NDLI: Mechanistic insights into hydroacylation with non-chelating aldehydes† †Electronic supplementary information (ESI) available: Materials and methods, reaction procedures, characterization data. CCDC 1012849. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc0202

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Mechanistic insights into hydroacylation with non-chelating aldehydes† †Electronic supplementary information (ESI) available: Materials and methods, reaction procedures, characterization data. CCDC 1012849. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc0202

Content Provider	Semantic Scholar
Author	Murphy, Stephen K. Bruch, Achim Dong, Vy M.
Copyright Year	2015
Abstract	The combination of a small-bite-angle diphosphine bis(dicyclohexylphosphino)methane (dcpm) and [Rh(cod)OMe]2 catalyses the hydroacylation of 2-vinylphenols with a wide range of non-chelating aldehydes. Here we present a detailed experimental study that elucidates the factors contributing to the broad aldehyde scope and high reactivity. A variety of catalytically relevant intermediates were isolated and a [Rh(dcpm)(vinylphenolate)] complex was identified as the major catalytically relevant species. A variety of off-cycle intermediates were also identified that can re-enter the catalytic cycle by substrate- or 1,5-cyclooctadiene-mediated pathways. Saturation kinetics with respect to the 2-vinylphenol were observed, and this may contribute to the high selectivity for hydroacylation over aldehyde decarbonylation. A series of deuterium labelling experiments and Hammett studies support the oxidative addition of Rh to the aldehyde C-H bond as an irreversible and turnover-limiting step. The small bite angle of dcpm is crucial for lowering the barrier of this step and providing excellent reactivity with a variety of aldehydes.
Starting Page	174
Ending Page	180
Page Count	7
File Format	PDF HTM / HTML
PubMed reference number	25580215
Journal	Medline
Volume Number	6
Alternate Webpage(s)	http://www.rsc.org/suppdata/sc/c4/c4sc02026j/c4sc02026j1.pdf
Journal	Chemical science
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article

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