Complexes of rhenium(V) with cyclic sulfides: Catalysts of hydrogenation and isomerization of olefins

Gvinter, L. I.; Borunova, N. V.; Akhmadieva, R. G.; Antseva, N. V.; Yusupova, N. A.; Numanov, I. U.; Sharf, V. Z.

doi:10.1007/bf01455466

Cited by 3 publications

(3 citation statements)

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“…Gvinter et al synthesized various rhenium complexes from oxopentachloro(oxopentabromo)rhenic acid with cyclic sulfurcontaining ligands, viz., thiophane and 2-propylthiophane, and examined their activity toward the hydrogenation and isomerization of olefins and dienes. 846 They showed that the catalytic activity of the complexes was a function of the ligand environment, the nature of the substrate, the reaction conditions, and the solvent used in the experiments. They studied the reactions in methanol and toluene and demonstrated that the rate of conversion in methanol was higher than in toluene.…”

Section: Miscellaneous Transition Metal Catalystsmentioning

confidence: 99%

Isomerization of Allylbenzenes

et al. 2015

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Section: Miscellaneous Transition Metal Catalystsmentioning

confidence: 99%

Isomerization of Allylbenzenes

et al. 2015

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“…To our knowledge, this is the first successful Zselective isomerization of this important class of alkenes. 3,44,45 Alcohols and ketones are not tolerated by 1, but catalysis with 1 proceeds with silyl ethers (protected alcohol) and acetals (protected ketone), with slightly lower Z selectivity and high regioselectivity (<1% other internal isomers) (entries 9 and 11). Moreover, 1 is compatible with silyl groups despite a decrease in the Z selectivity and regioselectivity (<2% other internal isomers) (entry 10).…”

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confidence: 96%

“…1 can also selectively isomerize various phenylpropenoids (allylarenes, entries 4–8) with high Z selectivity. To our knowledge, this is the first successful Z -selective isomerization of this important class of alkenes. ,, …”

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Highly Z-Selective Double Bond Transposition in Simple Alkenes and Allylarenes through a Spin-Accelerated Allyl Mechanism

et al. 2021

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Double-bond transposition in alkenes (isomerization) offers opportunities for the synthesis of bioactive molecules, but requires high selectivity to avoid mixtures of products. Generation of Z-alkenes, which are present in many natural products and pharmaceuticals, is particularly challenging because it is usually less thermodynamically favorable than generation of the E isomers. We report a β-dialdiminate-supported, high-spin cobalt(I) complex that can convert terminal alkenes, including previously recalcitrant allylbenzenes, to Z-2-alkenes with unprecedentedly high regioselectivity and stereoselectivity. Deuterium labeling studies indicate that the catalyst operates through a π-allyl mechanism, which is different from the alkyl mechanism that is followed by other Z-selective catalysts. Computations indicate that the triplet cobalt(I) alkene complex undergoes a spin state change from the restingstate triplet to a singlet in the lowest-energy C−H activation transition state, which leads to the Z product. This suggests that this change in spin state enables the catalyst to differentiate the stereodefining barriers in this system, and more generally that spin-state changes may offer a route toward novel stereocontrol methods for first-row transition metals.

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Piperylene—A Versatile Basic Chemical in Catalysis

Behr

Neubert

2013

ChemCatChem

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Today’s industrial chemistry heavily relies on petrochemical feedstocks, and most of the starting compounds are available from the convenient steam cracking of hydrocarbons. In particular, the short‐chain key compounds ethene and propene take center stage. In addition, low‐molecular‐weight conjugated dienes such as butadiene and isoprene have remarkable importance in the production of polymers and fine chemicals. Another, so far clearly underrated, short‐chain conjugated diene is piperylene (1,3‐pentadiene), which is also available from the steam cracking of naphtha. The goal of this review is to illustrate the high potential of piperylene as a suitable starting compound in the area of fine chemicals by using transition‐metal catalysis.

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Complexes of rhenium(V) with cyclic sulfides: Catalysts of hydrogenation and isomerization of olefins

Cited by 3 publications

References 1 publication

Isomerization of Allylbenzenes

Isomerization of Allylbenzenes

Highly Z-Selective Double Bond Transposition in Simple Alkenes and Allylarenes through a Spin-Accelerated Allyl Mechanism

Piperylene—A Versatile Basic Chemical in Catalysis

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