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58149316788
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In the chemical formula, the designations α or β and 1 or 2 refer to the carbopalladation that occur at α or β position of the 1-alkyne employed, and C-Si bond occurring at terminal or internal carbon of the 1-alkene counterpart, respectively
-
In the chemical formula, the designations α or β and 1 or 2 refer to the carbopalladation that occur at α or β position of the 1-alkyne employed, and C-Si bond occurring at terminal or internal carbon of the 1-alkene counterpart, respectively.
-
-
-
-
41
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58149277906
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Immediate reaction products consist of α's (> 90%), a little β isomer (<5%) and others on the basis of GLC analysis, the latter two being hardly isolated at this stage.
-
Immediate reaction products consist of α's (> 90%), a little β isomer (<5%) and others on the basis of GLC analysis, the latter two being hardly isolated at this stage.
-
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42
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0036032368
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3 = tris{2,2″, 6,6″ - tetramethyl-m-terphenyl-5′-yl}-phosphine: a) K. Goto, Y. Ohzu, H. Sato, T. Kawashima, Phosphorus, Sulfur Silicon Relat. Elem. 2002, 177, 2179.
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3 = tris{2,2″, 6,6″ - tetramethyl-m-terphenyl-5′-yl}-phosphine: a) K. Goto, Y. Ohzu, H. Sato, T. Kawashima, Phosphorus, Sulfur Silicon Relat. Elem. 2002, 177, 2179.
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44
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58149277893
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In this regard, it should be mentioned that, in the hydrosilylative cross-coupling of 1-heptyne with 1-hexene (3 equiv) in the presence of catalyst A, P(C6F5)3 caused very rapid conversion at room temperature, giving rise to products (55% yield) in 7a (α-l):9a (β-1, 22:78 (see, Table 3, Entry 3, footnote e, Thus, the fact that phenylacetylene, 1b (α-1, 2b (α-2, 3b (β-l, 85:15 (Table 1, Entry 5, and 1-heptyne show contrasting regioselectivities well reinforces that P(C6F5)3 as a ligand exhibits a reversed electronic effect on the hydropalladation step for these two alkynes
-
3 as a ligand exhibits a reversed electronic effect on the hydropalladation step for these two alkynes.
-
-
-
-
45
-
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58149306522
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3-Butyl-2-methylenebutanolide = 4-Butyl-3-methylene-4,5-dihydro-2(3H) furanone: E. Roeder, H. Krauss, Ann. Chim. 1992, 177.
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a) 3-Butyl-2-methylenebutanolide = 4-Butyl-3-methylene-4,5-dihydro-2(3H) furanone: E. Roeder, H. Krauss, Ann. Chim. 1992, 177.
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46
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2-Methylene-3-phenylbutanolide: H. Nishiyama, H. Yokoyama, S. Narimatsu, K. Itoh, Tetrahedron Lett. 1982, 23, 1267.
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b) 2-Methylene-3-phenylbutanolide: H. Nishiyama, H. Yokoyama, S. Narimatsu, K. Itoh, Tetrahedron Lett. 1982, 23, 1267.
-
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47
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0035831161
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Reversivility of the hydropalladation in the Pd-catalyzed alkadiynes has not been established. However, reversible silylpalladation in the case of alkadienes under similar reaction conditions are discussed. See
-
Reversivility of the hydropalladation in the Pd-catalyzed alkadiynes has not been established. However, reversible silylpalladation in the case of alkadienes under similar reaction conditions are discussed. See: X. Wang, H. Chakrapani, C. N. Stengone, R. A. Widenhoefer, J. Org. Chem. 2001, 66, 1755.
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48
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58149296714
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With regard to this discussion, Hayashi et al. have observed that the reaction of [Pd(η3-C3H5)Cl]2 with HSiEt3 in the presence of a diphosphine generates a Pd 0L2 species together with ClSiEt3 and propene. The reaction with HSiCl3 and PPh3 should also produce a Pd0 species. See: Y. Uozumi, H. Tsuji, T. Hayashi, J. Org. Chem. 1998, 63, 6137; Hydrosilylation of 1,5- and 1,3-cyclooctadiene has long been known to be catalyzed easily by various types of Pt catalysts: K. Yamamoto, M. Kumada, J. Organometal. Chem. 1968, 13, 131
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0 species. See: Y. Uozumi, H. Tsuji, T. Hayashi, J. Org. Chem. 1998, 63, 6137; Hydrosilylation of 1,5- and 1,3-cyclooctadiene has long been known to be catalyzed easily by various types of Pt catalysts: K. Yamamoto, M. Kumada, J. Organometal. Chem. 1968, 13, 131.
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49
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58149277902
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3 will be discussed elsewhere: N. Takaoka, B.S. Thesis, Tokyo University of Science, Yamaguchi, 2004.
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3 will be discussed elsewhere: N. Takaoka, B.S. Thesis, Tokyo University of Science, Yamaguchi, 2004.
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0842342512
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A cationic arylpalladium species is known to undergo a facile alkene insertion in the Mizoroki-Heck reaction: F. Ozawa, T. Hayashi, J. Am. Chem. Soc. 1991, 113, 1417;
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A cationic arylpalladium species is known to undergo a facile alkene insertion in the Mizoroki-Heck reaction: F. Ozawa, T. Hayashi, J. Am. Chem. Soc. 1991, 113, 1417;
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58149311652
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3 (X = Cl or OEt) and not consonant with those by CAS (9CI).
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3 (X = Cl or OEt) and not consonant with those by CAS (9CI).
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