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Compound 2 constitutes a formal synthesis of D-myo-inositol-1,4,5-triphosphate 1 (Figure 2) and was in agreement with reported spectral data; see ref 9d.
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(a) KH, THF, 0°C, 8 h; 80% (2:3 = 16:1).
-
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-
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50
-
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0141550205
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note
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(b) KHMDS, THF, -78°C, 6 h; 50-88% (2:3 = 6-20:1).
-
-
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51
-
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0141773512
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note
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tBu, THF, 0°C, 2 h; 33% (2:3 = 6:1).
-
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-
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52
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0141661585
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note
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tBu, 18-C-6, THF, 0°C, 1 h; 58% (2:3 = 16:1).
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note
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13C NMR, optical rotation, and HRMS compared to literature values.
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55
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0141773511
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note
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Diastereoselectivity of silylallylboration en route to the stereotetrad in 11 has been improved by using the acetonide-protected aldehyde 21 (cf. 8), which gave β-hydroxyallylsilane 22 with > 15:1 dr. Compound 22 readily underwent RCM to provide cyclohexene 23 in good yield. Further elaboration of 23 to cyclitol derivatives will be reported in our subsequent papers in this series.
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