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20444439700
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note
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Although a higher yield (92%) was realized when this reaction was carried out in neat DABCO, the reaction was completed after 30 days at room temperature. The coexistence of MeOH remarkably reduced the reaction time. We confirmed that 3-hydroxyquinuclidine (neat) also accelerates the reaction without a loss of the yield of 9.
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9
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0000516236
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and references therein
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For the acceleration of the Baylis-Hillman reaction in the presence of MeOH, see: Aggarwal, V. K.; Mereu, G. T.; Tarver, R.; McCague, R. J. Org. Chem. 1998, 63, 7183-7189 and references therein.
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11
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33845552447
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In place of DMPU, HMPA was also effective, although the yield of 11 was somewhat reduced. The phosphate-buffered solution was crucial to sustain the silyl protecting group. For the effect of the polar aprotic solvents, see: Hutchins, R. O.; Taffer, I. M. J. Org. Chem. 1983, 48, 1360-1362.
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20444433712
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note
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In the NOE experiment of 13, a remarkable (22%) signal enhancement of the CHO proton was observed when the β-vinyl proton was irradiated. Thus, the geometrical structures of 11-13 were ascertained.
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13
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0012016624
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