10.1002/ejoc.201801703
European Journal of Organic Chemistry
FULL PAPER
8.0 Hz, 1H, CH-1), 2.22 (ddt, J = 10.7, 7.4, 3.6 Hz, 1H, CH-5),
1.02 (s, 9H, 3 x CH3). 13C NMR (101 MHz, CDCl3): δ 159.4 (C=O),
144.5 (Cq Q), 138.1 (Cq Ph), 137.3 (Cq Ph), 134.6, 128.7, 128.6,
128.5, 128.1, 128.0, 127.9, 127.8, 127.4, 127.0, 126.6 (10 x CH
Ar, 4 x CH Q), 121.2 (Cq Q), 84.6 (tBu-CH-OH). 80.0 (C-3), 75.4
(CH2Ph), 74.9 (C-2), 72.6 (CH2Ph), 66.3 (C-4), 61.3 (C-7), 51.5
(C-1), 49.2 (C-6), 44.2 (C-5), 38.5 (C(CH3)3), 25.9 (3 x CH3). ESI-
MS (m/z): 586.3 [M+H+]
(C-4), 72.9 (C-3), 69.9 (C-7), 68.2 (C-2), 47.7 (C-6), 46.5 (C-1),
34.3 (C-5). HRMS: calcd. for [C23H21F3N3O5]+ 476.14333; found
476.14255.
β-D-conduritol
CF3-Q-aziridine
(6b):
Obtained
from
cyclohexene 6a (300 mg, 0.72 mmol) as an orange oil in 66%
yield (305 mg, 0.47 mmol). 1H NMR (400 MHz, CDCl3): δ 8.17 (dd,
J = 7.8, 1.2 Hz, 1H, CH Q), 7.92 – 7.79 (m, 2H, 2 x CH Q), 7.61
(ddd, J = 8.3, 5.2, 3.2 Hz, 1H, CH Q), 7.45 – 7.28 (m, 12H, 12 x
CH Ar), 7.28 – 7.14 (m, 2H, 2 x CH Ar), 7.07 – 6.96 (m, 1H, CH
Ar), 4.97 (d, J = 11.3 Hz, 1H, CHHPh), 4.90 – 4.81 (m, 2H, 2 x
CHHPh), 4.79 (d, J = 11.2 Hz, 1H, CHHPh), 4.71 (dd, J = 11.3,
6.6 Hz, 2H, 2 x CHHPh), 4.41 (dd, J = 7.2, 3.7 Hz, 1H, CH-6), 3.99
(td, J = 7.0, 6.1, 2.9 Hz, 2H, CH-3, CH-5), 3.93 (d, J = 7.2 Hz, 1H,
α-D-gluco-cyclitol CF3-Q-aziridine (2b): Obtained from
cyclohexene 2a (40 mg, 0.161 mmol) as an orange oil in 55%
yield (43 mg, 0.089 mmol). 1H NMR (500 MHz, CDCl3): δ 8.21 (d,
J = 7.7 Hz, 1H, CH Q), 7.90 – 7.80 (m, 2H, 2 x CH Q), 7.62 (ddd,
J = 8.2, 6.2, 2.1 Hz, 1H, CH Q), 7.50 (dd, J = 7.6, 2.1 Hz, 2H, 2 x
CH Ar), 7.42 – 7.33 (m, 3H, 3 x CH Ar), 5.54 (s, 1H, CHPh), 4.47
(dd, J = 10.7, 4.7 Hz, 1H, CH-7a), 4.10 (d, J = 7.2 Hz, 1H, CH-2),
4.06 (dd, J = 7.2, 4.5 Hz, 1H, CH-1), 3.84 (dd, J = 11.8, 10.7 Hz,
1H, CH-7b), 3.73 (dd, J = 10.3, 7.8 Hz, 1H, CH-3), 3.66 (br s, 1H,
OH), 3.45 (d, J = 7.2 Hz, 1H, CH-6), 3.30 (t, J = 10.5 Hz, 1H, CH-
4), 2.85 (br s, 1H, OH), 2.38 (dddd, J = 12.0, 10.5, 4.7, 1.8 Hz, 1H,
CH-5). 13C NMR (126 MHz, CDCl3): δ 160.8 (C=O), 143.9 (Cq Q),
142.4 (q, J = 36.6 Hz, CCF3), 137.4 (Cq Ph), 135.4, 129.8, 129.4,
128.8, 128.5, 126.8, 126.3 (10 x CH Ar, 4 x CH Q), 122.7 (Cq Q),
128.2 (q, JCF = 278.2 Hz, CF3), 102.3 (CHPh), 80.0 (C-4), 73.6 (C-
3), 72.2 (C-2), 68.8 (C-7), 43.8 (C-1), 41.4 (C-6), 37.4 (C-5).
HRMS: calcd. for [C23H21F3N3O5]+ 476.1433; found 476.1423;
calcd. for [C23H20F3N3NaO5]+ 498.1252; found 498.1244.
CH-1), 3.55 – 3.42 (m, 2H, CH-2, CH-4), 2.59 (br s, 1H, OH). 13
C
NMR (101 MHz, CDCl3): δ 161.0 (C=O), 143.5 (q, J = 34.9 Hz,
CCF3), 142.9, 138.6, 138.5 (3 x Cq Ph), 137.6, 135.2, 129.5, 128.7,
128.6, 128.5, 128.3, 128.1, 128.0, 127.8, 126.6 (15 x CH Ar, 4 x
CH Q), 123.2 (Cq Q), 117.3 (q, JCF = 277.6 Hz, CF3), 83.6, 80.2,
79.8 (3 x CH), 75.8, 75.7, 73.9 (3 x CH2 Ph), 71.4 (CH), 42.6 (CH-
6), 40.6 (CH-1). HRMS: calcd. for [C36H33F3N3O5]+: 644.2372;
found 644.2368; calcd. for [C36H32F3N3NaO5]+: 666.2192; found
666.2189.
β-D-xylo-cyclitol CF3-Q-aziridine (8b): Obtained from
cyclohexene 8a (300 mg, 0.97 mmol) as an orange oil in 45%
yield (233 mg, 0.43 mmol) and 37% starting material recovered
(112 mg, 0.36 mmol). 1H NMR (400 MHz, CDCl3): δ 8.19 (dt, J =
8.0, 1.1 Hz, 1H, CH Q), 7.88 – 7.81 (m, 2H, 2 x CH Q), 7.65 –
7.58 (m, 1H, CH Q), 7.43 – 7.29 (m, 7H, 7 x CH Ar), 7.27 – 7.19
(m, 2H, 2 x CH Ar), 7.07 – 7.00 (m, 1H, CH Ar), 4.99 (d, J = 11.2
Hz, 1H, CHHPh), 4.80 (d, J = 2.1 Hz, 2H, 2 x CHHPh), 4.67 (d, J
= 11.2 Hz, 1H, CHHPh), 4.03 – 3.95 (m, 2H, CH-2, CH-6), 3.77
(d, J = 7.2 Hz, 1H, CH-1), 3.65 (td, J = 10.5, 5.4 Hz, 1H, CH-4),
3.30 (dd, J = 10.0, 8.2 Hz, 1H, CH-3), 2.65 – 2.54 (m, 2H, CH-5a,
OH), 1.74 (ddd, J = 14.2, 10.9, 3.5 Hz, 1H, CH-5b). 13C NMR (101
MHz, CDCl3): δ 160.8 (C=O), 144.1 (Cq Q), 143.5 (q, J = 36.4 Hz,
CCF3), 138.4, 137.7 (2 x Cq Ph), 135.0, 129.4, 128.7, 128.7, 128.5,
128.1, 128.0, 126.6 (10 x CH Ar, 4 x CH Q), 123.2 (Cq Q), 118.3
(q, JCF = 275.4 Hz, CF3), 84.63= (C-3), 80.4 (C-2), 75.1 (CH2Ph),
73.0 (CH2Ph), 65.7 (C-4), 41.4, 41.1 (C-1, C-6), 30.6 (C-5).
HRMS: calcd. for [C29H27F3N3O4]+: 538.1954; found 538.1960;
calcd. for [C29H26F3N3NaO4]+: 560.1773; found 560.1779.
β-D-galacto-cyclitol CF3-Q-aziridine (4b): Obtained from
cyclohexene 4a (470 mg, 2.05 mmol) as an orange oil in 49%
yield (225 mg, 1.00 mmol) and 15% starting material recovered.
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1
[α]D = +69.4 (c = 0.5, CHCl3). H NMR (400 MHz, CDCl3): δ =
8.22 – 8.16 (d, J = 7.6 Hz, 1H, CH Q), 7.88 – 7.80 (m, 2H, 2 x CH
Q), 7.62 (ddd, J = 8.2, 6.3, 2.1 Hz, 1H, CH Q), 7.42 – 7.21 (m, 9H,
CH Ar), 7.15 – 7.07 (m, 1H, CH Ar), 4.93 (d, J = 10.9 Hz, 1H,
CHHPh), 4.78 (d, J = 11.6 Hz, 1H, CHHPh), 4.76 (d, J = 10.8 Hz,
1H, CHHPh), 4.67 (d, J = 11.8 Hz, 1H, CHHPh), 4.29 (d, J = 8.6
Hz, 1H, CH-2), 4.23 (dd, J = 11.6, 8.2 Hz, 1H, CH-7a), 4.10 (br s,
1H, CH-4), 3.99 (dd, J = 11.6, 5.8 Hz, 1H, CH-7b), 3.94 (dd, J =
7.9, 3.0 Hz, 1H, CH-6), 3.53 (br s, 1H, OH), 3.45 – 3.36 (m, 2H,
CH-1, CH-3), 2.65 (d, J = 8.0 Hz, 1H, OH), 2.19 (br s, 1H, CH-5).
13C NMR (101 MHz, CDCl3): δ 160.1 (C=O), 143.5 (Cq Q), 141.4
(q, J = 35.5 Hz, CCF3), 138.0 (Cq Ph), 137.9 (Cq Ph), 135.3, 129.8,
128.6, 128.5, 128.4, 128.3, 128.1, 127.9, 126.9 (10 x CH Ar, 4 x
CH Q), 122.8 (Cq Q), 118.1 (q, JCF = 275.0 Hz, CF3), 82.9 (C-3),
77.5 (C-2), 74.8 (CH2Ph), 71.9 (CH2Ph), 67.3 (C-4), 61.9 (C-7),
49.1 (C-1), 44.0 (C-6), 41.0 (C-5). HRMS: calcd. for
[C30H29F3N3O5]+: 568.2059; found 568.2061; calcd. for
[C30H28F3N3NaO5]+: 590.1879; found 590.1882.
α-L-ido-cyclitol CF3-Q-aziridine (10b): Obtained from
cyclohexene 10a (2.9 g, 5.57 mmol) as an orange oil in 43% yield
20
1
1.79 g, 2.40 mmol). [α]D = + 1.2 (c = 1, CHCl3). H NMR (400
MHz, CDCl3): δ = 8.25 (d, J = 7.9 Hz, 1H, CH Ar), 7.87 (d, J = 3.6
Hz, 2H, 2 x CH Ar), 7.67 – 7.63 (m, 1H, CH Ar), 7.49 – 7.25 (m,
19H, 19 x CH Ar), 7.14 (t, J = 7.4 Hz, 1H, CH Ar), 4.87 (d, J = 11.1
Hz, 1H, CHHPh), 4.84 (s, 2H, 2 x CHHPh), 4.78 (d, J = 11.1 Hz,
1H, CHHPh), 4.74 (d, J = 11.6 Hz, 1H, CHHPh), 4.67 – 4.57 (m,
3H, 3 x CHHPh), 4.22 (d, J = 7.3 Hz, 1H, CH-6), 4.06 (d, J = 7.0
Hz, 1H, CH-3), 4.00 (d, J = 7.4 Hz, 1H, CH-1), 3.98 – 3.96 (m, 1H,
CHHPh), 3.78 – 3.69 (m, 3H, CH-2, CH-4, CHHPh), 2.99 – 2.93
(m, 1H, CH-5). 13C NMR (101 MHz, CDCl3): δ = 160.7 (C=O),
144.0 (Cq Ar Q), 143.4 (q, J = 34.1 Hz, CCF3), 139.0, 138.6, 138.3,
138.1 (Cq Ar), 134.9, 129.3, 128.6, 128.5, 128.4, 128.0, 127.9,
127.8, 127.7, 127.6, 126.6 (20 x CH Ar, 4 x CH Q), 123.2 (Cq Q),
118.2 (q, J = 276.68 Hz, CF3), 80.7 (C-4/2), 80.2 (C-3), 76.0 (C-
4/2), 75.2, 73.4, 73.2, 73.1 (4 x CH2Ph), 67.6 (C-7), 44.2 (C-6),
41.2 (C-1), 38.0 (C-5). HRMS: calcd. for [C44H40F3N3O5]+
α-D-galacto-cyclitol CF3-Q-aziridine (5b): Obtained from
cyclohexene 5a (550 mg, 2.2 mmol) as an orange oil in 61% yield
(643 mg, 1.35 mmol). H NMR (400 MHz, CDCl3): δ 8.18 – 8.09
1
(m, 1H, CH Q), 7.80 – 7.70 (m, 2H, 2 x CH Q), 7.55 (ddd, J = 8.3,
6.4, 2.0 Hz, 1H, CH Q), 7.40 (dq, J = 5.2, 2.9 Hz, 2H, 2 x CH Ar),
7.34 – 7.23 (m, 3H, 3 x CH Ar), 5.39 (s, 1H, CHPh), 4.37 – 4.23
(m, 2H, CH-2, CH-7a), 4.14 – 4.03 (m, 2H, CH-4, CH-7b), 3.90
(dd, J = 7.7, 4.1 Hz, 1H, CH-1), 3.68 – 3.57 (m, 2H, CH-3, CH-4),
2.08 (s, 1H, CH-5). 13C NMR (101 MHz, CDCl3): δ 160.3 (C=O),
143.6 (Cq Q), 141.8 (q, J = 36.0 Hz, CCF3), 137.9 (Cq Ph), 135.0,
129.5, 129.0, 128.4, 128.1, 126.6, 126.2 (5 x CH Ar, 5 x CH Q),
122.4 (Cq Q), 114.0 (q, JCF = 277.8 Hz, CF3), 101.1 (CHPh), 77.5
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