Homogeneous catalysis. Transition-metal-catalyzed Claisen rearrangements

Schenck, Terry G.; Bosnich, B.

doi:10.1021/ja00293a041

Cited by 142 publications

(53 citation statements)

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“…This Pd(II) versus Pd(0) selectivity was further confirmed by Schenck and Bosnich who studied the rearrangement of allyl imidates using palladium(0), palladium(II), rhodium(I) and iridium(I) [65]. The mechanisms for these reactions were elucidated using a series of chiral substrates and, substrates with specific deuterium labels.…”

Section: Scheme 25supporting

confidence: 55%

Palladium(II)-Catalysed Rearrangement Reactions

Fanning¹,

Jamieson²,

Sutherland³

2006

COC

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The synthesis of new carbon-carbon and carbon-heteroatom bonds in a stereochemically well defined manner still presents a challenge in modern synthetic methodology. An important class of reactions, which can carry out the aforementioned transformations, are the [3,3]-sigmatropic rearrangements. These rearrangements have traditionally been carried out thermally at high temperatures. However, the discovery that these transformations can be accelerated by Pd(II) at ambient temperature has led to more widespread use of these reactions for the synthesis of biologically active and pharmaceutically important molecules.This review presents an overview of the use of palladium(II) catalysis for the acceleration of three of the most commonly used rearrangements in organic chemistry, namely, the Cope, Claisen and aza-Claisen rearrangements. In particular, the mechanism of catalysis, stereochemical outcome and synthetic application of these reactions will be discussed.

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Section: Scheme 25supporting

confidence: 55%

Palladium(II)-Catalysed Rearrangement Reactions

Fanning¹,

Jamieson²,

Sutherland³

2006

COC

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“…The reagent 1-tertbutylimidazoledazole [32] was prepared using published procedures. The Imidoyl chloride was prepared by heating the starting amide and phosphorous pentachloride under vacuum in the absence of solvent [33,34]. (1) tert-Butylimidazole (5.25 g, 42 mmol) was added to an empty Schlenk in a nitrogen glove box.…”

Section: General Proceduresmentioning

confidence: 99%

A nonenolizable imino-N-heterocyclic carbene ligand and corresponding silver (I) metal complex

Coleman

Dastgir

Barnett

et al. 2005

Journal of Organometallic Chemistry

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“…In a study of metal catalyzed aza-Claisen rearrangements, Bosnich proposed that cationic Rh(I) bisphosphine catalysts could undergo oxidative addition to generate a rhodium π-allyl intermediate with the amide anion still bound to rhodium. 22 Analogously, we considered oxidative addition of the allylic sulfoxide to generate a rhodium π-allyl sulfenate complex. A relevant model system was designed to minimize computational cost while maintaining relevance to the experimental system.…”

Section: Resultsmentioning

confidence: 99%

Dynamic Kinetic Resolution of Allylic Sulfoxides by Rh-Catalyzed Hydrogenation: A Combined Theoretical and Experimental Mechanistic Study

et al. 2013

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A dynamic kinetic resolution (DKR) of allylic sulfoxides has been demonstrated by combining the Mislow [2,3]-sigmatropic rearrangement with catalytic asymmetric hydrogenation. The efficiency of our DKR was optimized by using low pressures of hydrogen gas to decrease the rate of hydrogenation relative to the rate of sigmatropic rearrangement. Kinetic studies reveal that the rhodium complex acts as a dual-role catalyst and accelerates the substrate racemization while catalyzing olefin hydrogenation. Scrambling experiments and theoretical modeling support a novel mode of sulfoxide racemization which occurs via a rhodium π-allyl intermediate in polar solvents. In non-polar solvents, however, the substrate racemization is primarily uncatalyzed. Computational studies suggest that the sulfoxide binds to rhodium via O–coordination throughout the catalytic cycle for hydrogenation.

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Homogeneous catalysis. Transition-metal-catalyzed Claisen rearrangements

Cited by 142 publications

References 0 publications

Palladium(II)-Catalysed Rearrangement Reactions

Palladium(II)-Catalysed Rearrangement Reactions

A nonenolizable imino-N-heterocyclic carbene ligand and corresponding silver (I) metal complex

Dynamic Kinetic Resolution of Allylic Sulfoxides by Rh-Catalyzed Hydrogenation: A Combined Theoretical and Experimental Mechanistic Study

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