Rhodium-Catalyzed Carbonylation of Cyclopropyl Substituted Propargyl Esters: A Tandem 1,3-Acyloxy Migration [5 + 1] Cycloaddition

Shu, Dongxu; Li, Xiaoxun; Zhang, Min; Robichaux, Patrick J.; Guzei, Ilia A.; Tang, Weiping

doi:10.1021/jo300973r

Cited by 48 publications

(9 citation statements)

References 88 publications

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“…In 2011, the Tang group reported an interesting example that involved the generation of allenylcyclopropanes in situ (Scheme ). , This transformation was initiated by the Rh (I)-catalyzed 1,3-acyloxy migration (Saucy–Marbet rearrangement) of propargyl esters 233 , which lead to the formation of allenylcyclopropanes 233 . Subsequently, ring expansion of the allenyl esters 233 occurs to form alkylidene metallacyclohexene intermediates 234 .…”

Section: C–c Bond Cleavage Of Nonactivated Vcpsmentioning

confidence: 99%

Transition Metal-Catalyzed Selective Carbon–Carbon Bond Cleavage of Vinylcyclopropanes in Cycloaddition Reactions

et al. 2020

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In this review, transition metal-catalyzed methodologies and applications that exploit C−C bond cleavage of vinylcyclopropanes (VCPs) are summarized with a focus on cycloaddition and related addition reactions. Transition metals, including palladium, nickel, iron, ruthenium, rhodium, cobalt, and iridium, can catalyze the cleavage of C−C bonds in activated or nonactivated VCPs. Additionally, these bond-breaking reactions can occur as intraor intermolecular processes. The properties of activated and nonactivated VCPs are discussed in the Introduction. Various transition metal-catalyzed cycloaddition and addition reactions involving the cleavage of C−C bonds in activated VCPs are then discussed in the next chapter. The transition metal-catalyzed cycloadditions involving the cleavage of C−C in nonactivated VCPs are summarized in the following chapter. Finally, challenges and potential opportunities are outlined in the last chapter.CONTENTS 3.3. Applications 131 4. Conclusions and Outlook 133

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Section: C–c Bond Cleavage Of Nonactivated Vcpsmentioning

confidence: 99%

Transition Metal-Catalyzed Selective Carbon–Carbon Bond Cleavage of Vinylcyclopropanes in Cycloaddition Reactions

et al. 2020

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“…9). 78,79 A general method was soon developed by the Yu group for the direct [5+1] annulation of VCPs which used [Rh(dppp)]SbF6 or [Rh(dppp)]OTf as catalysts, (Fig. 10).…”

Section: [3+2] Annulationsmentioning

confidence: 99%

Beyond geminal diesters: increasing the scope of metal-mediated vinylcyclopropane annulations while decreasing pre-activation

2018

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The utilization of unactivated substrates in annulation reactions provides access to complex products without the need for subsequent removal of the activating group. Vinylcyclopropanes (VCPs), occurring naturally in several monoterpene natural products, are an important building block for organic chemistry, and can be activated by electron withdrawing substituents directly on the cyclopropane to facilitate ring opening reactions. However, many VCPs that lack these activated groups remain reactive with several group 8, 9 and 10 transition metals, by alternative modes of activation, forming metallacycles. These useful intermediates produce annulation products in reactions with unsaturated π-units, providing rapid access to new carbocycles. Several formal cycloadditions that incorporate unactivated VCPs as substrates have been developed, including [5 + 2], [5 + 2 + 1], [5 + 1 + 2 + 1], [3 + 2], [3 + 2 + 1], [5 + 1], and others, using Rh, Ni, Ru, Ir, Fe and Co based catalysts. Mono- and polycyclic ring systems have been made using these methods with their utility demonstrated through the synthesis of complex natural products. This review will summarize the annulations of VCPs that lack geminal diesters, but retain reactivity via transition metal catalysts.

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“…In the same year, Tang and co-workers developed two different types of tandem reactions for the synthesis of highly functionalized cyclohexenones from cyclopropyl substituted propargyl esters (Scheme 52) [164]. First, different catalysts such as Au, Rh, Ag, and Pd were tested, but no reaction occurred or only the formation of enone.…”

Section: %mentioning

confidence: 99%

Rhodium-Catalyzed Carbonylative Synthesis of Heterocycles

Feng¹,

Wu²

2015

Topics in Heterocyclic Chemistry

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Rhodium-Catalyzed Carbonylation of Cyclopropyl Substituted Propargyl Esters: A Tandem 1,3-Acyloxy Migration [5 + 1] Cycloaddition

Cited by 48 publications

References 88 publications

Transition Metal-Catalyzed Selective Carbon–Carbon Bond Cleavage of Vinylcyclopropanes in Cycloaddition Reactions

Transition Metal-Catalyzed Selective Carbon–Carbon Bond Cleavage of Vinylcyclopropanes in Cycloaddition Reactions

Beyond geminal diesters: increasing the scope of metal-mediated vinylcyclopropane annulations while decreasing pre-activation

Rhodium-Catalyzed Carbonylative Synthesis of Heterocycles

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