Cyclobutylidenecyclopropane: New Synthesis and Use in 1,3-Dipolar Cycloadditions − A Direct Route to Spirocyclopropane-Annulated Azepinone Derivatives

Meijere, Armin de; Seebach, Malte von; Kozhushkov, Sergei I.; Boese, Roland; Bläser, Dieter; Cicchi, Stefano; Dimoulas, Tula; Brandi, Alberto

doi:10.1002/1099-0690(200110)2001:20<3789::aid-ejoc3789>3.0.co;2-o

Cited by 16 publications

(17 citation statements)

References 30 publications

(13 reference statements)

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“…To gain insights with regard to the hybridization at C 1 and C 2 , and to assess the nature of bound iron in the complex, we initially compared the C 1 -C 2 bond length (1.401 Å) of 24 with X-ray crystallographic data for the length of the terminal C]C of 1,1disubstituted allenes (1.29 Å), 15 and for the corresponding C 1 -C 2 bond of methylenecyclopropanes (1.467 Å). 16 This comparison shows that the C 1 -C 2 bond of 24 is similar to the bonding length which characterizes the analogous carbocycle. In addition, the C 1 -C 2 -C 3 bond angle (149.21 ) of 24 shows considerable deviation from linearity.…”

Section: Resultsmentioning

confidence: 79%

Studies of iron-mediated Pauson–Khand reactions of 1,1-disubstituted-allenylsilanes: mechanistic implications for a reactive three-membered iron metallacycle

et al. 2013

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Section: Resultsmentioning

confidence: 79%

Studies of iron-mediated Pauson–Khand reactions of 1,1-disubstituted-allenylsilanes: mechanistic implications for a reactive three-membered iron metallacycle

et al. 2013

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“…Experimentally, 1,3-DC of nitrone 34 with CBCP gave exclusively isoxazolidine 35 featuring the cyclopropane ring on position 4 of the isoxazolidine ring ( 13 ). 37 …”

Section: Results and Discussionmentioning

confidence: 99%

“Cyclopropylidene Effect” in the 1,3-Dipolar Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational Rationalization

et al. 2021

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The regioselectivity in the 1,3-dipolar cycloaddition (1,3-DC) between five-membered cyclic nitrone and methylenecyclopropane (MCP) has been studied through density functional theory (DFT) calculations. The computational study of 1,3-DC with different 1-alkyl- (or 1,1-dialkyl)-substituted alkenes and the comparison with MCP have evidenced that the electrostatic interaction has a central role in the regioselectivity of the reactions. It has been observed that the electronic effect of the substituent (donor or attractor groups) determines the polarization of the alkene double bond and the reaction mechanism, consequently determining the interaction with nitrones and favoring an orientation between this moiety and the dipolarophile.

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“…Indeed, the thermal rearrangement can occur only under “Flash Vacuum Thermolysis” (FVT) conditions (500 °C, 0.2 mmHg) giving azepinones 27 in modest yields besides other open chain isomers, like 28 , and other products of H‐shift (Scheme 14 in comparison to Scheme 1). [21,23] …”

Section: Comparison Between 5‐spirocyclopropane‐ and 5‐spirocyclobutamentioning

confidence: 99%

Synthesis of β‐Lactams and β‐Homoprolines by Fragmentative Rearrangement of 5‐Spirocyclopropaneisoxazolidines Mediated by Acids

Cordero

Brandi

2020

The Chemical Record

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Azetidinones and β‐amino acids serve as useful building blocks in synthetic organic chemistry and their structural motifs are often found in biologically active compounds. Due to the importance of these compounds, several synthetic strategies have been developed and availability of new synthetic approaches is highly desirable. In this account, we describe the development of an original method that allows the preparation of β‐lactam and β‐homoproline derivatives not easily accessible through traditional processes. The serendipitous discovery made in our lab in 2000 involved the formation of a β‐lactam by heating a mixture of an alkylidenecyclopropane tethered to a formyl group with N‐methylhydroxylamine hydrochloride. Investigation of the process resulted in disclosing an alternative synthetic method of azetidinones based on an acid induced fragmentative rearrangement of cycloadducts of nitrones with suitable methylenecyclopropane derivatives. Herein, the scope of this process is reviewed. In addition, both experimental and computational studies of the mechanism for this peculiar fragmentative rearrangement are presented.

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Cyclobutylidenecyclopropane: New Synthesis and Use in 1,3-Dipolar Cycloadditions − A Direct Route to Spirocyclopropane-Annulated Azepinone Derivatives

Cited by 16 publications

References 30 publications

Studies of iron-mediated Pauson–Khand reactions of 1,1-disubstituted-allenylsilanes: mechanistic implications for a reactive three-membered iron metallacycle

Studies of iron-mediated Pauson–Khand reactions of 1,1-disubstituted-allenylsilanes: mechanistic implications for a reactive three-membered iron metallacycle

“Cyclopropylidene Effect” in the 1,3-Dipolar Cycloaddition of Nitrones to Alkylidene Cyclopropanes: A Computational Rationalization

Synthesis of β‐Lactams and β‐Homoprolines by Fragmentative Rearrangement of 5‐Spirocyclopropaneisoxazolidines Mediated by Acids

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