Theoretical Study of Ruthenium(0)-Catalyzed Transfer Hydrogenative Cycloaddition of Cyclohexadiene and Norbornadiene with 1,2-Diols to Form Bridged Carbocycles

Tian, Zhong‐Qun; Li, Ting; Wu, Xiajun; Li, Juan

doi:10.1021/acs.joc.8b03276

Cited by 4 publications

(2 citation statements)

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“…181 Remarkably, the transformation is redox-independent and can be conducted from the diol, ketol, or 1,2-dione oxidation levels (not shown). The proposed mechanism, which was corroborated by computational studies performed by Li in 2019, 182 is initiated by 1,2-dione-norbornadiene oxidative coupling to form an oxaruthenacycle, which inserts the appendant ketone to form a dioxaruthenacycle. Ketol-mediated transfer hydrogenolysis of the dioxaruthenacycle delivers the exo-cycloadduct and regenerates the requisite ketone.…”

Section: [2+2+2] Cycloadditions Of Cod and Nbd As 2 2πmentioning

confidence: 94%

Ruthenium-Catalyzed Cycloadditions to Form Five-, Six-, and Seven-Membered Rings

Doerksen

Hodík

et al. 2021

Chem. Rev.

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Ruthenium-catalyzed cycloadditions to form five-, six-, and seven-membered rings are summarized, including applications in natural product total synthesis. Content is organized by ring size and reaction type. Coverage is limited to processes that involve formation of at least one C–C bond. Processes that are stoichiometric in ruthenium or exploit ruthenium as a Lewis acid (without intervention of organometallic intermediates), ring formations that occur through dehydrogenative condensation-reduction, σ-bond activation-initiated annulations that do not result in net reduction of bond multiplicity, and photochemically promoted ruthenium-catalyzed cycloadditions are not covered.

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Section: [2+2+2] Cycloadditions Of Cod and Nbd As 2 2πmentioning

confidence: 94%

Ruthenium-Catalyzed Cycloadditions to Form Five-, Six-, and Seven-Membered Rings

Doerksen

Hodík

et al. 2021

Chem. Rev.

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“…The authors proposed that, following rhodium-catalyzed C(sp 3 )–H bond activation, an allylic alcohol can coordinate to the rhodium catalyst, thereby bringing it in close proximity to the coupling partner and enabling a facile 1,2-migratory insertion to generate a new C–C bond. In general, allyl alcohols have been highly explored in C–C bond-forming Heck-type pathways controlled by the directing capacity of alkoxide, and modern advances have seen the employment of new metal catalysts and an expanded range of coupling partners. − …”

Section: Chain Functionalizationmentioning

confidence: 99%

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Cook,

Newman

2024

Chem. Rev.

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Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods for their functionalization require them to first be converted into a more activated derivative, while recent years have seen a vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can be used toward this goal. These transformations are broadly classified into three categories. Deoxygenative functionalizations, representing derivatization of the C−O bond, enable the alcohol to act as a leaving group toward the formation of new C−C bonds. Etherifications, characterized by derivatization of the O−H bond, represent classical reactivity that has been modernized to include mild reaction conditions, diverse reaction partners, and high selectivities. Lastly, chain functionalization reactions are described, wherein the alcohol group acts as a mediator in formal C−H functionalization reactions of the alkyl backbone. Each of these three classes of transformation will be discussed in context of intermolecular arylation, alkylation, and related reactions, illustrating how catalysis can enable alcohols to be directly harnessed for organic synthesis.

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Mechanism and Origin of Chemoselectivity of Ru-Catalyzed Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones

Liu

Tang

et al. 2020

J. Org. Chem.

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Ru-catalyzed cross-coupling of secondary alcohols with only byproducts H 2 and H 2 O provides a green synthetic strategy to prepare β-disubstituted ketones. Density functional theory (DFT) calculations were performed with the coupling of 1-phenylethanol and cyclohexanol as a model reaction to gain deeper mechanistic insights herein. The mechanistic details of the main reaction and the key steps of possible side reactions were clarified, and the obtained results are consistent with reported selectivity. Hydrogenation of α,β-unsaturated ketones and dehydrogenation of ruthenium hydride intermediate are direct chemoselectivity-determining stages. The hydrogenation via 1,4-addition generates more stable intermediates, being favored over that via 1,2-addition, and thus avoids the formation of alkene products. The conjugation and π−π stacking effects of phenyl and the weak electronic effect of alkyls explain the dominance of specific ketone products in the hydrogenation stage. Hydrogenation of ketone products is kinetically operative but not exergonic enough to stop the irreversible dihydrogen release in an open reaction system, and thus alcohol products are absent. Furthermore, water evaporation in aldol condensation is found to be a double-edged sword, as it can accelerate the hydrogenation stage to prevent α,β-unsaturated ketones from being the main products but decrease the selectivity therein from thermodynamics overall.

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Theoretical Study of Ruthenium(0)-Catalyzed Transfer Hydrogenative Cycloaddition of Cyclohexadiene and Norbornadiene with 1,2-Diols to Form Bridged Carbocycles

Cited by 4 publications

References 84 publications

Ruthenium-Catalyzed Cycloadditions to Form Five-, Six-, and Seven-Membered Rings

Ruthenium-Catalyzed Cycloadditions to Form Five-, Six-, and Seven-Membered Rings

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Mechanism and Origin of Chemoselectivity of Ru-Catalyzed Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones

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