Recent aspects of cyclopropanone chemistry

Wasserman, Harry H.; Clark, George M.; Turley, Patricia C.

doi:10.1007/3-540-06648-9_9

Cited by 35 publications

(28 citation statements)

References 123 publications

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“…1). These results allow us to establish that the X 2 -Y 3 bonds in molecules (1), (2) and (3) are quite unstable.…”

Section: -Y 3 Bondmentioning

confidence: 88%

“…If these two critical points coalesce, they annihilate corresponding to bond rupture and concomitant ring opening. In molecules (1), (2) and (3), the X 2 -Y 3 bonds have relatively large e (0.67, 2.03 and 4.61, respectively) compared to unstrained species (e.g., e = 0.01 for C-C bond in cyclohexane). In addition, in all these molecules, the RCP is closer to the X 2 -Y 3 BCP than to the C 1 -X 2 and C 1 -Y 3 BCPs (see Fig.…”

Section: -Y 3 Bondmentioning

confidence: 99%

“…Moreover, a-lactones (oxiran-2-ones) are three-membered heterocyclic rings that have been invoked as intermediates in a variety of organic reactions [7][8][9][10]. Many of the chemical reactions of the a-lactones have been explained by invoking a higher-energy ring-opened zwitterionic form (2). The relative stability of ring-closed form (1) versus ring-opened form (2) is dependent on the substituent R. Calculations have predicted that for the parent a-lactone (R=H), ring-closed form (1) is significantly lower in energy than ring-opened form (2) [11][12][13][14][15].…”

Section: Introductionmentioning

confidence: 99%

“…Many of the chemical reactions of the a-lactones have been explained by invoking a higher-energy ring-opened zwitterionic form (2). The relative stability of ring-closed form (1) versus ring-opened form (2) is dependent on the substituent R. Calculations have predicted that for the parent a-lactone (R=H), ring-closed form (1) is significantly lower in energy than ring-opened form (2) [11][12][13][14][15]. It is well known that an exocyclic double bond increases the ring strain energy of three-membered rings carbocycles and heterocycles [16][17][18].…”

Section: Introductionmentioning

confidence: 99%

“…The chemistry of cyclopropanones is of considerable interest because of their reactivity and great potential as intermediates in organic syntheses [1,2]. In addition, the chemistry of small-ring heterocycles as oxiranes (epoxides) and aziridines is too of interest since they are among the most widely used intermediates in organic synthesis [3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

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Theoretical characterization of the chemical bonds of some three-membered ring compounds through QTAIM theory

Duarte

Miranda

Silva³

et al. 2015

Struct Chem

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In this paper, we investigate the nature of the carbonyl and the intraring C-C, C-N, C-O, N-N, O-O and N-O bonds of cyclopropanone and the following cyclopropanone derivatives: aziridine-2-one (1); oxirane-2-one (2); 1,2-diaziridine-3-one (3); 1,2-dioxirane-3-one (4); 1,2-oxaziridine-3-one (5); cyclopropane-1,2-dione (6); aziridine-2,3-dione (7); and oxirane-2,3-dione (8). The intramolecular distribution of the electronic charge density and the L(r) = -r 2 q(r) function have been investigated within the framework of the quantum theory of atoms in molecule theory. This methodology allowed us to characterize the bonds of cyclopropanone and the cyclopropanone derivatives studied here.

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“…1). These results allow us to establish that the X 2 -Y 3 bonds in molecules (1), (2) and (3) are quite unstable.…”

Section: -Y 3 Bondmentioning

confidence: 88%

Section: -Y 3 Bondmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Theoretical characterization of the chemical bonds of some three-membered ring compounds through QTAIM theory

Duarte

Miranda

Silva³

et al. 2015

Struct Chem

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The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives

Kun

Kulinkovich

2012

Organic Reactions

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Cyclopropanes are characterized by high ring‐strain energy and have been employed as useful building blocks in organic synthesis. The incorporation of a heteroatom donor substituent such as OH, OR, NR2, or SR on the ring imparts enhanced reactivity. Hydroxycyclopropanes (cyclopropanols) in particular have been thoroughly studied due to their facile ring cleavage. Among several known methods, a new method for preparation of cyclopropanols involves dialkoxytitanacyclopropane‐mediated cyclopropanation (the Kulinkovich cyclopropanation) of esters with Grignard reagent in the presence of titanium isopropoxide. The striking feature of this method is the facile formation of a three‐membered ring from a simple Grignard reagent which acts as a 1,2‐dicarbanion equivalent through a pivotal dialkoxytitana‐cycloproapne intermediate. These reactions benefit from the availability of inexpensive reagents, ease of operation, and high selectivity for cis ‐dialkylcyclopropanols. This cyclopropanation reaction has since been extended to other carboxylic derivatives to provide convenient access to several heteroatom‐substituted cyclopropanes. The objective of this chapter is to provide an updated, comprehensive coverage of the literature on the Kulinkovich cyclopropanation reaction and related processes. Key mechanistic issues are summarized.

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PhotochemicalRing Contraction of 2‐Ethoxypyrrolin‐5‐ones to Cyclopropanone Derivatives: tert ‐Butyl N ‐(1‐Ethoxycyclopropyl)carbamate

Crockett

Koch

2003

Organic Syntheses

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Photochemical ring contraction of 2‐ethoxypyrrolin‐5‐ones to cyclopropanone derivatives: tert ‐butyl N ‐(1‐ethoxycyclopropyl)carbamate intermediate: silver salt of succinimide intermediate: 6.26 g. (0.0493 mole) of redistilled 2‐ethoxypyrrolin‐5‐one product: tert ‐butyl N ‐(1‐ethoxycyclopropyl)carbamate

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Recent aspects of cyclopropanone chemistry

Cited by 35 publications

References 123 publications

Theoretical characterization of the chemical bonds of some three-membered ring compounds through QTAIM theory

Theoretical characterization of the chemical bonds of some three-membered ring compounds through QTAIM theory

The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives

PhotochemicalRing Contraction of 2‐Ethoxypyrrolin‐5‐ones to Cyclopropanone Derivatives: tert ‐Butyl N ‐(1‐Ethoxycyclopropyl)carbamate

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