Rh<sup>I</sup>‐Catalyzed Benzo/[7+1] Cycloaddition of Cyclopropyl‐Benzocyclobutenes and CO by Merging Thermal and Metal‐Catalyzed CC Bond Cleavages

Xiao-yue, FU; Xiang, Yu; Yu, Zhi‐Xiang

doi:10.1002/chem.201405712

Cited by 45 publications

(19 citation statements)

References 77 publications

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“…With the highly diastereomerically pure benzo-fused bridged cyclic compounds 2 in hand, we hypothesized that if a Schmidt rearrangement reaction can be performed (Fig. 4), which would further extended the structural diversity [49][50][51][52][53] based on this [4 + 4] annulation strategy. In addition, it may be considered as a reaction surrogate for using the oxindole 3 as the annulation substrate, which has been an elusive substrate in C-C bond activation due to the more reactive amide bonds.…”

Section: Resultsmentioning

confidence: 99%

Regioselective activation of benzocyclobutenones and dienamides lead to anti-Bredt bridged-ring systems by a [4+4] cycloaddition

Zhang

Wang

2021

Nat Commun

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To the best of our knowledge, bridgehead carbon benzofused-bridged ring systems have previously not been accessible to the synthetic community. Here, we describe a formal type-II [4 + 4] cycloaddition approach that provides fully sp2-carbon embedded anti-Bredt bicyclo[5.3.1] skeletons through the Rh-catalyzed C1–C8 activation of benzocyclobutenones (BCBs) and their coupling with pedant dienamides. Variously substituted dienamides have been coupled with BCBs to provide a range of complex bicyclo[5.3.1] scaffolds (>20 examples, up to 89% yield). The bridged rings were further converted to polyfused hydroquinoline-containing tetracycles via a serendipitously discovered transannular 1,5-hydride shift/Prins-like cyclization/Schmidt rearrangement cascade.

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Section: Resultsmentioning

confidence: 99%

Regioselective activation of benzocyclobutenones and dienamides lead to anti-Bredt bridged-ring systems by a [4+4] cycloaddition

Zhang

Wang

2021

Nat Commun

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“…In 2015, a new Rh(I)-catalyzed [7 + 1] cycloaddition between intermediates 465 and CO was developed to produce benzocyclooctenones 468 (Scheme 62). 149 In this reaction, a thermal electrocyclic ring opening of the four-membered rings in cyclopropyl-benzocyclobutenes 464 (CP-BCBs) generates the seven-carbon synthons 465. A Rh-catalyzed oxidative addition then converts 465 into eight-membered metallacycles 466.…”

Section: Rhodium Catalysismentioning

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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“…Chem. 2020, 40, 3536～3558 In 2014, Yu and coworkers [72] developed a rhodium-catalyzed benzo-[7＋1] cycloaddition (Scheme 19). They proposed that cyclopropyl-benzocyclobutenes (CP-BCBs) 19-1 can be converted under high temperature to BDCP intermediates, which could then undergo [7＋1] cycloaddition, as the same as that shown in Scheme 18.…”

Section: [7＋1] Cycloadditionsmentioning

confidence: 99%

Transition-Metal-Catalyzed Cycloadditions for the Synthesis of Eight-Membered Carbocycles: an Update from 2010 to 2020

Wang¹,

Yu²

2020

Chin. J. Org. Chem.

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Eight-membered carbocycles are widely found in natural products with significant biological activities and other molecules ranging from perfumes to potential materials. Therefore, accessing these eight-membered carbocycle embedded molecules is important for drug discovery, biological investigation, fragrance industry, material development and many other fields. However, the synthesis of eight-membered carbocycles is still posing challenges to synthetic chemists. Hence, tremendous efforts have been endeavored by many leading chemists to discover and develop new reactions in order to synthesize eight-membered carbocycles. Among these reactions, transition-metal-catalyzed cycloadditions of [m＋n], [m＋n＋o], [m＋ n＋o＋p] have evolved as powerful tools to achieve this aim. This topic has been reviewed in 2010. Summarized here are many new developments in this field and applications of the previously developed reactions in natural product synthesis since then.

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Rh^I‐Catalyzed Benzo/[7+1] Cycloaddition of Cyclopropyl‐Benzocyclobutenes and CO by Merging Thermal and Metal‐Catalyzed CC Bond Cleavages

Cited by 45 publications

References 77 publications

Regioselective activation of benzocyclobutenones and dienamides lead to anti-Bredt bridged-ring systems by a [4+4] cycloaddition

Regioselective activation of benzocyclobutenones and dienamides lead to anti-Bredt bridged-ring systems by a [4+4] cycloaddition

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

Transition-Metal-Catalyzed Cycloadditions for the Synthesis of Eight-Membered Carbocycles: an Update from 2010 to 2020

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RhI‐Catalyzed Benzo/[7+1] Cycloaddition of Cyclopropyl‐Benzocyclobutenes and CO by Merging Thermal and Metal‐Catalyzed CC Bond Cleavages

Cited by 45 publications

References 77 publications

Regioselective activation of benzocyclobutenones and dienamides lead to anti-Bredt bridged-ring systems by a [4+4] cycloaddition

Regioselective activation of benzocyclobutenones and dienamides lead to anti-Bredt bridged-ring systems by a [4+4] cycloaddition

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

Transition-Metal-Catalyzed Cycloadditions for the Synthesis of Eight-Membered Carbocycles: an Update from 2010 to 2020

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Rh^I‐Catalyzed Benzo/[7+1] Cycloaddition of Cyclopropyl‐Benzocyclobutenes and CO by Merging Thermal and Metal‐Catalyzed CC Bond Cleavages