Structural Determination of the Ozonides Derived from Mono-substituted Alkenes

Hon, Yung‐Son; Lu, Lyan Ywan; Chang, R.‐C.; Chu, Kuan-Po

doi:10.3987/com-91-5663

Cited by 13 publications

(5 citation statements)

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“…The 2 J (H,H) coupling constant between H a and H b , as well as 4 J between H c and both H a and H b are close to 0 Hz, which explains the surprising absence of a coupling in the spectrum ( Fig. ) …”

Section: Resultsmentioning

confidence: 81%

Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

Brunner

Hintermann

2016

Helvetica Chimica Acta

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An asymmetric catalytic total synthesis of (S)‐10‐hydroxystearic acid (1) for comparison of its absolute configuration to that of samples obtained by fermentative hydration of oleic acid is reported. The synthesis involves two catalytic key‐steps, namely Ru‐catalyzed anti‐Markovnikov hydration of 9‐decynoic acid (7) to 10‐oxodecanoic acid (5), followed by titanium‐mediated asymmetric catalytic addition of dioctylzinc (25) to 5 in presence of the chiral ligand N,N’‐((1R,2R)‐cyclohexane‐1,2‐diyl)bis(1,1,1‐trifluoromethanesulfonamide) (6). The synthesis is short and efficient and avoids use of protecting groups. Ozonolysis of 10‐undecynoic acid (9) to 5 provides an alternative entry point into the synthetic route. The double dehydrobromination of (ω,ω‐1)‐dibromoalkanoic acids to ω‐alkynoic acids under a variety of conditions was investigated with 10,11‐dibromoundecanoic acid (11) as model substrate and using qNMR to quantify all reaction products. The synthetic approaches presented here have the potential to be generalized to the asymmetric catalytic synthesis of a variety of n‐hydroxy‐fatty acids.

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Section: Resultsmentioning

confidence: 81%

Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

Brunner

Hintermann

2016

Helvetica Chimica Acta

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“…A small amount of the crude mixture was sampled for 1 H NMR analysis to determine the conversion of alkene and to measure the molar ratio of carbonyl product and secondary ozonide by 1 H NMR integration. The NMR characterization of the secondary ozonide was assisted by a report from Hon and co-workers . The rest of the crude mixture was purified by column chromatography on silica gel to provide the carbonyl product.…”

Section: Methodsmentioning

confidence: 99%

“…(±)-Acetyl-β-citronellol ( 3 ) (190 mg, 0.96 mmol) was treated with 2 wt % Coolade solution (1.5 mL, [ 3 ] = 0.6 M). The 1 H NMR integration of the crude mixture indicated the molar ratio of the carbonyl ( 3a ) to the secondary ozonide ( 3c ) = 2:1 ( 3a / 3c = 67:37). After purification, 3-methyl-6-oxohexyl acetate ( 3a ) was obtained as a colorless liquid (124 mg, 73%).…”

Section: Methodsmentioning

confidence: 99%

“…The NMR characterization of the secondary ozonide was assisted by a report from Hon and co-workers. 71 The rest of the crude mixture was purified by column chromatography on silica gel to provide the carbonyl product.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…"On water" ozonolysis (Table 3, entry 6): the ozonolysis without Coolade and without the reductive workup step was performed as described in the general procedure employing a biphasic mixture of (±)-acetyl-β-citronellol (3) (184 mg, 0.93 mmol) in water (1.5 mL, [3] = 0.6 M). The 1 H NMR integration of the crude mixture indicated the molar ratio of the carbonyl (3a) to the secondary ozonide (3c) 71 = 2:1 (3a/3c = 67:33). After purification, methyl-6oxohexyl acetate (3a) was obtained as a colorless liquid (103 mg, 62%).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Surfactant-Assisted Ozonolysis of Alkenes in Water: Mitigation of Frothing Using Coolade as a Low-Foaming Surfactant

et al. 2022

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Aqueous-phase ozonolysis in the atmosphere is an important process during cloud and fog formation. Water in the atmosphere acts as both a reaction medium and a reductant during the ozonolysis. Inspired by the atmospheric aqueous-phase ozonolysis, we herein report the ozonolysis of alkenes in water assisted by surfactants. Several types of surfactants, including anionic, cationic, and nonionic surfactants, were investigated. Although most surfactants enhanced the solubility of alkenes in water, they also generated excessive foaming during the ozone bubbling, which led to the loss of products. Mitigation of the frothing was accomplished by using Coolade as a nonionic and low-foaming surfactant. Coolade-assisted ozonolysis of alkenes in water provided the desired carbonyl products in good yields and comparable to those achieved in organic solvents. During the ozonolysis reaction, water molecules trapped within the polyethylene glycol region of Coolade were proposed to intercept the Criegee intermediate to provide a hydroxy hydroperoxide intermediate. Decomposition of the hydroxy hydroperoxide led to formation of the carbonyl product without the need for a reductant typically required for the conventional ozonolysis using organic solvents. This study presents Coolade as an effective surfactant to improve the solubility of alkenes while mitigating frothing during the ozonolysis in water.

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Analytical and Safety Aspects of Organic Peroxides and Related Functional Groups

Zabicky

2009

Patai's Chemistry of Functional Groups

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Introduction Hydrogen Peroxide Oxidation Indices Hydroperoxides Peroxyacids and their Functional Derivatives Dialkyl Peroxides Ozonides Miscellaneous Functions Bearing the O  O Group Safety Issues Acknowledgments

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Structural Determination of the Ozonides Derived from Mono-substituted Alkenes

Cited by 13 publications

References 0 publications

Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

Surfactant-Assisted Ozonolysis of Alkenes in Water: Mitigation of Frothing Using Coolade as a Low-Foaming Surfactant

Analytical and Safety Aspects of Organic Peroxides and Related Functional Groups

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