Access to All‐Carbon Spirocycles through a Carbene and Thiourea Cocatalytic Desymmetrization Cascade Reaction

Zhuo, Shitian; Zhu, Tingshun; Zhou, Liejin; Mou, Chengli; Chai, Huifang; Lu, Yunpeng; Pan, Lu-Tai; Jin, Zhichao; Robin, Yonggui

doi:10.1002/ange.201810638

Cited by 23 publications

(11 citation statements)

References 96 publications

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“… 19 − 22 Most of these reactions proceed via a single catalysis cycle ( Figure 1 A), and there are limitations associated with the use of single NHC catalysis. 23 − 25 In recent years, NHC catalysis has witnessed an expansion by a move toward dual catalysis in which NHC catalysis is merged with acid catalysis, 26 − 33 hydrogen-bond catalysis, 34 , 35 transition-metal catalysis, 36 − 43 or others 44 − 49 ( Figure 1 B). In these processes, the NHC catalysis cycle is interwoven with a second catalysis cycle, where the two cycles have a common intermediate.…”

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confidence: 99%

Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis

2021

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N-Heterocyclic carbene (NHC) catalysis has emerged as a versatile tool in modern synthetic chemistry. Further increasing the complexity, several processes have been introduced that proceed via dual catalysis, where the NHC organocatalyst operates in concert with a second catalytic moiety, significantly enlarging the reaction scope. In biological transformations, multiple catalysis is generally used to access complex natural products. Guided by that strategy, triple catalysis has been studied recently, where three different catalytic modes are merged in a single process. In this Communication, direct α-C–H acylation of various alkenes with aroyl fluorides using NHC, sulfinate, and photoredox cooperative triple catalysis is reported. The method allows the preparation of α-substituted vinyl ketones in moderate to high yields with excellent functional group tolerance. Mechanistic studies reveal that these cascades proceed through a sequential radical addition/coupling/elimination process. In contrast to known triple catalysis processes that operate via two sets of interwoven catalysis cycles, in the introduced process, all three cycles are interwoven.

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Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis

2021

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“…Molecules with a spirocyclo [4,5]decane skeleton have good biological properties due to the important moiety of the quaternary carbon center, which is widely present in various pharmaceutical molecules and natural bioactive products, such as spirojatamol, erythrodiene and cedrene, etc [1][2][3][4][5][6]. However, the key part of the structure of the scaffold containing quaternary carbon is di cult to construct directly in the synthesis due to the large steric repulsion [7][8][9][10][11]. The development of an effective synthesis method is also one of the synthesis problems that need to be overcome, and it has also attracted a large number of chemists to carry out related research work [12][13][14][15].…”

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confidence: 99%

DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether

Zhao¹,

Huo²,

Zhou³

2021

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The DFT calculation of the B3LYP level was carried out to explore the reaction mechanism of the synthesis of spirocyclo[4, 5]decane skeleton by gold-catalyzed allenyl compounds. The more accurate energy under the CH3CN solvent in the experiment is calculated by the single point energy of the SMD model. Computational studies have shown that the reaction consists of three main steps: intramolecular cycloaddition of the end group carbon atoms of allenyl and vinyl groups, the semipinacol rearrangement process in which the four-membered ring is reconstructed into the five-membered ring, the elimination reaction releases the catalyst and obtains the product. The calculation results show that Zheng et al. reported that the gold-catalyzed synthesis reaction can easily occur under the experimental conditions due to its low activation free energy (12.42–16.79 kcal/mol). Furthermore, it was found that the MOMO(CH2)2 substituent has higher reactivity than the corresponding reactant of the phenyl substituent.

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Section: Introductionmentioning

confidence: 99%

DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether

2021

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The DFT calculation of the B3LYP level was carried out to explore the reaction mechanism of the synthesis of spirocyclo [4,5]decane skeleton by gold-catalyzed allenyl compounds. The more accurate energy under the CH3CN solvent in the experiment is calculated by the single point energy of the SMD model. Computational studies have shown that the reaction consists of three main steps: intramolecular cycloaddition of the end group carbon atoms of allenyl and vinyl groups, the semipinacol rearrangement process in which the four-membered ring is reconstructed into the ve-membered ring, the elimination reaction releases the catalyst and obtains the product. The calculation results show that Zheng et al. reported that the gold-catalyzed synthesis reaction can easily occur under the experimental conditions due to its low activation free energy (12.42-16.79 kcal/mol). Furthermore, it was found that the MOMO(CH 2 ) 2 substituent has higher reactivity than the corresponding reactant of the phenyl substituent.

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Access to All‐Carbon Spirocycles through a Carbene and Thiourea Cocatalytic Desymmetrization Cascade Reaction

Abstract: Access to all-carbon spirocycles through a carbene and thiourea cocatalytic desymmetrization cascade reaction

Cited by 23 publications

References 96 publications

Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis

Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis

DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether

DFT study on the gold(I)-catalyzed cycloaddition and rearrangement reactions of allene-containing allylic silyl ether

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