72.77-72.56 (m), 72.2, 70.7, 69.35-69.16 (m) [(6 ¥ Ins CH) + Glyc
2-CH], 66.38-66.22 (m), 62.26-63.20 (m), 62.82-62.79 (2C, m),
62.61-62.50 (2C, m), 61.77-61.71 (m) [(2 ¥ Glyc CH2O) + (5 ¥
POCH2CH2CN)], 57.0 (OCH2Me), 46.9, 46.7 (CH2NCH2), 36.07
(0.6C), 36.04 (0.4C), 35.82 (0.4C), 35.75 (0.6C), 34.11, 33.96, 33.5,
33.0, 31.9 (2C), 29.7 (4C), 29.5 (2C), 29.31 (4C), 29.24, 29.22,
29.14 (2C), 29.11 (2C), 27.22 (2C), 27.18 (2C), 24.8 (2C), 23.9,
23.1, 22.7 (2C) (34 ¥ CH2), 19.61-19.54 (m, 5 ¥ CH2CN), 15.1
(OCH2Me), 14.1 (2C, 2 ¥ Me) ppm; dP (162 MHz, CDCl3) -2.90
(0.4P), -3.08 (0.2P), -3.17 (0.2P), -3.27 (0.2P), -3.50 (1P), -3.65
(1P) ppm; LRMS (ESI+) m/z (%) found [M+H]+ 1591.7 (77),
[M+Na-C13H16ClNO]+ 1376.6 (100), [M-C13H16ClNO]+ 1354.6
(97).
5 (a) A. C. Schmid, H. M. Wise, C. A. Mitchell, R. Nussbaum and R.
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9485; (i) L. Qiao, Y. Ho, F. Nan, G. Powis and A. P. Kozikowski, Org.
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1998, 39, 3965; chemical catalytic chiral induction: (k) B. R. Sculimbrene,
Y. Xu and S. J. Miller, J. Am. Chem. Soc., 2004, 126, 13182; enzymatic
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C.-S. Chen, Chem. Commun., 1994, 2125 (q) D.-S. Wang, A.-L. Hsu,
X. Song, C.-M. Chiou and C.-S. Chen, J. Org. Chem., 1998, 63, 5430;
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7 (a) C. B. Reese, Tetrahedron, 2002, 58, 8893; (b) V. Amarnath and A. D.
Broom, Chem. Rev., 1977, 77, 183; (c) S. L. Beaucage and R. P. Iyer,
Tetrahedron, 1992, 48, 2223.
8 D. van Aken, L. M. C. Paulissen and H. M. Buck, J. Org. Chem., 1981,
46, 3189.
9 R. J. Kubiak and K. S. Bruzik, J. Am. Chem. Soc., 2001, 123,
1760.
10 W. Li, C. Schultz, J. Llopis and R. Y. Tsien, Tetrahedron, 1997, 53,
12017.
11 (a) D. C. Billington, Chem. Soc. Rev., 1989, 18, 83; (b) B. V. L. Potter,
Nat. Prod. Rep., 1990, 7, 1; (c) B. V. L. Potter and D. Lampe, Angew.
Chem., Int. Ed. Engl., 1995, 34, 1933; (d) M. S. Shashidhar, ARKIVOC,
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Das, Chem. Rev., 2003, 103, 4477.
12 T. R. Pettitt, S. K. Dove, A. Lubben, S. D. J. Calaminus and M. J. O.
Wakelam, J. Lipid Res., 2006, 47, 1588.
13 (a) P. R. J. Gaffney and C. B. Reese, J. Chem. Soc., Perkin Trans. 1,
2001, 192; (b) P. R. J. Gaffney and C. B. Reese, Bioorg. Med. Chem.
Lett., 1997, 7, 3171.
14 (a) F. Han, M. Hayashi and Y. Watanabe, Tetrahedron, 2003, 59, 7703;
(b) F. Han, M. Hayashi and Y. Watanabe, Chem. Lett., 2003, 32, 46;
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8509; (f) F. Han, M. Hayashi and Y. Watanabe, Chem. Lett., 2003, 32,
724.
Dioleoyl phosphatidyl-myo-inositol 4,5-diphosphate, 1b. Fully
protected dioleoyl PtdInsP2 7 (115 mg, 0.072 mmol) was taken up
in MeCN (0.9 mL) to which was added TmsCl (0.18 mL, 1.4 mmol,
20 eq.) and Barton’s base (0.21 mL, 1.8 mmol, 25 eq.). The reaction
was stirred at rt for 16 h, then the solvent was evaporated under
reduced pressure and the residue was evaporated from MeCN (3 ¥
5 mL). The resulting mixture was triturated with Et2O, then the
filtrate was evaporated to dryness and taken up in 1M methanolic
ammonia (2 mL). After 25 min the solution was evaporated under
reduced pressure and the residue was dissolved in 80% acetic acid
(5 mL). After 3 h, the solvent was stripped off under reduced
pressure and the residue re-evaporated from EtOH (3 ¥ 10 mL).
The solids were triturated with DCM and then with MeCN to
give the title compound as a near-colourless solid (61 mg, 88%).
d
H (400 MHz, d4-AcOH-D2O-CDCl3 4:2:1 v/v) 5.44-5.37 (4H, m,
=
2 ¥ HC CH), 5.35-5.30 (1H, m, Glyc 2-H), 4.50-4.43 (2H, m),
4.34 (1H, bs), 4.27-4.08 (5H, m) [(4 ¥ Ins H) + (2 ¥ Glyc OCH2)],
4.02 (1H, bt, J 9.5, Ins-H), 3.78 (1H, bd, J 9.6, Ins 3-H), 2.42
(2H, t, J 7.5), 2.35 (2H, t, J 7.7) (2 ¥ CH2CO2) 2.11-2.04 (8H,
m, 2 ¥ CH2CHCHCH2), 1.69-1.59 (4H, m, 2 ¥ CH2CH2CO2),
1.43-1.29 (40H, m, 20 ¥ CH2), 0.93 (6H, t, J 6.8, 2 ¥ Me) ppm; dC
(100 MHz, CDCl3) 174.46, 174.27 (2 ¥ CO2), 129.9 (2C), 129.6 (2C)
(2 ¥ HCCH), 78.56-78.38 (m), 77.31-77.19 (m), 75.8 (d, J 5.3), 70.9
(2C, b), 70.52-70.34 (m), 70.3 [(6 ¥ Ins CH) + Glyc 2-CH], 63.97-
63.82 (m), 63.0 (2 ¥ Glyc CH2O), 34.19, 34.07, 31.9 (2C), 29.80,
29.77, 29.72 (2C), 29.51 (2C), 29.37-29.08 (10C, m), 27.2 (4C),
24.96, 24.83, 22.6 (2C) (28 ¥ CH2), 13.9 (2C, 2 ¥ Me) ppm; dP
(162 MHz, CDCl3) 0.77, 0.33, -1.12 ppm; HRMS (ESI-) m/z (%)
found [M-H]- 1021.4791 (58), C45H84O19P3 requires 1021.4820,
[M-2H+Na]- 1043.4681 (44), [M-2H]2- 510.2282 (100).
15 (a) Y. Watanabe, T. Nakamura and H. Mitsumoto, Tetrahedron Lett.,
1997, 38, 7407; (b) Y. Watanabe and M. Nakatomi, Tetrahedron Lett.,
1998, 39, 1583; (c) Y. Watanabe and M. Nakatomi, Tetrahedron, 1999,
55, 9743.
Acknowledgements
16 (a) R. J. Kubiak and K. S. Bruzik, J. Org. Chem., 2003, 68, 960; (b) K. M.
Pietrusiewicz, G. S. Salamonczyk, K. S. Bruzik and W. Wieczorek,
Tetrahedron, 1992, 48, 5523; (c) K. S. Bruzik and M.-D. Tsai, J. Am.
Chem. Soc., 1992, 114, 6361.
Funding from the UK Medical Research Council (PRJG, grant no.
G 120/709) and Biotechnology and Biological Sciences Research
Council (NP, grant no. 28/B17388) are gratefully acknowledged.
17 (a) R. J. Kubiak and K. S. Bruzik, Bioorg. Med. Chem. Lett., 1997, 7,
1231; (b) H. Zhang, N. Markadieu, R. Beauwens, C. Erneux and G. D.
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