1,2‐Chiralitätstransfer bei der Synthese von Cyclopropanen

Wessig, Pablo; Mühling, Olaf

doi:10.1002/ange.200501481

Cited by 9 publications

(2 citation statements)

References 53 publications

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“…Thus, owing to a hyperconjugative interaction between the C–X σ bond and the semi‐filled π orbital of the excited carbonyl group, the reactants 57 prefer conformation TS‐A in the initial hydrogen transfer step in which the leaving group is arranged pseudoaxially with respect to the cyclic transition state. This phenomenon gave us the idea of developing an entirely new stereoselection principle based on a 1,2‐chirality transfer 33c. The principle of this approach is portrayed in simplified terms in Scheme .…”

Section: Synthetic Applicationsmentioning

confidence: 99%

“…To verify the postulated stereochemical course depicted in Scheme it was necessary to determine the absolute configuration of the preferentially formed enantiomers of compounds 60f – i , which was achieved in most cases by vibrational circular dichroism (VCD) 43. By this method, which is based on a comparison of experimental and calculated VCD spectra, we unambiguously determined the absolute configurations of 60f – h 33c…”

Section: Synthetic Applicationsmentioning

confidence: 99%

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Spin‐Center Shift (SCS) – A Versatile Concept in Biological and Synthetic Chemistry

Wessig

Muehling

2007

Eur J Org Chem

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Reactions involving radical intermediates are nowadays an inherent part of organic chemistry and the impressive progress in this area in recent decades has contributed to the understanding of many biological processes and provided many valuable methods for preparative chemists. By analyzing the mechanism of some biochemical transformations involving radical intermediates a common principle emerges. If at the atom adjacent to an α‐hydroxy or α‐alkoxy radical a leaving group is tethered a rapid elimination takes place and the spin density is shifted by one atom. This concept, called the spin‐center shift (SCS), considerably extends the scope of some radical reactions. This microreview provides an overview of both biochemical examples of the SCS concept and synthetic applications. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Synthetic Applicationsmentioning

confidence: 99%

Section: Synthetic Applicationsmentioning

confidence: 99%

Spin‐Center Shift (SCS) – A Versatile Concept in Biological and Synthetic Chemistry

Wessig

Muehling

2007

Eur J Org Chem

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Copper‐Catalyzed (2+1) Annulation of Acetophenones with Maleimides: Direct Synthesis of Cyclopropanes

Manna

Antonchick

2015

Angewandte Chemie

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A practical copper‐catalyzed direct oxidative cyclopropanation of electron‐deficient alkenes with acetophenone derivatives is reported. The dehydrogenative annulation involves a double CH bond functionalization at the α‐position of the ketone using di‐tert‐butyl peroxide as oxidant. The broad scope of the reaction and excellent functional‐group tolerance is demonstrated for the stereoselective synthesis of fused cyclopropanes. The developed transformation revealed an unprecedented reactivity for copper‐catalyzed processes.

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Dehydroxylative Alkylation of α‐Hydroxy Carboxylic Acid Derivatives via a Spin‐Center Shift

Peng

Zhang

et al. 2022

Angewandte Chemie

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A strategically distinct dehydroxylative alkylation reaction of α‐hydroxy carboxylic acid derivatives with alkenes is developed. The reaction starts with the attack of a 4‐dimethylaminopyridine (DMAP)‐boryl radical to the carbonyl oxygen atom, followed by a spin‐center shift (SCS) to trigger the C−O bond scission. The resulting α‐carbonyl radicals couple with a wide range of alkenes to furnish various alkylated products. This strategy allows for the efficient conversion of a wide array of α‐hydroxy amides and esters derived from several biomass molecules and natural products to value‐added compounds. Experimental and computational studies verified the reaction mechanism.

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1,2‐Chiralitätstransfer bei der Synthese von Cyclopropanen

Cited by 9 publications

References 53 publications

Spin‐Center Shift (SCS) – A Versatile Concept in Biological and Synthetic Chemistry

Spin‐Center Shift (SCS) – A Versatile Concept in Biological and Synthetic Chemistry

Copper‐Catalyzed (2+1) Annulation of Acetophenones with Maleimides: Direct Synthesis of Cyclopropanes

Dehydroxylative Alkylation of α‐Hydroxy Carboxylic Acid Derivatives via a Spin‐Center Shift

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