Computational study on the mechanisms of [2+3] and [2+2] cycloisomerization reaction catalyzed by gold complex

Zhao, Fubo; Lv, Kang; Liu, Tao

doi:10.1016/j.jorganchem.2018.08.016

Cited by 8 publications

(4 citation statements)

References 54 publications

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“…Based on a detailed computational study, Liu et al suggested that the two fused rings were formed via a stepwise cyclization. 683 A similar regiodivergent scenario was found independently by the groups of Toste and Mascarenãs in the gold(I)-catalyzed intermolecular cycloadditions of allenedienes 621. substrates can undergo either (4 + 2) or (4 + 3) cycloadditions to form 6-or 7-membered carbocycles, respectively, via a ligandcontrolled bifurcated mechanism from intermediate 623 (Scheme 135A). 678,682 Interestingly, two specific allenedienes evolve by means of gold(I)-catalyzed [2 + 2] cycloaddition to release fused cyclobutanes 622 and 622′ instead of forming larger rings (Scheme 135B).…”

Section: Synthesis Of Cyclobutanessupporting

confidence: 59%

“…The ligand effect on this transformation was investigated using multivariate analysis, concluding that the selectivity-determining step, which was proposed to be a concerted cyclization to form both rings, was significantly affected by the steric properties of the ligand. Based on a detailed computational study, Liu et al suggested that the two fused rings were formed via a stepwise cyclization …”

Section: Construction Of 4-membered Rings Catalyzed By Goldsupporting

confidence: 57%

“…Based on a detailed computational study, Liu et al suggested that the two fused rings were formed via a stepwise cyclization. 683 …”

Section: Construction Of 4-membered Rings Catalyzed By Goldmentioning

confidence: 99%

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Gold-Catalyzed Synthesis of Small Rings

et al. 2020

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Three- and four-membered rings, widespread motifs in nature and medicinal chemistry, have fascinated chemists ever since their discovery. However, due to energetic considerations, small rings are often difficult to assemble. In this regard, homogeneous gold catalysis has emerged as a powerful tool to construct these highly strained carbocycles. This review aims to provide a comprehensive summary of all the major advances and discoveries made in the gold-catalyzed synthesis of cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, and their corresponding heterocyclic or heterosubstituted analogs.

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Section: Synthesis Of Cyclobutanessupporting

confidence: 59%

Section: Construction Of 4-membered Rings Catalyzed By Goldsupporting

confidence: 57%

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Gold-Catalyzed Synthesis of Small Rings

et al. 2020

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“…Paton and Maseras computationally investigated σ-coordinated Au(I) allenyl cation structures, where these structures were recognized as intermediates in the hydroalkoxylation of allenes reaction . This triggered a number of experimental and computational reports of the functionalization of allenes with a variety of nucleophiles and metals, particularly hydration, , hydroamination, , and hydroalkoxylation, , where gold has been extensively investigated. − Although these studies were mostly focused on kinetics, ligand efficiency, and reversibility aspects of the reactions, a complete account of the reaction mechanism of the hydroalkoxylation of allene is yet to be presented.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Insights into [NHC]Au(I) Catalyzed Hydroalkoxylation of Allenes: A Unified Reaction Valley Approach Study

2021

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Hydroxylation is an effective approach for the synthesis of carbon–oxygen bonds and allylic ethers. The [NHC]Au(I) catalyzed intermolecular hydroalkoxylation of allene was studied at the DFT and Coupled Cluster level of theory. Using the Unified Reaction Valley Approach (URVA), we carry out a comprehensive mechanistic analysis of [NHC]Au(I)-catalyzed and noncatalyzed reactions. The URVA study of several possible reaction pathways reveal that the [NHC]Au(I) catalyst enables the hydroalkoxylation reaction to occur via a two step mechanism based upon the Au ability to switch between π- and σ-complexation. The first step of the mechanism involves the formation of a CO bond after the transition state with no energy penalty. Following the CO bond breakage, the OH bond breaks and CH bond forms during the second step of the mechanism, as the catalyst transforms into the more stable π–Au complex. The URVA results were complemented with local vibrational mode analysis to provide measures of intrinsic bond strength for Au(I)-allene interactions of all stationary points, and NBO analysis was applied in order to observe charge transfer events along the reaction pathway. Overall, the π–Au CC interactions of the products are stronger than those of the reactants adding to their exothermicity. Our work on the hydroxylation of allene provides new insights for the design of effective reaction pathways to produce allylic ethers and also unravels new strategies to form C–O bonds by activation of CC bonds.

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The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2018

Herndon

2019

Coordination Chemistry Reviews

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Computational study on the mechanisms of [2+3] and [2+2] cycloisomerization reaction catalyzed by gold complex

Cited by 8 publications

References 54 publications

Gold-Catalyzed Synthesis of Small Rings

Gold-Catalyzed Synthesis of Small Rings

Theoretical Insights into [NHC]Au(I) Catalyzed Hydroalkoxylation of Allenes: A Unified Reaction Valley Approach Study

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2018

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