Oxygen: The Key to Stereoelectronic Control in Chemistry

Alabugin, Igor V.; Kuhn, Leah

doi:10.1021/acsinfocus.7e7009

Cited by 5 publications

(1 citation statement)

References 186 publications

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“…Considering that oxygen is an essential element of life and that the O–O bond is an isostere of a C–C bond, there is a great interest in exploring stabilized − organic peroxides as a new medicinally interesting region of the molecular universe . Alkene ozonolysis provides a conceptually appealing way for the efficient introduction of O–O bonds into organic molecules because it leads to the transient formation of reactive carbonyl oxide species (i.e., the Criegee intermediates, CIs). , This highly electrophilic 1,3-dipole has broad synthetic potential, which is, nevertheless, still largely untapped.…”

Section: Introductionmentioning

confidence: 99%

Interrupted Dance of Five Heteroatoms: Reinventing Ozonolysis to Make Geminal Alkoxyhydroperoxides from C═N Bonds

Yaremenko,

Fomenkov,

Budekhin

et al. 2024

J. Org. Chem.

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Four heteroatoms dance in the cascade of four pericyclic reactions initiated by ozonolysis of C�N bonds. Switching from imines to semicarbazones introduces the fifth heteroatom that slows this dance, delays reaching the thermodynamically favorable escape path, and allows efficient interception of carbonyl oxides (Criegee intermediates, CIs) by an external nucleophile. The new three-component reaction of alcohols, ozone, and oximes/semicarbazones greatly facilitates synthetic access to monoperoxyacetals (alkoxyhydroperoxides).

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Section: Introductionmentioning

confidence: 99%

Interrupted Dance of Five Heteroatoms: Reinventing Ozonolysis to Make Geminal Alkoxyhydroperoxides from C═N Bonds

Yaremenko,

Fomenkov,

Budekhin

et al. 2024

J. Org. Chem.

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Ethers as Building Blocks for the Synthesis and Modification of N‐Heterocycles

Grishin,

Mulina,

et al. 2024

Asian J Org Chem

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The use of C‐H compounds as reactive partners in a variety of transformations represents the state of the art in synthetic methodology. In this review, we have summarized the main achievements in using ethers as building blocks for the construction and modification of one of the basic platforms of organic chemistry, nitrogen‐containing heterocycles. Ethers, previously considered mainly as solvents, are excellent CH‐partners, capable of generating radical or cationic reactive species under the action of HAT agents and oxidants. The challenge in this field is the still limited number of heterocyclic systems and other starting reagents, with which the processes can be carried out selectively due to closer bond dissociation energies and oxidation potentials of heterocycles, reactive intermediates and ethers. However, the fine‐tuning of the reaction system using electro‐ and photochemical approaches and a deep understanding of the reaction pathways make the use of ethers as C‐H reagents a promising synthetic strategy.

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Carbon Dioxide Stability and C═O π-Bond Strengths

Kass

2024

J. Org. Chem.

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π-Bond energies for a series of C�O containing compounds including carbon dioxide are determined using G3 and W1 calculations. These two computational methods give results that are in good accord, and in the latter case span a 37 kcal mol −1 range from 75 (CH 2 �O) to 112 (CO 2 ) kcal mol −1 . This sensitivity to substituent effects on the π-bond strength is attributed to Coulombic interactions between the oppositely charged carbon and oxygen atoms in the carbon− oxygen double bond. In contrast, carbon−carbon π-bond energies of a related series of compounds are found to be relatively constant (i.e., the variation is only 3 kcal mol −1 ). The C�O π-bond strengths are also found to linearly correlate with the atomic charge at carbon as well as heats of hydration and hydrogenation.

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Oxygen: The Key to Stereoelectronic Control in Chemistry

Cited by 5 publications

References 186 publications

Interrupted Dance of Five Heteroatoms: Reinventing Ozonolysis to Make Geminal Alkoxyhydroperoxides from C═N Bonds

Interrupted Dance of Five Heteroatoms: Reinventing Ozonolysis to Make Geminal Alkoxyhydroperoxides from C═N Bonds

Ethers as Building Blocks for the Synthesis and Modification of N‐Heterocycles

Carbon Dioxide Stability and C═O π-Bond Strengths

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