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G.C. Bazan, G. Rodriguez, A.J. Ashe, S. Al-Ahmad, J.W. Kampf, Organometallics 16 (1997) 2492
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Bazan, G.C.1
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K. Mach, P. Sedmera, L. Perusova, H. Antropiusova, B. Hanus, F. Turecek, Tetrahedron Lett. 23 (1982) 1105.
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Mach, K.1
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Hanus, B.5
Turecek, F.6
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16
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0033515599
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For Ru(I)-catalyzed processes
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For Ru(I)-catalyzed processes: Y. Yamamoto, N. Ohkoshi, M. Kameda, K. Itoh, J. Org. Chem. 64 (1999) 2178
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J. Org. Chem.
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Yamamoto, Y.1
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D. Walther, T. Döhler, K. Heubach, O. Klobes, B. Schweder, H.Z. Görls, Anorg. Allg. Chem. 625 (1999) 923.
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Görls, H.Z.6
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22
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0034673335
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For processes catalyzed by group IV alkoxide complexes
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For processes catalyzed by group IV alkoxide complexes: S. Okamoto, T. Livinghouse, J. Am. Chem. Soc. 122 (2000) 1223
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Okamoto, S.1
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B. Schweder, D. Walther, T. Döhler, O. Klobes, H. Görls, J. Prakt. Chem. 341 (1999) 736
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M.G. Thorn, J.E. Hill, S.A. Waratuke, E.S. Johnson, P.E. Fanwick, I.P. Rothwell, J. Am. Chem. Soc. 119 (1997) 8630.
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Fanwick, P.E.5
Rothwell, I.P.6
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26
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0035477778
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For Pd-catalyzed processes
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For Pd-catalyzed processes: K.L. Bray, J.P.H. Charmant, I.J.S. Fairlamb, G.C. Lloyd-Jones, Chem. Eur. J. 7 (2001) 4205
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Bray, K.L.1
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Grigg, R.1
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0001525502
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For Pt-catalyzed processes
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For Pt-catalyzed processes: N. Chatani, N. Furukawa, H. Sakurai, S. Murai, Organometallics 15 (1996) 901
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(1996)
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Chatani, N.1
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Bright, A.1
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Shaw, B.L.5
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49
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0344290123
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Because a syn-coplanar arrangement of atoms is required for β-hydride elimination and because the palladium atom and the tertiary β-hydrogen atom of cis- V are positioned on opposite faces of the cyclopentyl ring, elimination of the tertiary β-hydrogen atom, which would ultimately lead to formation of 4,4-dicarbomethoxy-1,2-dimethylcyclopentene, in precluded. Conversely, one of the secondary β-hydrogen atoms of cis- V is positioned syn to the palladium atom, and β-elimination of this hydrogen atom leads to exclusive formation of chiral cyclopentene 3
-
Because a syn-coplanar arrangement of atoms is required for β-hydride elimination and because the palladium atom and the tertiary β-hydrogen atom of cis- V are positioned on opposite faces of the cyclopentyl ring, elimination of the tertiary β-hydrogen atom, which would ultimately lead to formation of 4,4-dicarbomethoxy-1,2-dimethylcyclopentene, in precluded. Conversely, one of the secondary β-hydrogen atoms of cis- V is positioned syn to the palladium atom, and β-elimination of this hydrogen atom leads to exclusive formation of chiral cyclopentene 3
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55
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0001334715
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B. M. Trost, & I. Fleming (Eds.), Oxford: Pergamon
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Schore N.E. in: Trost B.M. Fleming I. (Eds.), Comprehensive Organic Synthesis 5 1991 1037 Pergamon Oxford
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(1991)
Comprehensive Organic Synthesis
, vol.5
, pp. 1037
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Schore, N.E.1
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56
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0344290125
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In a separate experiment, dienes 5 and 5a were shown to undergo palladium-catalyzed cycloisomerization at rates that differed by <10%
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In a separate experiment, dienes 5 and 5a were shown to undergo palladium-catalyzed cycloisomerization at rates that differed by <10%.
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57
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0344290124
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4
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4.
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63
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0345152426
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Contrary to popular opinion, in most cases the organometallic species that accumulates under catalytic conditions lies within the catalytic cycle [24], and documented examples where the organometallic species that accumulates under catalytic conditions lies outside the catalytic cycle are rare [25]
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Contrary to popular opinion, in most cases the organometallic species that accumulates under catalytic conditions lies within the catalytic cycle [24], and documented examples where the organometallic species that accumulates under catalytic conditions lies outside the catalytic cycle are rare [25].
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88
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0344722059
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Note that the magnitude of the difference in the rate of the cycloisomerization of 5 relative to the cycloisomerization of 1 need not correspond to the difference in stability between oxo chelate complexes 4 and A. Rather, the reduced stability of palladium oxo complex A relative to palladium carbonyl chelate complex 4 likely changes the turnover-limiting step in the palladium-catalyzed cycloisomerization of 5 relative to that observed in the palladium-catalyzed cycloisomerization of 1 (olefin displacement from intermediate cis- VII). In a similar manner, we have no evidence that indicates that A is formed in the cycloisomerization of 5 catalyzed by 2. Rather, DFT calculations suggest that if A is formed cycloisomerization of 5, it will not serve as a thermodynamic sink as does 4 in the cycloisomerization of 1
-
Note that the magnitude of the difference in the rate of the cycloisomerization of 5 relative to the cycloisomerization of 1 need not correspond to the difference in stability between oxo chelate complexes 4 and A. Rather, the reduced stability of palladium oxo complex A relative to palladium carbonyl chelate complex 4 likely changes the turnover-limiting step in the palladium-catalyzed cycloisomerization of 5 relative to that observed in the palladium-catalyzed cycloisomerization of 1 (olefin displacement from intermediate cis- VII). In a similar manner, we have no evidence that indicates that A is formed in the cycloisomerization of 5 catalyzed by 2. Rather, DFT calculations suggest that if A is formed cycloisomerization of 5, it will not serve as a thermodynamic sink as does 4 in the cycloisomerization of 1
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90
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0345152418
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We thank a reviewer for alerting our attention to the relationship between the cationic nature of the catalyst and the tendency to form stable oxochelate complexes
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We thank a reviewer for alerting our attention to the relationship between the cationic nature of the catalyst and the tendency to form stable oxochelate complexes.
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92
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0345584265
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Molecular Simulations, DMol3, Molecular Simulations Inc., San Diego, CA
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Molecular Simulations, DMol3, Molecular Simulations Inc., San Diego, CA, 2001.
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