Cyclopropyl carbenoid insertion into alkenylzirconocenes—a convergent synthesis of alkenylcyclopropanes and alkylidenecyclopropanes

Thomas, E. J.; Kasatkin, Alexander N.; Whitby, Richard J.

doi:10.1016/j.tetlet.2006.10.132

Cited by 27 publications

(6 citation statements)

References 39 publications

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“…This methodology represented the first Whitby et al demonstrated that the cyclopropyl carbenoid insertion into alkenylzirconocenes constituted a convergent synthesis of alkylidenecyclopropanes. [104] Indeed, the insertion of cyclopropyl carbenoid 184 into alkenylzirconocene 185 afforded the corresponding allylzirconium species 186 which reacted with aldehydes to give the corresponding alkylidenecyclopropanes 187a, b in moderate to good yields, as shown in Scheme 59.…”

Section: Miscellaneous Reactionsmentioning

confidence: 99%

Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives

Audran

Pellissier

2010

Adv Synth Catal

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Since the methylenecyclopropane moiety is found in many biologically active natural substances, the synthesis of methylene-and alkylidenecyclopropanes remains a considerable challenge. In addition, an attractive feature is their surprising stability, accompanied by a high level of strain, conferring on them an otherwise unattainable chemical reactivity. The growing interest in the chemistry of these compounds has in its turn stimulated the development of alternative approaches to their skeleton, aimed at selectively introducing structural and chemical diversification. The three principal methods to synthesize these important compounds are based on the formation of the cyclopropane ring, the use of preformed cyclopropanes, and the use of preformed methyleneand alkylidenecyclopropanes.

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Section: Miscellaneous Reactionsmentioning

confidence: 99%

Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives

Audran

Pellissier

2010

Adv Synth Catal

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“…The insertion of isocyanides into MC bonds is one of the powerful means for carbon chain construction, and has been utilized as a key step in organic synthesis 1–8. The resulting η 2 ‐iminoacyl–metal intermediates in this process, such as η 2 ‐iminoacylZr complexes,2, 3 can be conveniently converted to one‐carbon elongated products such as imines,7b aldehydes,7c–f or nitriles7g, h through the cleavage of various chemical bonds, including ZrC, CN, and N‐R’ bonds (Scheme a). η 2 ‐IminoacylZr complexes also displayed other useful reactivities, including reductive elimination (Scheme b),2n [1,2]‐alkyl shift of nonacyl ZrC bonds (Scheme c),4, 5f and other types of rearrangements 5.…”

Section: Introductionmentioning

confidence: 99%

Efficient One‐Pot Synthesis of N‐Containing Heterocycles by Multicomponent Coupling of Silicon‐Tethered Diynes, Nitriles, and Isocyanides through Intramolecular Cyclization of IminoacylZr Intermediates

Zhang

2010

Chemistry A European J

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An efficient multicomponent synthesis of 5-azaindoles and dihydropyrrolo[3,2-c]azepines was achieved by zirconocene-mediated coupling of silicon-tethered diynes, nitriles, and isocyanides. The synthesis, structures, and intramolecular cyclization of mono- and bis(iminoacyl)--Zr intermediates were investigated to elucidate the reaction process. Upon hydrolysis, the isolated mono(iminoacyl)--Zr intermediates underwent intramolecular cyclization to afford tetrasubstituted 5-azaindoles, whereas intramolecular cyclization of bis(iminoacyl)--Zr intermediates led to the formation of dihydropyrrolo[3,2-c]azepines. The structure of a bis(iminoacyl)--Zr intermediate, formed through insertion of two molecules of CyNC into the Zr--C bond, and structures of two dihydropyrrolo[3,2-c]azepines were characterized by single-crystal X-ray structural analysis.

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“…1, bottom). Because Whitby's 3-component cyclization results in either heteroatom-or vinyl-substitution at this position, 21,22 we considered the alternative synthetic approach that is outlined in Fig. 1, where the installation of R 3 would be accomplished through functionalization of tetrasubstituted olefin 1.…”

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confidence: 99%

Development of a new class of liver receptor homolog-1 (LRH-1) agonists by photoredox conjugate addition

Cornelison

Cato

Johnson

et al. 2020

Preprint

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Article history:Received Revised Accepted Available online LRH-1 is a nuclear receptor that regulates lipid metabolism and homeostasis, making it an attractive target for the treatment of diabetes and non-alcoholic fatty liver disease. Building on recent structural information about ligand binding from our labs, we have designed a series of new LRH-1 agonists that further engage LRH-1 through added polar interactions. While the current synthetic approach to this scaffold has, in large part, allowed for decoration of the agonist core, significant variation of the bridgehead substituent is mechanistically precluded. We have developed a new synthetic approach to overcome this limitation, identified that bridgehead substitution is necessary for LRH-1 activation, and described an alternative class of bridgehead substituents for effective LRH-1 agonist development. We determined the crystal structure of LRH-1 bound to a bridgehead-modified compound, revealing a promising opportunity to target novel regions of the ligand-binding pocket to alter LRH-1 target gene expression..

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Cyclopropyl carbenoid insertion into alkenylzirconocenes—a convergent synthesis of alkenylcyclopropanes and alkylidenecyclopropanes

Cited by 27 publications

References 39 publications

Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives

Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives

Efficient One‐Pot Synthesis of N‐Containing Heterocycles by Multicomponent Coupling of Silicon‐Tethered Diynes, Nitriles, and Isocyanides through Intramolecular Cyclization of IminoacylZr Intermediates

Development of a new class of liver receptor homolog-1 (LRH-1) agonists by photoredox conjugate addition

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