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Volumn 687, Issue 2, 2003, Pages 498-507

Erratum: "Dramatic effect of homoallylic substitution on the rate of palladium-catalyzed diene cycloisomerization" (Journal of Organometallic Chemistry (2003) vol. 687 (498-507) 10.1016/j.jorganchem.2003.09.046);Dramatic effect of homoallylic substitution on the rate of palladium-catalyzed diene cycloisomerization

Author keywords

Diene cycloisomerization; Homoallylic substitution; Palladium catalyzed

Indexed keywords

ALKADIENE; ALKANE DERIVATIVE; ALLYL COMPOUND; CHELATE; CYANIDE; CYCLOPENTENE DERIVATIVE; HEPTANE; MALONIC ACID DERIVATIVE; METHYL GROUP; ORGANOFLUORINE DERIVATIVE; OXIDE; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE;

EID: 0344012078     PISSN: 0022328X     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.jorganchem.2004.06.001     Document Type: Erratum
Times cited : (14)

References (96)
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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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    • B. M. Trost, & I. Fleming (Eds.), Oxford: Pergamon
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  • 56
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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%
    • 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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    • 4
    • 4.
  • 63
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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]
    • 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].
  • 88
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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
  • 90
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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
    • 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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    • Molecular Simulations, DMol3, Molecular Simulations Inc., San Diego, CA
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.