Strain-Release-Controlled [4 + 2 + 1] Reaction of Cyclopropyl-Capped Diene-ynes/Diene-enes and Carbon Monoxide Catalyzed by Rhodium

Li, Chen‐Long; Yang, Yusheng; Zhou, Yi; Duan, Zhao-Chen; Yu, Zhi‐Xiang

doi:10.1021/jacs.3c00134

Cited by 7 publications

(8 citation statements)

References 70 publications

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Section: Resultsmentioning

confidence: 99%

“…Geometry optimizations of all of the minima and transition states were carried out with the BMK functional in the gas phase, and the def2-TZVP basis set was used for all atoms. The BMK functional performed well in our previously reported [4 + 2 + 1] cycloaddition of cyclopropyl-capped diene-ynes/diene-enes with CO and was used in this study as well. Enthalpy and Gibbs free energy corrections were obtained through frequency analyses at 298 K. Solvent effects were considered based on gas-phase-optimized structures using the same basis set and functional.…”

Section: Methodsmentioning

confidence: 99%

“…This strain (which is actually called angular strain) can be estimated to be around 12 kcal/mol by comparing the reaction thermodynamics for the hydrogenation of CP-capped diene and common diene shown in Scheme 2. 8 A comparison of Gibbs free energy profiles of model reactions 1 and 2 shows that the CO coordination, CO insertion, and reductive elimination steps are very similar. For ).…”

Section: Computational Study On the Mechanisms Of [4 + 1] Reactions O...mentioning

confidence: 98%

“…This conclusion can also be kept if one considers the pathway of TS2b→IN4b→TS3b for model reaction 1 because the strain release makes TS2b easier. Similar reactions driven by strain release from MCPs include Cope rearrangement of CP-capped 1,5-dienes by Tantillo and Gagne, 16 the Diels−Alder reaction of CP-capped dienes with alkenes, 17 and our recent [4 + 2 + 1] reaction of CP-capped diene-ynes/diene-enes and CO. 8 Here, we want to mention that, since we do not know the resting state of the [4 + 1] reactions, the activation free energy for model reaction 2 could be higher than 29.4 kcal/mol and the reaction would become more difficult. That is why reaction b in Scheme 1 failed.…”

Section: Computational Study On the Mechanisms Of [4 + 1] Reactions O...mentioning

confidence: 99%

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Rh-Catalyzed [4 + 1] Reaction of Cyclopropyl-Capped Dienes (but not Common Dienes) and Carbon Monoxide: Reaction Development and Mechanistic Study

Yang,

Li,

Zhu

et al. 2023

J. Am. Chem. Soc.

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reaction of dienes and carbon monoxide (CO) is the most straightforward and easily envisioned cyclization for the synthesis of fivemembered carbocycles, which are ubiquitously found in natural products and functional molecules. Unfortunately, no test of this reaction was reported, and consequently, chemists do not know whether such kind of reaction works or not. Herein, we report that the [4 + 1] reaction of common dienes and CO cannot work, at least under the catalysis of [Rh(cod)Cl] 2 . However, using cyclopropyl-capped dienes (also named allylidenecyclopropanes) as substrates, the corresponding [4 + 1] reaction with CO proceeds smoothly in the presence of [Rh(cod)Cl] 2 . This [4 + 1] reaction, with a broad scope, provides efficient access to five-membered carbocyclic compounds of spiro[2.4]hept-6-en-4-ones. The [4 + 1] cycloadducts can be further transformed into other molecules by using the unique chemistry of cyclopropyl groups present in these molecules. The mechanism of this [4 + 1] reaction has been investigated by quantum chemical calculations, uncovering that cyclopropyl-capped dienes are strained dienes and the oxidative cyclization step in the [4 + 1] catalytic cycle can release this (angular) strain both kinetically and thermodynamically. The strain release in this step then propagates to all followed CO coordination/CO insertion/reductive elimination steps in the [4 + 1] catalytic cycle, helping the realization of this cycloaddition reaction. In contrast, common dienes (including cyclobutyl-capped dienes) do not have such advantages and their [4 + 1] reaction suffers from energy penalty in all steps involved in the [4 + 1] catalytic cycle. The reactivity of ene-allenes for the [4 + 1] reaction with CO is also discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Computational Study On the Mechanisms Of [4 + 1] Reactions O...mentioning

confidence: 98%

Section: Computational Study On the Mechanisms Of [4 + 1] Reactions O...mentioning

confidence: 99%

See 2 more Smart Citations

Rh-Catalyzed [4 + 1] Reaction of Cyclopropyl-Capped Dienes (but not Common Dienes) and Carbon Monoxide: Reaction Development and Mechanistic Study

Yang,

Li,

Zhu

et al. 2023

J. Am. Chem. Soc.

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“…However, unlike five- or six-membered rings, seven-membered carbocycles are challenging to construct due to their ring strain and entropic disadvantages. In addition, the shortage of commercially available cycloheptanoid starting materials and the high reactivity of the cycloheptanoid intermediates leading to other side reactions make the construction of seven-membered carbocycles highly challenging . Intramolecular Michael addition reaction of α,β -unsaturated ketone represents an efficient strategy for synthesis of cyclic compounds .…”

mentioning

confidence: 99%

Approach to Seven-Membered Carbocycles via a Lewis Acid Catalyzed Intramolecular Michael Addition of Allenone

et al. 2023

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A straightforward strategy for constructing seven-membered carbocycles by employing a Lewis acid catalyzed intramolecular Michael addition of allenones is reported. It offers atom-economic access to synthetically important furan-fused bi- or tricyclic frameworks containing seven-membered carbocycles, which are widely found in natural products possessing various bioactivities. A number of seven-membered carbocycle-containing polycyclic frameworks bearing diverse functional groups were prepared in good to excellent yields. Furthermore, the application potential of this strategy was exemplified by the construction of the key skeletons of Caribenol A and Frondosin B.

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Transition‐Metal‐Catalyzed Transformations Involving the Heck Reaction

2023

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Elaborated molecular architectures including complex carbocycles, heterocycles, and polycyclic molecular structures represent an important class of organic compounds because they are ubiquitous structural units in a broad variety of biologically and pharmacologically relevant natural products, medicinal molecules, and functional materials. A major challenge in modern synthetic methodology is the development of strategically efficient and selective construction of these compounds from readily available starting materials. Transition‐metal‐catalyzed transformations involving Heck reaction as the pivotal step have afforded a powerful approach for accessing sophisticated polycyclic skeletons from a set of easy‐to handle starting materials, thus highlighting its potential significance in streamlining the drug discovery process. Over the past few decades, significant effort has been devoted to accessing complex polycyclic derivatives in efficient and versatile routes, and a number of powerful and direct synthetic strategies have been reported. In this review, the latest advances in transition‐metal‐catalyzed transformations involving Heck reaction as the critical step are summarized, which could be divided into six categories: 1) Heck/Sonogashira tandem reaction; 2) Heck/Suzuki tandem reaction; 3) Heck/Heck tandem reaction; 4) Heck/Hiyama tandem reaction; 5) Heck/Cacchi tandem reaction; 6) Heck/C−H bond functionalization tandem reaction.

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Strain-Release-Controlled [4 + 2 + 1] Reaction of Cyclopropyl-Capped Diene-ynes/Diene-enes and Carbon Monoxide Catalyzed by Rhodium

Cited by 7 publications

References 70 publications

Rh-Catalyzed [4 + 1] Reaction of Cyclopropyl-Capped Dienes (but not Common Dienes) and Carbon Monoxide: Reaction Development and Mechanistic Study

Rh-Catalyzed [4 + 1] Reaction of Cyclopropyl-Capped Dienes (but not Common Dienes) and Carbon Monoxide: Reaction Development and Mechanistic Study

Approach to Seven-Membered Carbocycles via a Lewis Acid Catalyzed Intramolecular Michael Addition of Allenone

Transition‐Metal‐Catalyzed Transformations Involving the Heck Reaction

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