CHAr), 125.1 (CAr-q),
119.8 (q, JCF = 331.1 Hz, 2CF3), 113.5 (2CHAr), 90.1
(CTf2), 55.2 (OCH3), 36.2 (CH2), 18.4 (6CH3), 11.5 (3CH);
2H, 2CHAr), 7.71 (m, 1H, CHAr), 7.59 (m, 2H, 2CHAr),
6.97 (m, 2H, 2CHAr), 3.88 (s, 3H, OCH3), 3.50 (s, 2H,
CH2); 13C NMR (75 MHz, CDCl3, 25 oC): = 163.0 (CAr-q
-
19F NMR (282 MHz, CDCl3, 25 C): = –70.29 (s, 6F,
o
OCH3), 141.9 (C=C-SO2Ph), 139.1 (C=C-SO2Ph), 137.5
(CAr-q), 135.0 (CHAr), 132.5 (2CHAr), 129.7 (2CHAr), 127.9
(2CHAr), 119.6 (q, JCF = 331.5 Hz, 2CF3), 119.5 (CAr-q),
114.3 (2CHAr), 84.2 (CTf2), 55.5 (OCH3), 35.9 (CH2); 19F
NMR (282 MHz, CDCl3, 25 oC): = –70.51 (s, 6F, 2CF3);
IR (CHCl3): = 1599 (C=C), 1386, 1101 (O=S=O), 1212
(C–F) cm–1; HRMS (ES): calcd for C19H18F6NO7S3 [M +
NH4]+: 582.0144; found: 582.0155.
2CF3); IR (CHCl3): = 1614 (C=C), 1379, 1106 (O=S=O),
1203 (C–F) cm–1; HRMS (ES): calcd for C22H31F6NO5S2Si
[M + NH4]+: 598.1546; found: 598.1566.
Bis(trifluoromethylsulfonyl)bis(trifluoromethylsulfonyl
)cyclobutene 24c. From 20 mg (0.047 mmol) of alkyne
22c, and after flash chromatography of the residue using
hexanes/ethyl acetate (1:1) as eluent gave compound 24c
1
(21 mg, 61%) as a colorless solid; mp 153–155 ºC; H
o
Bis(trifluoromethylsulfonyl)aminocyclobutene
11a.
NMR (300 MHz, acetone-d6, 25 C): = 7.60 (m, 2H,
From 20 mg (0.07 mmol) of alkyne 10a, and after flash
2CHAr), 6.96 (m, 2H, 2CHAr), 3.80 (s, 3H, OCH3), 3.66 (s,
chromatography of the residue using hexanes/ethyl acetate
2H, CH2), 3.51 (s, 2H, CH2-cyclobutenyl). The signal of
1
(95:5) as eluent gave compound 11a (38 mg, 94%) as a
CHTf2 is not visible in the H-RMN spectrum because of
1
o
colorless solid; mp 117–119 ºC; H NMR (300 MHz, C6D6, its acidity; 13C NMR (75 MHz, acetone-d6, 25 C): =
o
25 C): = 8.65 (d, 1H, J = 8.0 Hz, CHAr), 8.35 (s, 1H,
NCHAr), 7.40 (d, 1H, J = 8.3 Hz, CHAr), 7.15 (m, 1H,
CHAr), 6.98 (m, 1H, CHAr), 6.84 (m, 1H, CHAr), 6.65 (m,
4H, 4CHAr), 3.48 (s, 3H, CH3), 3.11 (s, 2H, CH2); 13C
161.3 (CAr-q-OCH3), 156.4 (C=C), 130.5 (C=C), 130.2
(2CHAr), 123.5 (CAr-q), 122.6 (q, JCF = 327.7 Hz, 2CF3),
120.9 (q, JCF = 331.1 Hz, 2CF3-cyclobutenyl), 114.9
(2CHAr), 86.9 (CTf2-cyclobutenyl), 61.2 (CTf2), 55.8
(OCH3), 37.5 (CH2-cyclobutenyl), 29.6 (CH2). The signal
of CHTf2 is visible in the 13C-RMN spectrum as a
quaternary carbon rather than as a CH because of the
o
NMR (75 MHz, C6D6, 25 C): = 164.0 (C=O), 152.9
(C=C-N), 136.4 (C=C-N), 132.5 (CHAr), 131.7 (CHAr),
129.1 (2CHAr), 128.4 (2CHAr), 128.2 (CAr-q), 126.9 (CAr-q),
125.0 (CHAr), 124.0 (CHAr), 123.0 (CHAr), 120.1 (q, JCF
=
deprotonation; 19F NMR (282 MHz, acetone-d6, 25 C):
o
330.8 Hz, 2CF3), 118.9 (CAr-q), 112.8 (CAr-qo), 112.0 (CHAr), = –72.04 (s, 6F, 2CF3-cyclobutenyl), –80.10 (s, 6F, 2CF3);
90.0 (CTf2), 51.0 (CH3), 31.1 (CH2); 19F NMR (282 MHz,
IR (acetone): = 1608 (C=C), 1380, 1099 (O=S=O), 1346,
1042 (O=S=O), 1192 (C–F) cm–1; HRMS (ES): calcd for
C17H16F12NO9S4 [M + NH4]+: 733.9511; found: 733.9513.
o
C6D6, 25 C): = –70.44 (s, 6F, 2CF3); IR (CH2Cl2): =
1711 (C=O), 1375, 1102 (O=S=O), 1196 (C–F) cm–1;
HRMS (ES): calcd for C22H19F6N2O6S2 [M + NH4]+:
585.0583; found: 585.0559.
Bis(trifluoromethylsulfonyl)thiocyclobutene 27a. From
15 mg (0.027 mmol) of azide 26a, and after flash
Bis(trifluoromethylsulfonyl)phosphinylcyclobutene 19b. chromatography of the residue using hexanes/ethyl acetate
From 53 mg (0.18 mmol) of alkyne 18b, and after flash
chromatography of the residue using hexanes/ethyl acetate
(95:5→9:1) as eluent gave compound 19b (99 mg, 94%) as
(8:2) as eluent gave compound 27a (17 mg, 85%) as a
1
yellow oil; H NMR (700 MHz, CDCl3, 25 oC): = 8.80 (s,
1H, CH-triazolyl), 7.87 (m, 2H, 2CHAr), 7.76 (m, 1H,
CHAr), 7.63 (m, 1H, CHAr), 7.54 (m, 4H, 4CHAr), 7.49 (m,
1H, CHAr), 3.68 (s, 2H, CH2); 13C NMR (175 MHz, CDCl3,
1
o
a colorless oil; H NMR (300 MHz, CDCl3, 25 C): =
8.06 (m, 2H, 2CHAr), 6.95 (m, 2H, 2CHAr), 4.76 (m, 2H,
2CH), 3.85 (s, 3H, OCH3), 3.50 (s, 2H, CH2), 1.37 (d, 6H,
J = 6.2 Hz, 2CH3), 1.27 (d, 6H, J = 6.2 Hz, 2CH3); 13C
o
25 C): = 165.9 (C=C-S), 139.5 (CAr-q-Tf), 136.1 (C=C-
S), 134.5 (CHAr), 133.7 (CHAr), 133.1 (CHAr), 131.8
(CHAr), 130.1 (CHAr), 129.5 (2CHAr), 129.3 (CAr-q), 128.1
(2CHAr), 127.4 (CAr-q), 127.1 (CHAr), 119.6 (q, JCF = 330.8
Hz, 2CF3), 119.4 (q, JCF = 324.4 Hz, CF3), 116.7 (CAr-q),
88.0 (CTf2), 35.5 (CH2); 19F NMR (282 MHz, CDCl3, 25
oC): = –70.44 (s, 6F, 2CF3), –78.50 (s, 3F, CF3); IR
(CHCl3): = 1385, 1104 (O=S=O), 1214 (C–F) cm–1;
o
NMR (75 MHz, CDCl3, 25 C): = 162.1 (CAr-q-OCH3),
145.6 (d, JCP = 9.9 Hz, C=C-P), 136.6 (d, JCP = 188.7 Hz,
C=C-P), 131.1 (2CHAr), 121.5 (CAr-q), 119.8 (q, JCF = 331.6
Hz, 2CF3), 114.0 (2CHAr), 86.3 (d, JCP = 35.8 Hz, CTf2),
72.5 (d, JCP = 5.6 Hz, 2CH), 55.3 (OCH3), 36.0 (d, JCP
=
=
7.9 Hz, CH2), 24.0 (d, JCP = 4.1 Hz, 2CH3), 23.7 (d, JCP
o
5.0 Hz, 2CH3); 19F NMR (282 MHz, CDCl3, 25 C): = –
7
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