Addition of secondary phosphines to a vinyl ether of diacetone-d-glucose: A new approach to optically active phosphines and their derivatives

Article abstract of DOI:10.1016/j.tetlet.2004.09.172

Secondary phosphines react readily with a vinyl ether of diacetone-d-glucose under radical initiation conditions to give, in high yield, anti-Markovnikov adducts, diorganyl{2-[3-O-(1,2:5,6-di-O-isopropylidene)-d- glucofuranosyloxy]ethyl}phosphines, which oxidize almost quantitatively upon reacting with air oxygen or elemental sulfur to form the corresponding optically active phosphine oxides or sulfides.

Full text of DOI:10.1016/j.tetlet.2004.09.172

Tetrahedron
Letters
Tetrahedron Letters 45 (2004) 9143–9145
Addition of secondary phosphines to a vinyl ether of
diacetone-D-glucose: a new approach to optically active
phosphines and their derivatives
Boris A. Trofimov,* Boris G. Sukhov, Svetlana F. Malysheva,
NatalÕya A. Belogorlova, Anatolii P. Tantsirev, Lidiya N. Parshina,
Ludmila A. Oparina, Sergey P. Tunik and Nina K. Gusarova
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 Favorsky Street, Irkutsk 664033, Russia
Received 12 July 2004; revised 15 September 2004; accepted 23 September 2004
Abstract—Secondary phosphines react readily with a vinyl ether of diacetone-D-glucose under radical initiation conditions to give,
in high yield, anti-Markovnikov adducts, diorganyl{2-[3-O-(1,2:5,6-di-O-isopropylidene)-D-glucofuranosyloxy]ethyl}phosphines,
which oxidize almost quantitatively upon reacting with air oxygen or elemental sulfur to form the corresponding optically active
phosphine oxides or sulfides.
Ó 2004 Elsevier Ltd. All rights reserved.
Optically active phosphines and their phosphoryl and
thiophosphoryl derivatives are widely applied in asym-
metric synthesis as efficient chiral ligands for transition
metal catalysts.1 Recently, interest has been shown in
chiral phosphine ligands with carbon-based chirality,
which are easier to prepare, whereas their transition
metal complexes are more efficient in asymmetric cata-
lysis.2 Therefore, the search for new convenient routes
to the synthesis of such prospective phosphorus-contain-
ing chiral ligands remains an important synthetic task.
One approach to this task involves the use of optically
active starting materials, which can be easily derived
from enantiomerically pure natural compounds.3 The
addition of secondary phosphines to alkenes4 (including
functional alkenes, such as alkyl vinyl ethers,5 alkyl
vinyl chalcogenides,6 vinyl pyrroles,7 vinyl pyridines,8
Herein we describe the synthesis of novel optically active
polyfunctional tertiary phosphines and their phosphoryl
and thiophosphoryl derivatives, based on the hydropho-
sphination of chiral vinyl ether 1 (readily prepared from
diacetone-D-glucose and acetylene under elevated9 or
atmospheric10 pressure as well as by transvinylation of
diacetone-D-glucose with an excess of isobutyl vinyl
ether11) with readily available secondary phosphines
2a,b.12 These phosphines add to the vinyl ether 1 regio-
specifically in the presence of azobisisobutyronitrile
(AIBN) at 65–70°C to form the corresponding optically
active tertiary diorganyl{2-[3-O-(1,2:5,6-di-O-isopropy-
lidene)-D-glucofuranosyloxy]ethyl}phosphines 3a,b in
high yield (Scheme 1, Table 1).13
Upon reacting with air, oxygen or elemental sulfur, the
phosphines 3a,b were quantitatively oxidized to the
etc.) represents
a
straightforward atom-economic
(ÔgreenÕ) approach to C–P bond formation.
O
O
O
O
6
6
5
7
7
5
O
O
AIBN
4
4
1
2
1
2
Keywords: Secondary phosphines; Vinyl ether of diacetone-D-glucose;
Addition; Radical initiation; Optically active tertiary phosphines; Ph-
osphine oxides and sulfides.
+
R2PH
O
8
O
8
3
3
9
65-70 ˚C
R2P
O
O
O
O
10
2a,b
3a,b
1
*
Corresponding author. Fax: +7 3952 419346; e-mail: mal@
irioch.irk.ru
Scheme 1.
0040-4039/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2004.09.172

9144
B. A. Trofimov et al. / Tetrahedron Letters 45 (2004) 9143–9145
2. (a) Petltkowska, W.; Gouygou, M.; Daran, J.-C.; Balav-
Table 1. Synthesis of phosphines 3a
oine, G.; Mikolajczyk, M. Tetrahedron Lett. 2001, 42, 12–
17; (b) Brunner, H. Top. Stereochem. 1988, 18, 129–247;
(c) Braunstein, P.; Naud, F. Angew. Chem., Int. Ed. 2001,
40, 680–699.
Entry
Reactants (mmol)
Time Product
yieldb (%)
(h)
1
2
1, 1.90 2a (R = n-Bu), 1.90 80
1, 2.86 2b (R = PhCH2CH2), 2.86 90
3a, 74
3b, 90
3. Komorov, I. V.; Spannenbeg, A.; Hoz, J.; Burner, A.
Chem. Commun. 2003, 2240–2241.
a All experiments were carried out under argon.
b Isolated yields.
4. (a) Casey, C. P.; Paulsen, E. L.; Beuttenmueller, E. W.;
Proft, B. R.; Matter, B. A.; Powell, D. R. J. Am. Chem.
Soc. 1999, 121, 63–70; (b) Brauer, D. J.; Kottsieper, K.
W.; Nickel, T.; Stelzer, O.; Sheldrick, W. S. Eur. J. Inorg.
Chem. 2001, 1251–1259; (c) Bunlaksananusorn, T.; Kno-
chel, P. Tetrahedron Lett. 2002, 43, 5817–5819.
5. (a) Dombek, B. D. J. Org. Chem. 1978, 43, 3408–3409; (b)
Malysheva, S. F.; Gusarova, N. K.; Belogorlova, N. A.;
Nikitin, M. V.; Gendin, D. V.; Trofimov, B. A. Zh.
Obshch. Khim. 1997, 67, 63–66.
O
O
O
O
O
air
S8
O
3a,b
O
O
toluene, 50 oC
hexane, r.t.
R2P
O
R2P
S
O
O
O
O
4a,b
5a,b
6. Trofimov, B. A.; Gusarova, N. K.; Malysheva, S. F.;
Ivanova, N. I.; Sukhov, B. G.; Belogorlova, N. A.;
Kuimov, V. A. Synthesis 2002, 2207–2210.
Scheme 2.
7. Trofimov, B. A.; Malysheva, S. F.; Sukhov, B. G.;
Belogorlova, N. A.; Schmidt, E. Yu.; Sobenina, L. N.;
Kuimov, V. A.; Gusarova, N. K. Tetrahedron Lett. 2003,
44, 2629–2632.
8. Gusarova, N. K.; Malysheva, S. F.; Belogorlova, N. A.;
Arbuzova, S. N.; Gendin, D. V.; Trofimov, B. A. Zh. Org.
Khim. 1997, 33, 1231–1234.
Table 2. Synthesis of phosphine oxides 4 and phosphine sulfides 5
Entry
Reactants
(mmol)
Temp- Time Solvent
erature (h)
Product
yielda
(%)
(mL)
(°C)
1
3a, 0.35 Air O2, 20–22
excess
15
Hexane, 2 4a, 98
9. MikhantÕev, B. I.; Lapenko, V. L. Zh. Obshch. Khim. 1957,
27, 2840–2841.
2
3
3a, 6.00 S8, 9.0
50
3
20
Toluene, 4 5a, 98
Hexane, 2 4b, 98
3b, 0.55 Air O2, 20–22
excess
3b, 0.97 S8, 1.39 50
10. Vinyl ether 1 was prepared by vinylation of diacetone-D-
glucose with acetylene in KOH/DMSO system under
atmospheric pressure (flow system, 105–115°C). Selected
analytical data for 1: bp 127–130°C (3mmHg), n2D0 1.4628,
4
3
Toluene, 5 5b, 85
a Isolated yields.
22
optical rotation ½aꢀD ꢁ26.7 (c 2.0, CCl4); lit.9: bp 115–
116°C (1.5mmHg), n2D0 1.468; lit.11: bp 68°C
optically active phosphine oxides 4a,b14 or phosphine
sulfides 5a,b,15 respectively (Scheme 2, Table 2).
20
(0.008mmHg), n2D0 1.4593, ½aꢀD ꢁ30.5 (c 1.0, CHCl3). IR
(film, cmꢁ1): 507, 531, 632, 694, 790 (shld), 837, 887, 936,
953 (d, CH@, CH2@), 1008, 1032 (shld), 1060, 1105 (shld),
1150, 1177, 1203 (m, COC, COCOC), 1245, 1283, 1315,
1323, 1351 (shld), 1366, 1380, 1441, 1477 (d, CH@, CH2,
CH), 1610, 1631, (m, C@C), 2887, 2927, 2980 (m, Me, CH2),
3060, 3110 (m, CH@, CH2@). 1H NMR (400MHz,
CDCl3): d 1.30 (s, 3H, Me), 1.33 (s, 3H, Me), 1.42 (s,
In summary, the atom-economic addition of secondary
phosphines to the optically active vinyl ether 1, which
is readily available from glucose, represents a convenient
approach to the synthesis of optically active sugar-based
tertiary phosphines and their derivatives. The polydent
phosphines, phosphine oxides, and phosphine sulfides
thus obtained, containing protected hydroxy functional-
ized tetrahydrofuran and dioxolane moieties, are prom-
ising chelating ligands for metal complex catalysts for
asymmetric synthesis.
3H, Me), 1.50 (s, 3H, Me), 4.01 (dd, 1H, 2J = 8.6Hz,
3
3J5,6 = 5.5Hz, H-6), 4.08 (dd, 1H, 2J = 8.6Hz, J5,6
=
6.1Hz, H-6), 4.14 (dd, 1H, Jcis = 6.7Hz, 2J = 2.2Hz,
3
3
3
@CHcis), 4.18 (dd, 1H, J4,5 = 7.7Hz, J3,4 = 3.0Hz, H-4),
4.30 (dt, 1H, J4,5 = 7.7Hz, J5.6 = 5.7Hz, H-5), 4.34 (d
3
3
3
1H, J3,4 = 3.0Hz, H-3), 4.38 (dd, 1H, Jtrans = 14.3Hz,
3
2J = 2.2Hz, =CHtrans), 4.58 (d, 1H, J1,2 = 3.7Hz, H-2),
3
3
3
5.87 (d, 1H, J1,2 = 3.7Hz, H-1), 6.38 (dd, 1H, Jtrans
=
3
Acknowledgements
14.3Hz, Jcis = 6.7Hz, @CHO). 13C NMR (100MHz,
CDCl3): d 25.17, 26.10, 26.61, 26.71 (4Me), 66.93 (C-6),
72.03 (C-5), 80.28 (C-3,4), 82.01 (C-2), 89.31 (@CH2),
105.02 (C-1), 108.98 and 111.76 (C-7,8), 149.94 (@CHO).
11. Black, W. A. P.; Dewar, E. T.; Rutherford, D. J. Chem.
Soc. 1963, 4433–4439.
Financial support from the Ministry of Industry, Sci-
ence and Technologies of the Russian Federation
(Grant No. NSH-2241.2003.3) and from the Competi-
tion Center for Fundamental Natural Sciences (Grant
No. E-02-5.0-60) is gratefully acknowledged.
12. (a) Arbuzova, S. N.; Brandsma, L.; Gusarova, N. K.;
Trofimov, B. A. Recl. Trav. Chim. Pays-Bas 1994, 113,
575–576; (b) Trofimov, B. A.; Brandsma, L.; Arbuzova, S.
N.; Malysheva, S. F.; Gusarova, N. K. Tetrahedron Lett.
1994, 35, 7647–7650.
References and notes
13. General procedure for the preparation of 3: An equimolar
mixture of secondary phosphine and vinyl ether of
diacetone-D-glucose was heated at 65–70°C in the pres-
ence of AIBN (0.5–1.5wt% of the reactantsÕ mass) in a
sealed ampoule. The crude product, a viscous undistillable
liquid, was purified by column chromatography on Al2O3
(diethyl ether) to give the phosphine 3 (Table 1).
1. (a) Asymmetric Catalysis in Organic Synthesis; Noyori, R.,
Ed.; John Wiley & Sons: New York, 1994; (b) Compre-
hensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A.,
Yamamoto, H., Eds.; Springer: Berlin, 1999; (c) Catalytic
Asymmetric Synthesis; Ojima, I., Ed., 2nd ed.; VCH:
Weinheim, 2000.

B. A. Trofimov et al. / Tetrahedron Letters 45 (2004) 9143–9145
9145
26
Compound 3a: colorless oil, ½aꢀD ꢁ15.6 (c 1.5, EtOH). 1H
Elemental analysis: Calcd for C22H41O7P (448.53): C,
58.91; H, 9.21; P, 6.91%. Found: C, 58.76; H, 9.43; P,
6.78%.
NMR (400.13MHz, CDCl3): d 0.90 (t, 6H, 3J = 6.4Hz,
Me, 1.30 (s, 3H, Me), 1.35 (s, 3H, Me), 1.38 (m, 10H,
CH2CH2CH2P), 1.43 (s, 3H, Me), 1.48 (m, 5H, C-10, Me),
1.66–1.70 (m, 2H, CH2P), 3.68–3.72 (m, 2H, H-9), 3.86 (d,
26
1
Compound 4b: colorless oil, ½aꢀD ꢁ1.9 (c 4.0, CCl4); H
NMR (400.13MHz, CDCl3): d 1.25 (s, 3H, Me), 1.29 (s,
3H, Me), 1.38 (s, 3H, Me), 1.48 (s, 3H, Me), 2.0–2.12 (m,
6H, H-10, CH2P), 2.80–2.98 (m, 4H, CH2Ph), 3.80–3.85
(m, 2H, H-9), 3.96–4.15 (m, 4H, H-3,4,6), 4.17–4.21 (m,
1H, H-5), 4.61 (d, 1H, 3J1,2 = 3.2Hz, H-2), 5.78 (d, 1H, H-
1), 7.16–7.28 (m, 10H, Ph). 13C NMR (100.69MHz): d
25.44, 26.23, 26.83, 26.98 (4Me), 27.81 (d, 2JP,C = 18.4Hz,
1H, J3,4 = 3.0Hz, H-3), 3.96 (dd, 1H, 2J = 8.3Hz,
3
3J5,6 = 5.5Hz, H-6), 4.06 (dd, 1H, 2J = 8.3Hz,
3J5,6 = 5.8Hz, H-6), 4.09 (dd, 1H, 3J4,5 = 6.8Hz,
3J3,4 = 3.0Hz, H-4), 4.12–4.16 (m, 1H, H-5), 4.51 (d, 1H,
3J1,2 = 3.1Hz, H-2), 5.92 (d, 1H, H-1). 13C NMR
3
(100.69MHz): d 13.85 (Me), 24.50 (d, JP,C = 10.7Hz,
CH2Me), 25.23, 25.50, 26.24 (3Me), 26.56 (d,
2
CH2Ph), 27.83 (d, JP,C = 17.7Hz, CH2Ph), 28.89 (d,
1JP,C = 12.0Hz, C-10), 26.90 (Me), 27.10 (d,
1JP,C = 63.0Hz, C-10), 30.82 (d, JP,C = 62.5Hz, CH2P),
1
2JP,C = 11.1Hz, CH2CH2P), 27.17 (d, JP,C = 11.5Hz,
CH2CH2P), 27.98 (d, JP,C = 14.4Hz, CH2P), 28.02 (d,
31.35 (d, JP,C = 62.5Hz, CH2P), 63.92 (d, JP,C = 2.8Hz,
C-9), 67.55 (C-6), 72.35 (C-5), 81.02 (C-4), 82.22
(C-3), 82.52 (C-2), 105.26 (C-1), 109.29 and 111.92
(C-7,8), 126.08 (C-p), 128.06 and 128.12 (C-o), 128.83
2
1
2
1
1JP,C = 14.6Hz, CH2P), 67.62 (C-6), 68.91 (d, JP,C
=
2
21.0Hz, C-9), 72.57 (C-5), 81.21 (C-3), 82.27 (C-4), 85.19
(C-2), 105.34 (C-1), 109.54 and 111.80 (C-7,8). 31P NMR
(161.98MHz): d ꢁ33.94. Elemental analysis: Calcd for
C22H41O6P (432.53): C, 61.09; H, 9.55; P, 7.16%. Found:
C, 61.05; H, 9.67; P, 7.39%.
3
(C-m), 140.91 (d, JP,C = 13.7Hz, C-i). 31P NMR (161.98
MHz): d 46.18. Elemental analysis: Calcd for C30H41O7P
(544.62): C, 66.16; H, 7.59; P, 5.69%. Found: C, 66.22; H,
7.32; P, 5.85%.
26
1
Compound 3b: colorless oil, ½aꢀ ꢁ7.1 (c 1.0, EtOH); H
NMR (400.13MHz, CDCl3): dD1.31 (s, 6H, Me), 1.43 (s,
3H, Me), 1.53 (s, 3H, Me), 1.73–1.81(m, 6H, H-10, CH2P),
2.71–2.86 (m, 4H, CH2Ph), 3.64–3.77 (m, 2H, H-9), 3.84
15. General procedure for the preparation of 5: A mixture of
phosphine 3 and elemental sulfur in toluene was heated at
50°C upon stirring under argon for 3h. The crude
product, a viscous undistillable liquid, was purified by
column chromatography on Al2O3 (hexane) to give the
phosphine sulfide 5 (Table 2).
3
(d, 1H, J3,4 = 2.7Hz, H-3), 3.99 (dd, 1H, 2J = 8.8Hz,
3
3J5,6 = 5.9Hz, H-6), 4.06 (dd, 1H, 2J = 8.8Hz, J5,6
=
26
3
3
5.9Hz, H-6), 4.09 (dd, 1H, J4,5 = 7.7Hz, J3,4 = 2.7Hz,
H-4), 4.34 (dd, 1H, 3J4,5 = 7.7Hz, 3J5,6 = 5.9Hz, H-5), 4.53
(d, 1H, J1,2 = 3.7Hz, H-2), 5.83 (d, 1H, H-1), 7.17–7.30
Compound 5a: yellow solid, mp 98–99°C (hexane), ½aꢀD
ꢁ7.1 (c 1.0, EtOH); 1H NMR (400.13MHz, CDCl3): d
0.90–0.95 (m, 6H, Me), 1.25 (s, 3H, Me), 1.31 (s, 3H, Me),
1.34 (s, 3H, Me), 1.41 (m, 4H, CH2Me), 1.48 (s, 3H, Me),
1.54–1.58 (m, 4H, CH2CH2P), 1.81–1.86 (m, 6H, H-10,
3
(m, 10H, Ph). 13C NMR (100.69MHz): d 23.44, 25.17,
1
25.23, 25.48 (4Me), 27.67 (d, JP,C = 14.9Hz, C-10), 29.38
1
(d, JP,C = 13.2, CH2P) 29.47 (d, JP,C = 13.6Hz, CH2P),
1
2
CH2P), 3.80–3.91 (m, 2H, H-9), 3.98 (dd, 1H, J = 8.5Hz,
2
32.23 (d, JP,C = 14.2Hz, CH2Ph), 67.55 (C-6), 68.66 (d,
3J5,6 = 5.5Hz, H-6), 4.03–4.07 (m, 2H, H-3,6), 4.08–4.14
(m, 1H, H-4), 4.18–4.25 (m, 1H, H-5), 4.72 (d, 1H,
3J1,2 = 3.3Hz, H-2), 5.82 (d, 1H, H-1). 13C NMR
(100.69MHz): d = 13.58 (Me), 23.78 (CH2Me), 24.03
2JP,C = 19.7Hz, C-9), 72.47 (C-5), 81.18 (C-4), 82.18 (C-3),
82.75 (C-2), 105.26 (C-1), 109.02 and 111.80 (C-7,8),
126.08 (C-p), 128.13 (C-o), 128.52 (C-m), 142.69 (d,
3JP,C = 10.4Hz, C-i), 142.73 (d, JP,C = 10.3Hz, C-i). 31P
(CH2Me), 24.50 (d, JP,C = 16.2Hz, CH2CH2P), 24.57 (d,
2JP,C = 16.2Hz, CH21CH2P), 25.42, 26.14, 26.72, 26.83
(4Me), 30.48 (d, JP,C = 49.9Hz, C-10), 31.30 (d,
3
2
NMR (161.98MHz): d ꢁ31.18. Elemental analysis: Calcd
for C30H41O6P (528.62): C, 68.17; H, 7.82; P, 5.86%.
Found: C, 68.39; H, 7.73; P, 5.65%.
1
1JP,C = 51.4Hz, CH2P), 32.38 (d, JP,C = 50.4Hz, CH2P),
64.26 (d, JP,C = 2.9Hz, C-9), 67.35 (C-6), 72.26 (C-5),
2
14. General procedure for the preparation of 4: A solution of
phosphine 3 in hexane was stirred at rt under air or O2
atmosphere. After reaction completion, as indicated by
TLC, the solvent was removed under reduced pressure to
afford phosphine oxide 4 (Table 2).
80.79 (C-4), 81.90 (C-3), 82.09 (C-2), 105.17 (C-1), 109.06
and 111.74 (C-7,8). 31P NMR (161.98MHz): d 46.73.
Elemental analysis: Calcd for C22H41O6PS (464.60): C,
56.88; H, 8.89; P, 6.67; S, 6.90%. Found: C, 56.98; H, 8.69;
P, 6.51; S, 6.72%.
26
1
Compound 4a: colorless oil, ½aꢀ ꢁ12.2 (c 0.5, CCl4); H
NMR (400.13MHz, CDCl3): dD0.89 (t, 6H, 3J = 7.2Hz,
Me, 1.21–1.31 (m, 4H, CH2Me), 1.28 (s, 3H, Me), 1.32–
1.39 (m, 2H, CH2CH2P), 1.33 (s, 3H, Me), 1.41 (s, 3H,
Me), 1.46 (s, 3H, Me), 1.47–1.58 (m, 3H, CH2CH2P),
1.63–1.71 (m, 2H, CH2P), 1.94–2.00 (m, 1H, CH2P), 2.22–
2.28 (m, 2H, H-10), 3.79–3.85 (m, 2H, H-9), 3.95 (dd, 1H,
26
Compound 5b: yellow solid, mp 87–88°C (hexane), ½aꢀD
ꢁ25.7 (c 1.0, CCl4). 1H NMR (400.13MHz, CDCl3): d
1.26 (s, 3H, Me), 1.29 (s, 3H, Me), 1.38 (s, 3H, Me), 1.47
(s, 3H, Me), 1.96–2.17 (m, 6H, H-10, CH2P), 2.89–2.94 (m,
4H, CH2Ph), 3.82–3.90 (m, 2H, H-9), 3.94–4.02 (m, 3H,
H-3,6), 4.05–4.12 (m, 1H, H-4), 4.14–4.20 (m, 1H, H-5),
3
3
2J = 8.6Hz, J5,6 = 5.3Hz, H-6), 4.03 (m, 1H, H-3), 4.12
4.73 (d, 1H, J1,2 = 3.3Hz, H-2), 5.78 (d, 1H, H-1), 7.16–
7.28 (m, 10H, Ph).13C NMR (100.69MHz): d 25.11, 26.14,
26.71, 26.86 (4Me), 28.60 (d, JP,C = 27.0Hz, CH2Ph),
3
(dd, 1H, 2J = 8.6Hz, J5,6 = 6.3Hz, H-6), 4.28–4.33 (m,
3
2
2H, H-4,5), 4.49 (d, 1H, J1,2 = 3.6Hz, H-2), 5.90 (d, 1H,
H-1). 13C NMR (100.69MHz): d 13.54 (Me), 23.56 (d,
3JP,C = 3.8Hz, CH2Me), 23.78 (d, 3JP,C = 3.8Hz, CH2Me),
24.15 (d, 2JP,C = 13.9Hz, CH2CH2P), 24.17 (d,
2JP,C = 14.8Hz, CH21CH2P), 25.07, 26.10, 26.68, 26.77
(4Me), 28.28 (d, JP,C = 66.1Hz, C-10), 28.34 (d,
1
1
30.90 (d, JP,C = 49.7Hz, C-10), 33.31 (d, JP,C = 48.4Hz,
1
CH2P), 34.19 (d, JP,C = 47.5Hz, CH2P), 64.23 (d,
2JP,C = 3.6Hz, C-9), 67.41 (C-6), 72.18 (C-5), 80.88 (C-
4), 81.93 (C-3), 82.20 (C-2), 105.14 (C-1), 109.15 and
111.80 (C-7,8), 126.51 and 126.54 (C-p), 128.06 and 128.18
1
3
1JP,C = 63.9Hz, CH2P), 28.80 (d, JP,C = 65.4Hz, CH2P),
(C-o), 128.68 (C-m), 140.52 (d, JP,C = 14.6Hz, C-i). 31P
2
63.78 (d, JP,C = 3.2Hz, C-9), 67.53 (C-6), 73.35 (C-5),
NMR (161.98MHz): d 48.03. Elemental analysis: Calcd
for C30H41O6PS (560.69): C, 64.27; H, 7.37; P, 5.52; S,
5.72%. Found: C, 64.45; H, 7.55; P, 5.35; S, 5.58%.
75.02 (C-4), 81.06 (C-3), 85.02 (C-2), 105.19 (C-1), 109.52
and 111.72 (C-7,8). 31P NMR (161.98MHz): d 48.39.