Regioselectivity of Pd-catalyzed<i>o</i>-carborane arylation: a theoretical view

Liu, Jiying; Fu, Dongmin; Chen, Zitong; Li, Tiantian; Qu, Lingbo; Li, Shijun; Zhang, Wenjing; Lan, Yu

doi:10.1039/d2qo00046f

Cited by 5 publications

(3 citation statements)

References 103 publications

(97 reference statements)

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“…The lanthanides usually exhibit a number of features in their organometallic chemistry that differ from those of the d -block metals. − The proposed mechanisms for La/Y-catalyzed deoxygenative reduction of tertiary amides with pinacolborane on the basis of DFT calculations are summarized in Scheme . The M(III)-hemiaminal species are found to be the active catalysts for all the three investigated catalysts.…”

Section: Results and Discussionmentioning

confidence: 99%

Exploration of Ligand-Centered Hydride Transfer in La/Y-Catalyzed Deoxygenative Reduction of Tertiary Amides with Pinacolborane

Gao

Chen

et al. 2023

Inorg. Chem.

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A number of rare-earth metals and actinides have proven to be active in a wide variety of atom-efficient transformations. As compared to the related organometallic catalysts, the detailed mechanisms for the rare-earth metal-catalyzed reactions remain largely unexplored. Herein, the detailed catalyst activation process and reaction mechanisms of deoxygenative reduction of amides with pinacolborane (HBpin) catalyzed by Y[N(TMS)2]3 and La[N(TMS)2]3 complexes as well as a La4(O)acac10 cluster are investigated by density functional theory calculations. The M(III)-hemiaminal complex is disclosed to be the active catalyst for both the complexes and the cluster. During catalyst activation for both the Y and La complexes, the H–B bond polarity results in the formation of a transient M(III)-hydride intermediate, which is converted into an on-cycle M(III)-hemiaminal complex via facile migratory insertion. However, this kind of La(III)-hydride species cannot be formed for the La cluster. Starting from the M(III)-hemiaminal complex, the reaction proceeds via the ligand-centered hydride transfer mechanism that involves B–O bond formation, hydride transfer to B, C–O cleavage within the hemiaminal borane, hydride transfer to C, and σ-bond metathesis. The additional HBpin molecule is vital for the first hydride transfer that leads to the formation of [H2Bpin]− species. Our calculations reveal several important cooperative effects of the HBpin component during the hydride transfer processes. The improved mechanistic insights will be helpful for further development of selective CO reduction.

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Section: Results and Discussionmentioning

confidence: 99%

Exploration of Ligand-Centered Hydride Transfer in La/Y-Catalyzed Deoxygenative Reduction of Tertiary Amides with Pinacolborane

Gao

Chen

et al. 2023

Inorg. Chem.

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“…Experimental 5 and theoretical 6 studies on palladium-catalysed B(4,5)-functionalization of o -carboranes have received great attention in recent years (Scheme 1a and b). 7 The reaction mechanism and regioselectivity origins of palladium-catalysed B(4,5)-functionalization of o -carboranes have been well understood.…”

Section: Introductionmentioning

confidence: 99%

Pd-NHC catalysed regioselective activation of B(3,6)–H of o-carborane – a synergy between experiment and theory

Zhang

Chass

et al. 2023

Dalton Trans.

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“…[27] In addition, for either the annulation or the alkenylation, the B(4)-H is specifically activated. As part of our ongoing investigation into origin of the selectivities for o-carborane functionalization, [20,28] herein, possible pathways for decarboxylation and the chemoselectivity and regioselectivity of this iridiumcatalyzed reaction between carboranyl carboxylic acids with alkynes have been studied by using the density functional theory (DFT) method, [29,30] intending to provide theoretical guidance for synthesis of novel carborane derivatives, especially when using carboxyl as the directing group.…”

Section: Introductionmentioning

confidence: 99%

Unraveling origin of chemoselectivity and regioselectivity of iridium‐catalyzed B(4)–H functionalization of o‐carborane by alkyne

Chen

Liu

et al. 2022

J of Physical Organic Chem

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Functionalization at target site is an extremely challenging subject for surface modification of o‐carborane. It is a common tactic to introduce a directing group onto the C(2)–H vertex to induce exclusive B(4,5)–H functionalizations. In this study, was investigated. The computational results indicate that the formal [4 + 2] annulation going via the reductive elimination mechanism has kinetic priority than alkenylation via the decarboxylation mechanism. This is in excellent agreement with the experimental results of carborano‐isocoumarin as the major product. Given the alkyne insertion product, the protonation of alkene is likely to occur before decarboxylation followed by protonation of carborane. The reductive elimination of HOPiv is the regioselectivity determining step, and the non‐covalent interaction analysis discloses that it is the steric repulsion of the methyl on C(1) atom of carborane towards the iridacycle and the Cp* group that causes the higher barrier for the B(3)–H activation, which finally leads to the specific B(4)–H functionalization.

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Regioselectivity of Pd-catalyzedo-carborane arylation: a theoretical view

Abstract: The mechanism and the regioselectivity of Pd-catalyzed B(4)–H arylation and B(4,5)–H diarylation for o-carborane with bidentate directing groups were investigated. The complete catalytic cycle involves Pd-mediated concerted metalation-deprotonation, oxidative addition,...

Cited by 5 publications

References 103 publications

Exploration of Ligand-Centered Hydride Transfer in La/Y-Catalyzed Deoxygenative Reduction of Tertiary Amides with Pinacolborane

Exploration of Ligand-Centered Hydride Transfer in La/Y-Catalyzed Deoxygenative Reduction of Tertiary Amides with Pinacolborane

Pd-NHC catalysed regioselective activation of B(3,6)–H of o-carborane – a synergy between experiment and theory

Unraveling origin of chemoselectivity and regioselectivity of iridium‐catalyzed B(4)–H functionalization of o‐carborane by alkyne

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