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Volumn 6, Issue 1, 2015, Pages 174-180

Mechanistic insights into hydroacylation with non-chelating aldehydes

Author keywords

[No Author keywords available]

Indexed keywords

CHELATION; METHANE; RHODIUM; RHODIUM COMPOUNDS;

EID: 84919346367     PISSN: 20416520     EISSN: 20416539     Source Type: Journal    
DOI: 10.1039/c4sc02026j     Document Type: Article
Times cited : (54)

References (65)
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    • We expected catalyst 11 to exhibit a faster rate than the optimized reaction because none of the Rh would be sequestered as the double salt of 4 and 9. The fact that 11 provides only a slightly higher initial TOF than the optimized reaction is likely a result of the low solubility of the t-BuOK-vinylphenol mixture and the lack of stirring during NMR analysis
    • B. R. James C. G. Young J. Organomet. Chem. 1985 285 321
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  • 48
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    • For examples of hydroacylation where deuterium scrambling is observed as a result of rate-limiting reductive elimination, see
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    • Ref. 6d Ref. 2d Ref. 2b To our knowledge, there are only two examples of olefin hydroacylation where reductive elimination has been ruled out as the rate-limiting step, see
    • I. F. D. Hyatt H. K. Anderson A. T. Morehead Jr A. L. Sargent Organometallics 2008 27 135
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    • Ref. 2k An intermolecular KIE experiment is appropriate for this system given that C-H bond cleavage is the first step in the catalytic cycle and our observed catalyst resting states ([Rh(dcpm)(vinylphenolate)]) and [Rh(dcpm)(vinylphenolate)(aldehyde)] directly precede aldehyde activation. For a discussion on KIEs in metal catalysis, see
    • M. C. Coulter P. K. Dornan V. M. Dong J. Am. Chem. Soc. 2009 131 6932
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  • 58
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    • + catalysed aldehyde decarbonylation, see ref. 18 In line with our observation of saturation kinetics with respect to the 2-vinylphenol, modifying the 2-vinylphenols at the 3 or 4 position also changes the reaction rate even though the substrate does not appear in the rate equation. More electron rich 2-vinylphenols appear to react slower than electron deficient substrates, but electron rich substrates also lead to unidentified side-products For the effect of electronics on oxidative addition, see
    • Z. Shen P. K. Dornan H. A. Khan T. K. Woo V. M. Dong J. Am. Chem. Soc. 2009 131 1077
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  • 64
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    • Branched-selective migratory insertion is generally fast and reversible for olefin hydroacylation, whereas linear-selective insertion has a higher barrier, see: Ref. 16b Ref. 2d Ref. 15g for a related example of the hydroformylation reaction, see
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.