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0025027968
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60
-
-
46849097018
-
-
Isolation not attempted. 31P NMR (THF) and MS data: 10a, δP 59.7 ppm, m, HRMS m/z 154.9930, M-H, C3H8O3PS- calcd 154.9937, 10b, δP 58.2 ppm, qu, 3J, 8.2 Hz, HRMS m/z 169.0100, M-H, C4H 10O3PS- calcd 169.0094, 10c, δP 55.9 ppm, q, 3J, 8.6 Hz, HRMS m/z 183.0270, M-H, C5H12O3PS, calcd 183.0250, 10d, δP 49.8 ppm, t, 3J, 8.0 Hz, HRMS m/z 197.0401, M-H, C6H14O3PS- calcd 197.0407
-
- calcd 197.0407).
-
-
-
-
61
-
-
1542353487
-
-
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62
-
-
46849102427
-
-
The most reliable method to check whether more reactive alcohols also choose to react via metaphosphate or not are kinetic studies. Since an alcohol molecule is not involved in the formation of metathiophosphate 8, neither in path A nor in path B (Scheme 2, the rates of these reactions were expected to be independent of the alcohol concentration. On the other hand, if the bimolecular displacement occurs (Scheme 2, path C) the overall reaction rate should display first-order dependence on the alcohol concentration. See, e.g, ref 31
-
The most reliable method to check whether more reactive alcohols also choose to react via metaphosphate or not are kinetic studies. Since an alcohol molecule is not involved in the formation of metathiophosphate 8, neither in path A nor in path B (Scheme 2), the rates of these reactions were expected to be independent of the alcohol concentration. On the other hand, if the bimolecular displacement occurs (Scheme 2, path C) the overall reaction rate should display first-order dependence on the alcohol concentration. See, e.g., ref 31.
-
-
-
-
65
-
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0000754970
-
-
Jankowski, S.; Quin, L. D.; Paneth, P.; O'Leary, M. H. J. Am. Chem. Soc. 1994, 116, 11675-11677.
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66
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0031568634
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68
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46849105728
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Hiresova, R.; Putilova, L.; Kullberg, M.; Stawinski, J. Collect. Symp. Ser. 2005, 7, 201-205.
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-
69
-
-
46849114793
-
-
P 51.0, 50.9 (neat t-BuOH), 50.7, 50.5 (THF), 51.3, 51.2 ppm (MeCN).
-
P 51.0, 50.9 (neat t-BuOH), 50.7, 50.5 (THF), 51.3, 51.2 ppm (MeCN).
-
-
-
-
70
-
-
0000546527
-
-
Friedman, J. M.; Freeman, S.; Knowles, J. R. J. Am. Chem. Soc. 1988, 110, 1268-1275.
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0028308541
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37049074347
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84912991868
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90
-
-
4243132841
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0028233855
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94
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0037074134
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Bollmark, M.1
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-
96
-
-
46849085248
-
-
Isolation not attempted. 31P NMR (THF) and MS data: 11b, δP 57.3, 57.0 ppm, HRMS m/z 667.1913, M-H, C33H36N2O 9PS- calcd 667.1885, 18, δP 113.5 ppm, HRMS m/z 683.1623, M-H, C33H 36N2O8PS2- calcd 683.1656, 19, δP 52.4, 52.2 ppm, HRMS m/z 715.1278[M-H, C33H36N2O 9PSe- calcd 715.1329
-
- calcd 715.1329).
-
-
-
-
100
-
-
46849121866
-
-
P-D = 224 Hz.
-
P-D = 224 Hz.
-
-
-
-
103
-
-
33846811414
-
-
Nawrot, B.; Widera, K.; Wojcik, M.; Rebowska, B.; Nowak, G.; Stec, W. J. FEBS J. 2007, 274, 1062-1072.
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-
107
-
-
0037132582
-
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108
-
-
0027230508
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-
110
-
-
46849117602
-
-
Excess of nucleosidic component 20 could be efficiently recovered during chromatography (see the Supporting information).
-
Excess of nucleosidic component 20 could be efficiently recovered during chromatography (see the Supporting information).
-
-
-
-
111
-
-
0025007536
-
-
Stawinski, J.; Thelin, M.; Westman, E.; Zain, R. J. Org. Chem. 1990, 55, 3503-3506.
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