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Volumn 15, Issue 42, 2009, Pages 11078-11082

Striking AcOH acceleration in direct intramolecular allylie amination reactions

Author keywords

Amination; C H activation; Density functional calculations; Palladium; Solvent effects

Indexed keywords

ACCELERATING EFFECT; ALLYLIC AMINATION; AMINATION REACTION; BENZOQUINONES; BIS-SULFOXIDE; C-H ACTIVATION; CATALYTIC CYCLES; CYCLISATIONS; DENSITY FUNCTIONAL CALCULATIONS; ORGANIC LAYERS; RE-OXIDATION; REACTION MIXTURE; ROUND-BOTTOM FLASKS; SOLVENT EFFECTS;

EID: 70350475266     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200901946     Document Type: Article
Times cited : (105)

References (58)
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    • For the synthesis of the cyclisation precursors see the Supporting In- formation.
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    • For sake of simplicity, benzoquinone, instead of phenylbenzoqui- none, is shown in the mechanism. However, these reactions work almost equally well with the former oxidizing agent.
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    • BQ-LL ligand exchange may take place prior (ref. [4c]) or after (see below) the cyclisation step
    • BQ-LL ligand exchange may take place prior (ref. [4c]) or after (see below) the cyclisation step.
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    • 2. equation represented
    • 2. equation represented
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    • 3-allyl)palladium complex intermediate. Alternatively, Echavarren (ref. [14b]) suggested that this solvent may promote pro- tonation of an acetate ligand bound to Pd, thereby facilitating the formation of a reactive cationic complex
    • 3-allyl)palladium complex intermediate. Alternatively, Echavarren (ref. [14b]) suggested that this solvent may promote pro- tonation of an acetate ligand bound to Pd, thereby facilitating the formation of a reactive cationic complex.
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    • -1. The largely positive AG° value implies that, even in the AcOH solvent, the equilibrium is unequivocally shifted toward the Pd° complex
    • -1. The largely positive AG° value implies that, even in the AcOH solvent, the equilibrium is unequivocally shifted toward the Pd° complex.
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    • II-catalysed allylic acetoxylation of olefins in acetic acid is a widely known process. See reference [4a], and references therein
    • II-catalysed allylic acetoxylation of olefins in acetic acid is a widely known process. See reference [4a], and references therein.
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    • Concerning this potential problem, the huge effective molarity asso- ciated with a five- or six-membered ring formation should override alternative intermolecular processes. Should a complex of type V be formed, this could re-enter the catalytic cycle through equilibration with II
    • Concerning this potential problem, the huge effective molarity asso- ciated with a five- or six-membered ring formation should override alternative intermolecular processes. Should a complex of type V be formed, this could re-enter the catalytic cycle through equilibration with II.
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    • 2 sug- gests that a further role of BQ in the catalytic experiments is activa- tion of step a or b (e.g., by ionisation). BQ activation of step c (ref. [4c]) without activation of steps a or b seems unlikely due to the evident irreversibility of step b
    • 2 sug- gests that a further role of BQ in the catalytic experiments is activa- tion of step a or b (e.g., by ionisation). BQ activation of step c (ref. [4c]) without activation of steps a or b seems unlikely due to the evident irreversibility of step b.
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    • 2SOMe (chiral isomer) was taken as a model of ligand LL for the computational study. A DFT study of the entire catalytic cycle will appear elsewhere
    • 2SOMe (chiral isomer) was taken as a model of ligand LL for the computational study. A DFT study of the entire catalytic cycle will appear elsewhere.
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    • The species corresponds to the second intermediate of the sequence shown in reference [H]. The calculations show that the proton, con- tested between the coordinated BQ molecule and acetate anion, in- variably leads to AcOH
    • The species corresponds to the second intermediate of the sequence shown in reference [H]. The calculations show that the proton, con- tested between the coordinated BQ molecule and acetate anion, in- variably leads to AcOH.
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    • II (Pd-C = 2.13 À); see: L. Xu, Q. Shi, X. Li, X. Jia, X. Huang, R. Wang, Z. Zhou, Z. Lin, A. S. C Chan
    • II (Pd-C = 2.13 À); see: L. Xu, Q. Shi, X. Li, X. Jia, X. Huang, R. Wang, Z. Zhou, Z. Lin, A. S. C Chan, Chem. Commun. 2003, 1666-1667.
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    • The enthalpies of some computed transition states are relatively high, also due to significant structural and electronic rearrange- ments, but it should be kept in mind that the studied process is ini- tially ter-molecular, hence entropically favoured
    • The enthalpies of some computed transition states are relatively high, also due to significant structural and electronic rearrange- ments, but it should be kept in mind that the studied process is ini- tially ter-molecular, hence entropically favoured.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.