Chalcogenophosphinates with Glucose Moieties via Todd–Atherton-Like Coupling
5
C3, DAG, 2JPC 6.5 Hz), 80.6 (d, C4, DAG, 3JPC 6.9 Hz),
84.5 (C2, DAG), 105.0 (C1, DAG), 109.6 (C7, DAG),
112.4 (C8, DAG), 126.5, 126.6 (Сp), 128.1, 128.4
by direct methods, and non-hydrogen atoms were
refined anisotropically using SHELX [15]. The co-
ordinates of the hydrogen atoms were calculated
from geometrical positions. CCDC 1009371 contains
the supplementary crystallographic data for this pa-
per. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via
3
(Со), 128.7, 128.8 (Сm), 140.3, 140.7 (2 d, Ci, JPС
3
14.7 Hz, JPС 16.4 Hz, respectively). 31P NMR
(CDCl3) δ: 106.6. Anal. Calcd for С28Н37O6PS: С,
63.14; Н, 7.00; Р, 5.82; S, 6.02. Found: С, 63.11; Н,
6.85; Р, 5.76; S, 5.98.
Hydrolysis of Diacetone-D-glucose Bis(2-phenyl-
ethyl)selenophosphinate 2c
Diacetone-D-glucose
phosphinate (2c). White powder, yield: 0.458
g (79%), mp 85–86°С (hexane), [α]
Bis(2-phenylethyl)seleno-
25
546
= –35.4°,
A
mixture of selenophosphinate 2c (0.062 g,
25
[α]
= –34.13° (1,4-dioxane). IR (KBr) (cm−1):
578
0.108 mmol) and 77% acetic acid (0.573 g) was
heated at 70°С for 5, and then evaporated in air
at room temperature. The residue was recrystal-
lized from the hexane–EtOH mixture to give 0.054
g (92%) of monoacetone-D-glycose selenophosphi-
nate 4, white solid, mp 139–140°C (hexane–EtOH).
IR (KBr) (cm−1): 3502, 3376, 3107, 3085, 3063, 3026,
2983, 2935, 1739, 1603, 1584, 1497, 1454, 1423, 1384,
1376, 1350, 1317, 1291, 1259, 1218, 1163, 1135, 1085,
1067, 1036, 1017, 980, 964, 947, 932, 915, 885, 858,
842, 809, 773, 758, 747, 716, 699, 662, 621, 580, 574,
555, 532, 497, 481, 457. 1H NMR (CDCl3) δ: 1.29,
1.49 (2 s, 6H, Me, MAG), 2.32–2.50 (m, 4H, CH2P),
2.86–3.05 (m, 4H, PhCH2), 3.68–3.72, 3.76–3.86 (m,
3H, H5,6, MAG), 4.10 (dd, 1H, H4, MAG, 4JPH 9.1 Hz,
3108, 3087, 3064, 3031, 2983, 2964, 2933, 2894,
1602, 1585, 1497, 1451, 1437, 1382, 1371, 1352,
1343, 1313, 1291, 1254, 1217, 1165, 1154, 1120,
1079, 1063, 1039, 1023, 992, 958, 946, 910, 895, 883,
858, 839, 784, 761, 752, 699, 635, 582, 572, 532, 507,
1
496, 469, 458, 384. H NMR (CDCl3) δ: 1.14, 1.28,
1.33, 1.47 (4 s, 12H, Me, DAG), 2.27–2.56 (m, 4H,
CH2P), 2.86–3.07 (m, 4H, PhCH2), 3.95–3.98 (m,
1H, H4, DAG), 4.06–4.12 (m, 3H, H5,6, DAG), 4.65
3
(d, 1H, H2, DAG, JHH 3.6 Hz), 4.99 (dd, 1H, H3,
3
3
DAG, JPH 13.3 Hz, JHH 2.3 Hz), 5.74 (d, 1H, H1,
3
DAG, JHH 3.6 Hz), 7.14–7.21, 7.23-7.29 (m, 10H,
Ph). 13С NMR (CDCl3) δ: 20.9, 22.1, 24.7, 25.2 (4 s,
2
Me, DAG), 22.6 (d, PhCH2, JPC 5.4 Hz), 33.0, 33.4
(2 d, CH2P, 1JPC 60.4 Hz, 1JPC 52.5 Hz, respectively),
3
3JHH 2.4 Hz), 4.42 (d, 1H, H2, MAG, JHH 3.7 Hz),
63.4 (C6, DAG), 67.8 (C5, DAG), 74.6 (d, C3, DAG,
5.06 (dd, 1H, H3, MAG, JPH 14.8 Hz, JHH 2.4 Hz),
5.85 (d, 1H, H1, MAG, 3JHH 3.7 Hz), 7.15–7.18, 7.21–
7.24, 7.26–7.32 (m, 10H, Ph). 13С NMR (CDCl3) δ:
26.3, 26.6 (2 s, Me, MAG), 29.0, 29.6 (2 s, PhCH2),
3
3
2JPC 5.2 Hz), 76.2 (d, C4, JPC 6.7 Hz, DAG), 80.0
3
(C2, DAG), 100.7 (C1, DAG), 105.3 (C7, DAG),
108.2 (C8, DAG), 122.2, 122.3 (Сp), 123.8, 124.1
3
(Со), 124.3, 124.4 (Сm), 135.8, 136.1 (2 d, Ci, JPС
1
1
37.0, 37.6 (2 d, CH2P, JPC 57.8 Hz, JPC 53.0 Hz,
3
14.8 Hz, JPС 16.5 Hz, respectively). 31P NMR
respectively), 64.1 (C6, MAG), 67.2 (C5, MAG), 78.1
1
(CDCl3) δ: 108.2 (s) (+d satellite, JPSe 786.8 Hz).
(d, C3, MAG, JPC 6.0 Hz), 80.1 (d, С4, MAG, JPC
4.7 Hz), 83.9 (C2, MAG), 105.1 (C1, MAG), 112.6 (C7,
MAG), 126.7, 126.8 (2 s, Cp), 128.2, 128.3 (2 s, Co),
128.7, 128.8 (2 s, Cm), 139.6, 139.7 (2 d, Ci, 3JPС 14.2
2
3
77Se NMR (CDCl3) δ: –290.9 (d, JPSe 786.8 Hz).
1
Anal. Calcd for С28Н37O6PSe: С, 58.03; Н, 6.44; Р,
5.34; Se, 13.62. Found: С, 58.11; Н, 6.52; Р, 5.29; Se,
13.59.
Hz, JPС 15.9 Hz, respectively). 31P NMR (CDCl3) δ:
3
1
109.4 (s) (+d satellite, JPSe 776.3 Hz). Anal. Calcd
for С25Н33O6PSe: С, 55.66; Н, 6.17; Р, 5.74; Se, 14.64.
Found: С, 55.57; Н, 6.13; Р, 5.59; Se, 14.59.
Crystal Structure Analysis of 2c
Crystal data: C28H37O6PSe (Mr = 579.50), mon-
The EPR spectra were recorded with an
X-band Bruker ELEXSYS E 580 spectrometer
(X-wave range 9.7 GHz). Precision of the mea-
surement of the g factor was 0.0002. CW EPR-
spectra were recorded at the following conditions:
amplitude modulation 0.3 G, receiver gain 60 dB,
time constant 0.02 s, conversion time 0.06 s, mi-
crowave power 0.6325 mW at room temperature.
PBN was added immediately after mixing of reagents
(10−2 mol/L). All experiments were carried out un-
der argon atmosphere. EPR data of adducts E, X =
O: g = 2.0061, aN = 14.3 G, aH = 4.8 G, aP = 11.0 G;
˚
oclinic, space group P 21, a = 14.1692(10) A,
˚
˚
b = 7.2867(5) A, c = 14.4753(10) A, α = 90, β
3
˚
= 109.656(2), γ = 90, V = 1407.44(17) A , Z =
2, T = 100.0 K, μ(MoKα) = 1.43 mm−1, Dcalc
=
1.367 g/cm3, 6790 reflections measured (5.72 ࣘ
2θ ࣘ
50.1), 5456 unique (Rint = 0.1132, Rsigma = 0.0829),
which were used in all calculations. The final R1
was 0.0403 (I > 2σ(I)), and wR2 was 0.0668 (all
data). Data were collected on a Bruker D8 Venture
˚
diffractometer with Mo Kα (λ = 0.71073 A) using the
φ and ω scans. The structure was solved and refined
Heteroatom Chemistry DOI 10.1002/hc