Di-<i>n</i>-butylbis(cyclopentadienyl)zirconium

Negishi, Ei‐ichi; Novák, Tibor

doi:10.1002/047084289x.rd071m

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“…In parallel, we experimentally started by investigating the reactivity of ω-ene cyclopropane 1a (with two identical groups; R 1 = R 2 ) into acyclic product 2a by addition of the Negishi reagent Cp 2 ZrC 4 H 8 , freshly prepared from Cp 2 ZrCl 2 and 2 equiv of n -BuLi at low temperature in Et 2 O as solvent (Scheme ). We were pleased to observe that the Negishi reagent enabled us to convert 1a into 2a as a single E -isomer after hydrolysis in a good isolated yield through the expected allylic C–H bond activation sequence followed by a selective C–C bond cleavage (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Among directionally selective alkene isomerization reactions, Negishi initially showed that treating an olefin with a low-valent zirconocene reagent (Cp 2 ZrC 4 H 8 ) efficiently enabled its long-range migration across methylene chains to, in this case, provide a conjugated diene (Scheme , part I) . This migration reaction, promoted by the later called Negishi reagent, was shown to occur through rapid and successively reversible allylic C–H bond activations.…”

Section: Introductionmentioning

confidence: 99%

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Zirconocene-Mediated Selective C–C Bond Cleavage of Strained Carbocycles: Scope and Mechanism

et al. 2018

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Several approaches using organozirconocene species for the remote cleavage of strained three-membered ring carbocycles are described. ω-Ene polysubstituted cyclopropanes, alkylidenecyclopropanes, ω-ene spiro[2.2]pentanes, and ω-ene cyclopropyl methyl ethers were successfully transformed into stereodefined organometallic intermediates, allowing an easy access to highly stereoenriched acyclic scaffolds in good yields and, in most cases, excellent selectivities. DFT calculations and isotopic labeling experiments were performed to delineate the origin of the obtained chemo- and stereoselectivities, demonstrating the importance of microreversibility.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%