10.1002/ejoc.202000346
European Journal of Organic Chemistry
FULL PAPER
Potassium
(trans-2,2-difluoro-3-phenylcyclopropyl)trifluoroborate
Potassium
(2,2-difluoro-7,10-dioxadispiro[2.2.46.23]dodecan-1-yl)-
(8a). Yield 12.4 g (67%) from 15.0 g of 7a. White solid, mp 176–178 °C.
1H NMR (400 MHz, DMSO-d6) δ 7.26 (t, J = 7.4 Hz, 2H), 7.19 – 7.08 (m,
3H), 2.35 (t, J = 10.2 Hz, 1H), 0.88 – 0.66 (m, 1H) ppm. 13C NMR (126
MHz, DMSO-d6) δ 137.4, 128.0, 127.3, 125.7, 118.0 (dd, J = 291.1,
282.2 Hz), 29.1 (t, J = 10.8 Hz), 23.0 (br s) ppm. 19F NMR (376 MHz,
DMSO-d6) δ –126.9 (d, J = 140.3 Hz, 1F), –133.3 (d, J = 140.3 Hz, 1F), –
138.0 – –139.8 (m, 3F) ppm. MS(APCI) m/z = 221 [M–K]–. Anal. Calcd.
for C9H7BF5K: C 41.57; H 2.71. Found: C 41.90; H 2.96.
trifluoroborate (8i). Yield 1.01 g (85%) from 1.00 g of 7i. White solid, mp
189–191 °C. 1H NMR (400 MHz, DMSO-d6) δ 3.84 (s, 4H), 1.77 – 1.63
(m, 2H), 1.61 – 1.47 (m, 4H), 1.43 – 1.35 (m, 2H), –0.04 (d, J = 22.3 Hz,
1H) ppm. 13C NMR (151 MHz, DMSO-d6) δ 122.3 (t, J = 288.3 Hz), 108.4,
63.6, 63.5, 33.9, 33.6, 29.9 (d, J = 4.6 Hz), 27.4 (t, J = 9.4 Hz), 25.7 (br s),
22.6 ppm. 19F NMR (376 MHz, DMSO-d6) δ –130.2 (d, J = 140.5 Hz, 1F),
–132.4 – –133.6 (m, 3F), –140.8 (d, J = 140.5 Hz, 1F) ppm. 11B NMR
(160 MHz, DMSO-d6) δ 3.9 – 0.5 (m) ppm. MS(APCI) m/z = [M – K – 3F
+ H2O + HCO2H]–. Anal. Calcd. for C10H13BF5KO2: C 38.73; H 4.23.
Found: C 38.42; H 3.86.
Potassium (2,2-difluorocyclopropyl)trifluoroborate (8b). Yield 16.5 g
(60%) from 20.0 g of 7b. White solid, mp 193–195 °C. 1H NMR (400 MHz,
DMSO-d6) δ 0.89 (t, J = 11.1 Hz, 1H), 0.79 (s, 1H), 0.29 (s, 1H) ppm. 13
C
Potassium
(5-(tert-butoxycarbonyl)-2,2-difluoro-5-azaspiro[2.3]-
NMR (126 MHz, DMSO-d6) δ 119.1 (t, J = 277.4 Hz), 15.6 (br s), 12.2
ppm. 19F NMR (376 MHz, DMSO-d6) δ –121.6 (d, J = 142.2 Hz, 1F), –
135.1 (d, J = 142.2 Hz, 1F), –138.9 (q, J = 47.8 Hz, 3F) ppm. MS(APCI)
m/z = 145 [M–K]–. Anal. Calcd. for C3H3BF5K: C 19.59; H 1.64. Found: C
19.20; H 1.93.
hexan-1-yl)trifluoroborate (8j). Yield 0.886 g (75%) from 1.00 g of 7j.
Beige solid, mp 180–182 °C. The compound was obtained as ca. 1:1
mixture of rotamers. 1H NMR (400 MHz, DMSO-d6) δ 4.01 – 3.79 (m, 2H),
3.79 – 3.62 (m, 2H), 1.38 (s, 9H), 0.49 – 0.28 (m, 1H) ppm. 13C NMR
(126 MHz, DMSO-d6) δ 155.5, 116.5 (dd, J = 288.5, 281.7 Hz), 78.6, 53.5
and 52.5, 52.4 and 51.3, 28.0, 23.2 (t, J = 10.9 Hz), 21.2 (br s) ppm. 19F
NMR (376 MHz, DMSO-d6) δ –129.2 (d, J = 145.7 Hz, 1F), –134.7 – –
136.1 (m, 3F), –142.8 (d, J = 145.7 Hz, 1F) ppm. MS(APCI) m/z = 286
[M–K]–. Anal. Calcd. for C10H14BF5KNO2: C 36.94; H 4.34; N 4.31. Found:
C 37.28; H 4.01; N 4.42.
Potassium (2,2-difluoro-3,3-dimethylcyclopropyl)trifluoroborate (8c).
Yield 4.25 g (65%) from 5.00 g of 7c. White solid, mp >185 °C (dec). 1H
NMR (400 MHz, DMSO-d6) δ 1.05 (s, 6H), –0.00 – –0.18 (m, 1H) ppm.
13C NMR (151 MHz, DMSO-d6) δ 122.4 (t, J = 289.2 Hz), 26.1 (br s), 22.5
(d, J = 6.0 Hz), 21.4 (t, J = 9.4 Hz), 15.8 (d, J = 6.0 Hz) ppm. 19F NMR
(376 MHz, DMSO-d6) δ –129.3 (d, J = 137.2 Hz, 1F), –132.8 (q, J = 48.8
Hz, 3F), –140.6 (d, J = 137.2 Hz, 1F) ppm. MS(APCI) = 171 [M – K – F +
OH]–. Anal. Calcd. for C5H7BF5K: C 28.33; H 3.33. Found: C 28.53; H
3.68.
Potassium (2,2-difluoro-5-(methoxycarbonyl)spiro[2.3]hexan-1-yl)tri-
fluoroborate (8k). Yield 2.13 g (70%) from 2.50 g of 7k. White solid, mp
100–102 °C. The compound was obtained as ca. 40:60 mixture of
diastereomers. 1H NMR (400 MHz, D2O) δ 3.74 (s, 1.8H), 3.72 (s, 1.2H),
3.35 – 3.18 (m, 1H), 2.59 – 2.46 (m, 1H), 2.44 – 2.28 (m, 3H), 0.53 –
0.39 (m, 1H) ppm. 1H NMR (400 MHz, DMSO-d6) δ 3.61 (s, 1.8H), 3.60
(s, 1.2H), 3.15 – 3.05 (m, 1H), 2.45 – 2.10 (m, 4H), 0.26 – –0.01 (m, 1H)
ppm. 13C NMR (126 MHz, D2O) δ 179.0 and 178.3, 118.4 (t, J = 285.7
Hz) and 117.7 (t, J = 284.8 Hz), 52.4, 33.4 and 33.0, 28.7 and 28.5, 27.0
and 26.4, 25.8, 21.2 (br s) ppm. 19F NMR (376 MHz, DMSO-d6) δ –128.7
(d, J = 141.8 Hz, 1F), –134.1 – –134.4 (m, 1.2F) and –134.4 – –134.8 (m,
1.8F), –141.7 (d, J = 141.8 Hz, 0.4F) and –142.0 (d, J = 141.8 Hz, 0.6F)
Potassium (2,2-difluoro-1-methylcyclopropyl)trifluoroborate (8d).
Yield 8.29 g (80%) from 7.75 g of 7d. White solid, mp 178–180 °C. 1H
NMR (400 MHz, DMSO-d6) δ 1.03 – 0.95 (m, 1H), 0.90 (s, 3H), 0.38 (dd,
J = 13.4, 5.1 Hz, 1H) ppm. 13C NMR (126 MHz, DMSO-d6) δ 120.8 (dd, J
= 288.4, 278.0 Hz), 19.0, 18.4 (br s), 15.9 – 15.6 (m) ppm. 19F NMR (376
MHz, DMSO-d6) δ –129.4 (d, J = 142.5 Hz, 1F), –135.3 (d, J = 142.5 Hz,
1F), –144.1 (q, J = 49.5 Hz, 3F) ppm. MS(APCI) m/z = 159 [M–K]–. Anal.
Calcd. for C4H5BF5K: C 24.27; H 2.55. Found: C 24.65; H 2.59.
ppm. MS(APCI) m/z
=
421 [C16H19B2F4O7]–. Anal. Calcd. for
C8H9BF5KO2: C 34.07; H 3.22. Found: C 33.95; H 3.41.
Potassium
(6-(tert-butoxycarbonyl)-2,2-difluoro-6-azaspiro[2.5]-
Potassium (6,6-difluorobicyclo[3.1.0]hexan-1-yl)trifluoroborate (8m).
Yield 4.18 g (65%) from 5.00 g of 7m. White solid, mp 126–128 °C. 1H
NMR (400 MHz, DMSO-d6) δ 1.92 – 1.69 (m, 3H), 1.66 – 1.49 (m, 2H),
1.46 – 1.25 (m, 2H) ppm. 13C NMR (126 MHz, DMSO-d6) δ 122.6 (dd, J =
295.5, 282.2 Hz), 31.4 (br s), 29.3 (t, J = 10.3 Hz), 29.2, 26.6, 25.2 (d, J =
6.5 Hz) ppm. 19F NMR (376 MHz, DMSO-d6) δ –123.2 (d, J = 146.8 Hz,
octan-1-yl)trifluoroborate (8g). Yield 2.10 g (90%) from 2.00 g of 7g.
White solid, mp 178–180 °C. 1H NMR (400 MHz, DMSO-d6) δ 3.40 – 3.13
(m, 4H), 1.67 – 1.56 (m, 1H), 1.54 – 1.41 (m, 2H), 1.39 (s, 9H), 1.31 –
1.24 (m, 1H), 0.09 – 0.00 (m, 1H) ppm. 13C NMR (151 MHz, DMSO-d6) δ
154.0, 121.6 (t, J = 288.1 Hz), 78.4, 43.8, 42.9, 31.9, 28.1, 26.8 (t, J = 9.5
Hz), 25.8 (br s), 25.4 ppm. 19F NMR (376 MHz, DMSO-d6) δ –130.0 (d, J
= 140.5 Hz, 1F), –132.3 – –133.0 (m, 3F), –140.5 (d, J = 140.5 Hz, 1F)
ppm. MS(APCI) m/z = 218 [M – K – OC(CH3)3 – 3F + 2OH]+, 236 [M – K
– CH2C(CH3)2 – 3F + 2OH + H]+. Anal. Calcd. for C12H18BF5KNO2: C
40.81; H 5.14; N 3.97. Found: C 40.64; H 5.18; N 4.17.
1F), –139.6 – –140.3 (m, 4F) ppm. MS(APCI) m/z = 118 [M – K – BF3
+
H]+. Anal. Calcd. for C6H7BF5K: C 32.17; H 3.15. Found: C 32.35; H 2.91.
Potassium (3-(tert-butoxycarbonyl)-7,7-difluoro-3-azabicyclo[4.1.0]-
heptan-6-yl)trifluoroborate (8n). Yield 54.2 g (84%) from 55.0 g of 7n.
Beige solid, mp 194–196 °C. The compound was obtained as ca. 7:3
mixture of rotamers. 1H NMR (400 MHz, DMSO-d6_d6) δ 3.62 (d, J = 14.4
Hz, 0.3H), 3.46 – 3.34 (m, 1H), 3.31 – 3.16 (m, 1H), 2.79 – 2.62 (m,
0.7H), 1.72 (d, J = 13.1 Hz, 1H), 1.55 – 1.16 (m, 3H), 1.36 (s, 9H) ppm.
13C NMR (126 MHz, DMSO-d6) δ 153.9, 119.4 (dd, J = 291.9, 279.6 Hz),
78.0, 36.5, 35.2, 28.1, 19.2 (d, J = 28.2 Hz), 17.5 (d, J = 45.5 Hz) ppm
(the signal of C near the boron atom was not registered due to its low
intensity). 19F NMR (376 MHz, DMSO-d6) δ –128.9 (d, J = 144.6 Hz,
0.5F) and –129.2 (d, J = 144.6 Hz, 0.5F), –143.1 (d, J = 144.6 Hz, 0.5F)
and –143.3 (d, J = 144.6 Hz, 0.5F), –144.1 – –145.1 (m, 3F) ppm.
MS(APCI) m/z = 300 [M–K]–. Anal. Calcd. for C11H16BF5KNO2: C 38.96;
H 4.76; N 4.13. Found: C 38.56; H 4.82; N 4.04.
Potassium
(2,2-difluoro-6-oxaspiro[2.5]octan-1-yl)trifluoroborate
(8h). Yield 1.23 g (82%) from 1.20 g of 7h. Beige solid, mp 166–169 °C.
1H NMR (400 MHz, DMSO-d6) δ 3.67 (ddd, J = 10.8, 6.9, 3.6 Hz, 1H),
3.58 (ddd, J = 10.8, 6.9, 3.6 Hz, 1H), 3.49 (ddd, J = 10.8, 6.9, 3.6 Hz, 1H),
3.42 (ddd, J = 10.8, 6.9, 3.6 Hz, 1H), 1.72 – 1.61 (m, 1H), 1.61 – 1.53 (m,
1H), 1.53 – 1.42 (m, 1H), 1.42 – 1.28 (m, 1H), 0.10 – –0.03 (m, 1H) ppm.
13C NMR (126 MHz, DMSO-d6) δ 121.6 (t, J = 288.7 Hz), 66.9, 66.7, 32.8,
26.6, 26.1 (t, J = 9.8 Hz), 25.6 (br s) ppm. 19F NMR (376 MHz, DMSO-d6)
δ –130.2 (d, J = 140.7 Hz, 1F), –132.1 – –133.1 (m, 3F), –140.8 (d, J =
140.7 Hz, 1F) ppm. MS(APCI) m/z = 365 [C14H19B2F4O5]–. Anal. Calcd.
for C7H9BF5KO: C 33.09; H 3.57. Found: C 33.42; H 3.65.
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