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

Wallbaum, Jan; Jones, Peter G.; Werz, Daniel B.

doi:10.1021/acs.joc.5b00330

Cited by 32 publications

(18 citation statements)

References 47 publications

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“…22 The diaryliodonium salts were employed as electrophiles to trap transient o-QM intermediates. Isotope experiments involving D-DMF, 13 C-DMF, and 18 O-DMF were also performed. For unsymmetrical diaryliodonium salts, they creatively integrated a p-anisyl ring to control the chemoselectivity, thereby allowing O-arylation with the other aryl group.…”

Section: Special Topic Synthesismentioning

confidence: 99%

Recent Advances in Construction of C(sp2)–O Bonds via Aryne Participated Multicomponent Coupling Reactions

Peng

Tan

2022

Synthesis

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Aryne chemistry is a powerful synthetic technique that forge new bonds on aromatic rings. The recent resurgence of aryne based multicomponent coupling strategy has led to an influx of methodologies for the mild synthesis of arene derivatives. In particular, these innovative discoveries broaden and streamlines approaches toward phenol ether motifs, which are prevalent structural component across a broad range of chemistry related research field. Herein, this review aims to provide a comprehensive overview on recent progress in construction of C(sp2)-O bonds via aryne induced multicomponent reactions. Special attention has been focused on elucidating the reaction design and mechanistic pathway.

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Section: Special Topic Synthesismentioning

confidence: 99%

Recent Advances in Construction of C(sp2)–O Bonds via Aryne Participated Multicomponent Coupling Reactions

Peng

Tan

2022

Synthesis

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“…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 . In the same year, Fernández, Sierra et al .…”

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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“…Since the first synthesis of cyclopropenones by Breslow, and Vol′pin,, numerous research efforts have been paid on exploring the synthetic value, properties,– and applications– of this fascinating class of compounds. There even was a vivid description for this kind of chemical compounds: “Having a simple appearance outside, yet full of wonder inside, cyclopropenone seems like a miniature carved ivory altarpiece in a Chinese curio box.” As far as we know, cyclopropenones have been utilized as useful building blocks in transition‐metal catalysis,– organocatalysis,, and cycloaddition reactions ,.…”

Section: Methodsmentioning

confidence: 99%

Organocatalytic Regiodivergent C−C Bond Cleavage of Cyclopropenones: A Highly Efficient Cascade Approach to Enantiopure Heterocyclic Frameworks

Cao

Fang

Liu

et al. 2018

Chemistry A European J

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Here a highly efficient cascade approach is reported that combines a cycloaddition reaction with a regioselective strain-release process to afford diverse heterocyclic frameworks through bifunctional catalysis. The cooperation of hydrogen-bonding network activation and a regiodivergent strain-assisted effect is the key to promoting this complex chemical transformation, leading to the generation of two different ring systems in high yields with excellent stereoselectivities. The reaction proceeded by a mechanism involving a "spring-loaded" intermediate with switchable C-C bond cleavages achieved by controllable ring-strain release. This reaction was also amenable to gram scale synthesis with only 0.1 mol % catalyst loading.

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

Cited by 32 publications

References 47 publications

Recent Advances in Construction of C(sp2)–O Bonds via Aryne Participated Multicomponent Coupling Reactions

Recent Advances in Construction of C(sp2)–O Bonds via Aryne Participated Multicomponent Coupling Reactions

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

Organocatalytic Regiodivergent C−C Bond Cleavage of Cyclopropenones: A Highly Efficient Cascade Approach to Enantiopure Heterocyclic Frameworks

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