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It is known that the 9-phenylxanthen-9-yl (pixyl) group and 9-phenylthioxanthyl (S-pixyl) are photochemically removable to release primary alcohols and nucleosides; 9b-c
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76949105590
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2O (2:3) (cell 3). The monochromatic light centres at 285 nm and was opaque above 325 nm and below 250 nm 11c
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35
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76949105734
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note
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Photoreactions of 8 have been carried out in different solvents such as MeCN, MeCN/water, DMSO/water, acetone/water, benzene/water, chloroform, chloroform/water, and methanol. The reactions in methanol and MeCN/water (9:1) seemed to provide better results Irradiation of 6 in MeOH (5 mM) with 0.5% (v/v) chloroform for 20 min with the Pyrex-filtered light resulted in complete removal of the MMTr group. Under the same reaction conditions, the Tr group could not be removed from 5, even after increasing chloroform in methanol to 10%. However, deprotection of Tr was observed after 20 min irradiation with a 3-phenylpropanol/5 ratio of 0.06:1 in MeOH/chloroform (1:1) and 0.15:1 in MeOH/chloroform (1:9). When these irradiated reaction solutions were kept in dark, the deprotection reactions gradually reached completion overnight, which clearly indicates the existance of photogenerated acidic substance(s) catalyzing the reactions. Furthermore, in control experiments, there was no sign of photoreactions when 5 and 6 were irradiated with the Pyrex-filtered light in MeOH, MeCN/water, chloroform, or MeCN/chloroform Utilization of photogenerated acids from sensitizers in protecting group installation have been recently reported, albeit the identity of some acids are not clear; 15b-c
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41
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0037456310
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