Synthesis, x-ray analysis, and acidolysis of exo- and endo-1-methylindene ozonides

Miura, Masahiro; Ikegami, Akio; Nojima, Màsatomo; Kusabayashi, Shigekazu; McCullough, Kevin J.; Nagase, Shigeru

doi:10.1021/ja00346a051

Cited by 19 publications

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“…Overall, the ozonides 2p and 3p are obtained in good yields in experiments 15 and 21 in the presence of H 2 SO 4 or p -TsOH·H 2 O, as long as the acids were used in a sufficiently large excess. This is a very interesting fact: in the Nojima’s studies, we can see that, in the presence of 10 mol % of SbSl 5 in CH 2 Cl 2 or 10 mol % ClSO 3 H in CH 2 Cl 2 or AcOH, bridged ozonides undergo intramolecular rearrangement with the subsequent formation of decomposition products …”

Section: Resultsmentioning

confidence: 91%

Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide

et al. 2018

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Reactions of 1,5-diketones with HO open an ozone-free approach to ozonides. Bridged ozonides are formed readily at room temperature in the presence of strong Brønsted or Lewis acids such as HSO, p-TsOH, HBF, or BF·EtO. The expected bridged tetraoxanes, the products of double HO addition, were not detected. This procedure is readily scalable to produce gram quantities of the ozonides. Bridged ozonides are stable and can be useful as building blocks for bioconjugation and further synthetic transformations. Although less stabilized by anomeric interactions than bis-peroxides, ozonides have an intrinsic advantage of having only one weak O-O bond. The role of the synergetic framework of anomeric effects in bis-peroxides is to overcome this intrinsic disadvantage. As the computational data have shown, this is only possible when all anomeric effects in bis-peroxides are activated to their fullest degree. Consequently, the cyclization selectivity is determined by the length of the bridge between the two carbonyl groups of the diketone. The generally large thermodynamic preference for the formation of cyclic bis-peroxides disappears when 1,5-diketones are used as the bis-cyclization precursors. Stereoelectronic analysis suggests that the reason for the bis-peroxide absence is the selective deactivation of anomeric effects in a [3.2.2]tetraoxanonane skeleton by a structural distortion imposed on the tetraoxacyclohexane subunit by the three-carbon bridge.

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Section: Resultsmentioning

confidence: 91%

Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide

et al. 2018

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“…In the case of cycloalkenes, the efficiency is notably influenced by many factors including the ring size and the substitution pattern. As an example, ozonolysis of 1-methyl-3-phenylindene ( 1c ) in an aprotic solvent such as CCl 4 has been found to give the corresponding ozonide 2c in high yield, while in the case of 1,3-dimethylindene ( 1a ), oligomeric material 3a is the predominant product . To obtain a deeper understanding for this substituent effect on the efficiency of ozonide formation, we have investigated ozonolyses of a series of 3-alkyl-substituted 1-methylindenes 1a − d under several conditions.…”

Section: Introductionmentioning

confidence: 99%

Ozonolyses of 1-Alkyl-Substituted 3-Methylindenes. Remarkable Effects of the Substituent Steric Bulk and the Stereochemistry of the Carbonyl Oxide Intermediates on the Efficiency of Ozonide Formation

et al. 1998

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Ozonolyses of 3-methyl- and 3-isopropyl-1-methylindenes (1a,b) in ether gave mainly the corresponding oligomers 3a,b, while in the case of 3-phenyl- and 3-tert-butyl-1-methylindenes (1c,d), the corresponding exo−endo mixtures of ozonides 2c,d were obtained in good yield, the exo isomer being the major one. The ozonolyses of two stereoisomeric keto vinyl ethers, (E)-16 and (Z)-16, demonstrated that the stereochemistry of the derived carbonyl oxide 5c exerts a remarkable influence on the course of the reaction. Particularly interesting is the fact that syn-5c having a proper geometry for the concerted cycloaddition provided ozonide 2c in high yield even in the presence of trifluoroacetophenone. The high degree of similarity in the nature and distribution of the products from the ozonolyses of keto olefin (E)-16 and 1-methyl-3-phenylindene (1c) would be consistent with their respective reactions proceeding predominantly through a common carbonyl oxide intermediate syn-5c.

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Chlorosulfonic Acid

Prabhakaran¹

2001

Encyclopedia of Reagents for Organic Synthesis

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Synthesis, x-ray analysis, and acidolysis of exo- and endo-1-methylindene ozonides

Cited by 19 publications

References 0 publications

Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide

Ozone-Free Synthesis of Ozonides: Assembling Bicyclic Structures from 1,5-Diketones and Hydrogen Peroxide

Ozonolyses of 1-Alkyl-Substituted 3-Methylindenes. Remarkable Effects of the Substituent Steric Bulk and the Stereochemistry of the Carbonyl Oxide Intermediates on the Efficiency of Ozonide Formation

Chlorosulfonic Acid

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