Synthesis of Oxaspiranic Compounds through [3 + 2] Annulation of Cyclopropenones and Donor–Acceptor Cyclopropanes

Rivero, Alexandra R.; Fernández, Israel; Arellano, Carmen Ramírez de; Sierra, Miguel Á.

doi:10.1021/jo502292y

Cited by 45 publications

(11 citation statements)

References 46 publications

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“…Therefore, we turned our attention to cyclopropenones. Because of their aromatic character and the resulting zwitterionic structure, they bear an extremely nucleophilic oxygen which has been used in various ring-opening and ring-enlargement processes . In addition, the strained three-membered ring decreases the steric congestion around the carbon–oxygen double bond, thus facilitating the reaction.…”

mentioning

confidence: 99%

Reacting Cyclopropenones with Arynes: Access to Spirocyclic Xanthene–Cyclopropene Motifs

Wallbaum¹,

Jones

Werz³

2015

J. Org. Chem.

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A formal insertion of two aryne moieties into the carbon-oxygen double bond of cyclopropenone has been realized. Spirocyclic xanthene-cyclopropene scaffolds were obtained. Mechanistically, a sequence of a formal [2 + 2]-cycloaddition followed by electrocyclic ring opening and a terminating [4 + 2]-type cycloaddition is postulated. The use of an electron-rich aryne precursor led to ring cleavage of the cyclopropene to afford an unprecedented xanthylium salt.

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mentioning

confidence: 99%

Reacting Cyclopropenones with Arynes: Access to Spirocyclic Xanthene–Cyclopropene Motifs

Wallbaum¹,

Jones

Werz³

2015

J. Org. Chem.

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“…Although the reactivity of D‐A cyclopropanes has been intensively investigated during the last decades, the use of a ferrocenyl group as donor in D‐A cyclopropane chemistry remains almost unexplored. To the best of our knowledge, only one isolated example of a [3+2] cycloaddition reaction of D‐A cyclopropane 1 r with diphenylcyclopropenone has been reported in the literature . Specifically, no arylation reactions with electron‐rich (hetero)arenes have been reported so far.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Functionalized Ferrocene Derivatives from Donor−Acceptor Cyclopropanes

González‐Pelayo

López

2018

ChemPlusChem

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The TfOH‐catalyzed reaction of aryl‐substituted donor–acceptor cyclopropane derivatives with ferrocene provided new functionalized ferrocene derivatives. This process exhibited a reasonable scope with respect to the cyclopropane component affording the corresponding alkylated ferrocene derivatives in useful yields. An alternative approach to these functionalized ferrocene derivatives involving arylation of a ferrocene‐decorated donor–acceptor cyclopropane derivative is also disclosed. Both processes rely on a facile regioselective ring‐opening of the donor−acceptor cyclopropane.

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“…In the same year, Fernández, Sierra et al . realized a Lewis acid promoted [3+2]‐cycloaddition of donor‐acceptor cyclopropanes (DAC) with cyclopropenones, affording various biologically important 4‐oxaspiro[2.4]hept‐1‐ene derivatives in good yields . Despite these elegant reports, it is still highly desirable to develop new [2+m]‐cycloaddition reactions of cyclopropenones, which will provide new appealing chemistry for the synthesis of more diverse spirocyclic structures.…”

Section: Methodsmentioning

confidence: 99%

[3+2]‐Cycloaddition of Azaoxyallyl Cations with Cyclopropenones and Cyclopropenethiones: Synthesis of Spirocyclic Oxazole and Thiazole Derivatives

2019

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A [3 + 2]-cycloaddition reaction of in-situ-formed azaoxyallyl cations with cyclopropenones and cyclopropenethiones for the synthesis of biologically important spirocyclic oxazole and thiazole derivatives is reported. This concise procedure exhibited good functional group tolerance under very mild conditions and provided the corresponding spirocyclic products in good to excellent yields.Cycloaddition reaction is one of the most powerful strategies to build molecular complexity into carbocycles and heterocycles., [1] Since it was firstly prepared by the group of Breslow and the group of Vol'pin in 1959, [2] cyclopropenones have been extensively applied into cycloaddition reactions due to their high reactivity profile in the preparation of diverse cyclic molecules. [3] Generally, cyclopropenones involved cycloaddition reactions can be divided into the following three categories: (a) [3 + m]-cycloaddition of cyclopropenones by C1À C2 single bond cleavage (Scheme 1, path A); [4] (b) [2 + m]-cycloaddition of the C=C double bond(Scheme 1, path B); [5] (c) [2 + m]-cycloaddition of carbonyl moiety in cyclopropenones, thus leading to the formation of spirocyclic compounds (Scheme 1, path C). [6] The first strain release CÀ C bond cleavage processes are generally proceeded with the assistance with organo-or transition-metal catalysts. Compared with this most intriguing and well-developed [3 + m]-cycloaddition process, application of latter two types of [2 + m]-cycloaddition strategy is relatively overlooked, especially for synthesis spirocyclic compounds.In 2015, Werz and co-workers reported the synthesis of spirocyclic xanthene-cyclopropene scaffolds by using [2 + 2]cycloaddition of cyclopropenones with arynes as the key step. [6b] In the same year, Fernández, Sierra et al. realized a Lewis acid promoted [3 + 2]-cycloaddition of donor-acceptor cyclopropanes (DAC) with cyclopropenones, affording various biologically important 4-oxaspiro[2.4]hept-1-ene derivatives in [a] S.General procedure: A flame-dried flask equipped with a magnetic stir bar was charged with 1 a (1.0 equiv., 0.2 mmol), 2 a (2.0 equiv., 0.4 mmol), K 2 CO 3 (2.0 equiv., 0.8 mmol) and HFIP (2.0 mL). After that, the reaction mixture was stirred at 50°C for 12 h. The solvent was then removed under reduced pressure with the aid of a rotary evaporator. The crude residue was purified by silica gel column chromatography to afford pure product 3 a as a white solid in 70% yield.

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Synthesis of Oxaspiranic Compounds through [3 + 2] Annulation of Cyclopropenones and Donor–Acceptor Cyclopropanes

Cited by 45 publications

References 46 publications

Reacting Cyclopropenones with Arynes: Access to Spirocyclic Xanthene–Cyclopropene Motifs

Reacting Cyclopropenones with Arynes: Access to Spirocyclic Xanthene–Cyclopropene Motifs

Synthesis of Functionalized Ferrocene Derivatives from Donor−Acceptor Cyclopropanes

[3+2]‐Cycloaddition of Azaoxyallyl Cations with Cyclopropenones and Cyclopropenethiones: Synthesis of Spirocyclic Oxazole and Thiazole Derivatives

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