Dirhodium(II) carboxylate-catalysed oxidation of allylic and benzylic alcohols

Moody, Christopher J.; Palmer, Francine N.

doi:10.1016/s0040-4039(01)02048-2

Cited by 28 publications

(7 citation statements)

References 18 publications

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“…Uemura and Patil left a mixture of cyclohexene/ tert -butyl hydroperoxide (TBHP) 1/1 to react in the presence of dirhodium tetraacetate in acetic acid for 3 days, after which the formation of 30% of cyclohexenone and traces of cyclohexenyl acetate (Scheme ) was disclosed . Twenty years later, Moody et al described the application of the same catalyst in the oxidation of allylic and benzylic alcohols to ketones …”

Section: Expanding Dirhodium(ii) Chemistrymentioning

confidence: 99%

“…83 Twenty years later, Moody et al described the application of the same catalyst in the oxidation of allylic and benzylic alcohols to ketones. 84 More recently, it was observed that dirhodium(II) carboxamidates have a much lower oxidation potential than dirhodium(II) carboxylates. 2,85 The cyclic voltammetry data collected for Rh the decrease in the electrophilicity of the rhodium moiety and also a decrease in the rhodium's positive charge.…”

Section: Expanding Dirhodium(ii) Chemistrymentioning

confidence: 99%

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Fine Tuning of Dirhodium(II) Complexes: Exploring the Axial Modification

et al. 2012

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Over the years, dirhodium(II) complexes have had an important role in the synthesis of numerous complex organic molecules because many useful transformations are mediated by this unique family of complexes. The recognized success of this class of catalysts relies on their bimetallic structure. They have a Rh−Rh bond, two axial ligands, and four bridging ligands responsible for controlling the catalyst electrophilicity and, in some cases, provide a mechanism for inducing asymmetry. The modification of the bridge ligand structure has been the main strategy to prepare new complexes, whereas the axial ligands have been considered to have a less important role in catalysis. This concept is changing, and over the past decade, the axial ligand modification was proven to be a valuable and simple strategy to prepare new complexes and achieve new reactivities. In this review a comprehensive overview of this topic is presented, with a particular focus on the changes induced by the axial coordination on the complex properties and reactivity.

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Section: Expanding Dirhodium(ii) Chemistrymentioning

confidence: 99%

Section: Expanding Dirhodium(ii) Chemistrymentioning

confidence: 99%

Fine Tuning of Dirhodium(II) Complexes: Exploring the Axial Modification

et al. 2012

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“…Dirhodium(II) complexes, specifically Rh 2 (OAc) 4 and Rh 2 (pfb) 4 (Figure ), have been reported to have limited activity for allylic oxidation of olefins with tert -butyl hydroperoxide (TBHP) . With poor yields that preclude wide application, little has been done to address the activation of peroxide by dirhodium. , Generally speaking, the most effective catalysts for allylic oxidation, as pointed out by Kochi, are those metals that readily undergo 1-electron redox processes, e.g., Fe 2+ ⇆ Fe 3+ , Cu 1+ ⇆ Cu 2+ , and Co 2+ ⇆ Co 3+ .…”

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confidence: 99%

Dirhodium(II) Caprolactamate: An Exceptional Catalyst for Allylic Oxidation

2004

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The oxidation of organic molecules represents a fundamentally important chemical process. Particularly important is allylic oxidation, whereby a single methylene unit is converted directly into a carbonyl group. In this communication, we report that dirhodium(II) caprolactamate [Rh2(cap)4] in combination with tert-butyl hydroperoxide (terminal oxidant) effectively catalyzes the allylic oxidation of a variety of olefins and enones. The reaction is completely selective, tolerant of air/moisture, and can be performed with as little as 0.1 mol % catalyst in minutes. A mechanistic proposal involving redox chain catalysis has been put forth, as well as evidence for the intermediacy of a higher valent dirhodium tert-butyl peroxy complex.

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“…Apparently, some oxidation tests with BA could be performed even at room temperature for 24 h but the amount of catalyst used in these examples was quite important. However, it can be noticed that other groups describing tests in so mild conditions in the literature proceeded with the addition of a base [50][51][52]. No structural changes upon the catalysis test could be detected.…”

Section: Apatite / Ru(iii) Catalystsmentioning

confidence: 99%

Aerobic Selective Oxidation of Alcohols and Alkanes overHydroxyapatite‐BasedCatalysts

Costentin

Launay

2022

Design and Applications of Hydroxyapatite‐Based Catalysts

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Selective oxidation catalysis is of prime importance for the production of many key intermediates. The control of selectivity in the presence of gaseous oxygen is quite challenging and requires the development of efficient catalysts. Thanks to their large composition range, resulting from the modulation of their stoichiometry and substitution ability, hydroxyapatites can be modified by many metals which make them original catalytic systems gathering both tunable acid-base properties and redox properties. In this chapter, we will show the interest of metal modified hydroxyapatite catalysts for various classes of oxidation reactions. Due to their large range of stability, they can be implemented either in liquid phase for aerobic oxidation of alcohols (Pd, Ru), or at very high temperature (> 600°C) for gas phase alkane oxidation, partial oxidation of methane (Rh, Ni) and oxidative dehydrogenation of other alkanes (V, Co…). The influence of the metal incorporation method (ion exchange, impregnation in excess of solution, or coprecipitation) on the metal dispersion and catalytic performance will be discussed. Finally, the role of the basic properties of hydroxyapatites in the alkane activation will be discussed.

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Dirhodium(II) carboxylate-catalysed oxidation of allylic and benzylic alcohols

Cited by 28 publications

References 18 publications

Fine Tuning of Dirhodium(II) Complexes: Exploring the Axial Modification

Fine Tuning of Dirhodium(II) Complexes: Exploring the Axial Modification

Dirhodium(II) Caprolactamate: An Exceptional Catalyst for Allylic Oxidation

Aerobic Selective Oxidation of Alcohols and Alkanes overHydroxyapatite‐BasedCatalysts

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