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Preliminary communication of this work has appeared: (a) Katsuhira, T.; Harada, T.; Maejima, K.; Osada, A.; Oku, A. J. Org. Chem. 1993, 58, 6166. (b) Harada, T. Osada, A.; Oku, A. Tetrahedron Lett. 1995, 36, 723.
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47
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10544226086
-
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note
-
The nature of leaving groups in 1 also influences to the acidity of acetylenic proton. Thus, deprotonation of mesylate 1a proceeded even at -60°C judging from 90% yield formation of allene 5a (entry 3). On the other hand, deprotonation of carbamate 1d did not proceed in appreciable rate at the same temperature.
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48
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10544240685
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note
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2Zn (n = 0-2) should also be present in the reaction mixture. Although these organozinc species were neglected in order to simplify the discussion, the same conclusion are deduced by considering these species.
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52
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10544256045
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note
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2SiH that would be produced initially in the reaction of the silylzincates with the terminal alkyne.
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69
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0028290720
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Harada, T.; Katsuhira, T.; Hattori, K.; Oku, A. Tetrahedron 1994, 50, 7987.
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Kondo, Y.; Takezawa, N.; Yamazaki, C.; Sakamoto, T. J. Org. Chem. 1994 59, 4717.
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Kondo, Y.1
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-
71
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10544245525
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note
-
The byproduct formation of isomeric allenic alcohols was observed in the reaction of silylzinc reagents 30a and 29a: the reactions with 2-methylpropanal and 6,6-dimethoxyhexanal gave 7-methyl-1-phenyl-5-(dimethylphenylsilyl)-3,4-octadien-6-ol (47a) (14%) and 11,11-dimethoxy-1-phenyl-5-(dimethylphenylsilyl)-3,4-undecadien-6-ol (47b) (11%), respectively.
-
-
-
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72
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10544250561
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note
-
2H]-42a (58%-d) were obtained in 77% and 7.8% yield, respectively.
-
-
-
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73
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10544221969
-
-
note
-
2BuZnLi. The difference in reactivity might be derived from the differences of ligands.
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