The Use of Cupric and Ferric Chlorides in the Trapping of Radical Intermediates and the Synthesis of Alkyl Chlorides

Kumamoto, Junji; Mare, H. E. De La; Rust, Frederick F.

doi:10.1021/ja01493a024

Cited by 30 publications

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“…Our reaction design was based on previous reports of Fe II transferring an electron to the a-alkoxy hydroperoxides generated upon ozonolysis of al-kenes in the presence of an alcohol. The resulting oxyradicals can subsequently engage in various forms of homolytic cleavage to produce alkenes, dimers, or halides (11)(12)(13)(14)(15)(16). Nevertheless, these methods often occur with poor efficiencies and/ or have limited utility.…”

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confidence: 99%

Hydrodealkenylative C(sp ³ )–C(sp ² ) bond fragmentation

Smaligo

Swain

Quintana

et al. 2019

Science

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Chemical synthesis typically relies on reactions that generate complexity through elaboration of simple starting materials. Less common are deconstructive strategies toward complexity—particularly those involving carbon-carbon bond scission. Here, we introduce one such transformation: the hydrodealkenylative cleavage of C(sp3)–C(sp2) bonds, conducted below room temperature, using ozone, an iron salt, and a hydrogen atom donor. These reactions are performed in nonanhydrous solvents and open to the air; reach completion within 30 minutes; and deliver their products in high yields, even on decagram scales. We have used this broadly functionality tolerant transformation to produce desirable synthetic intermediates, many of which are optically active, from abundantly available terpenes and terpenoid-derived precursors. We have also applied it in the formal total syntheses of complex molecules.

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confidence: 99%

Hydrodealkenylative C(sp ³ )–C(sp ² ) bond fragmentation

Smaligo

Swain

Quintana

et al. 2019

Science

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“…Journal of the American Chemical Society / 91:5 / February a A, the peroxide, 0.1 ml, was added to the ferrous sulfate (0.30 g) with and without ethyl sulfate. 6 B, the ferrous sulfate (0.30 g) was added to the 0.1 ml of peroxide with and without ethyl sulfate. peroxide in a typical experiment produces ethylene in somewhat higher yields.…”

Section: Resultsmentioning

confidence: 99%

Evidence and hypothesis for a "Taube bridge electron transfer" propagating to a remote site through .sigma. bonding. Formation of ethylene from monoethyl sulfate

Kumamoto¹,

Dollwet²,

Lyons³

1969

J. Am. Chem. Soc.

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stirred at -70°under a nitrogen atmosphere and phenyllithium10 (16 ml, 1.5 N in ether, 4 equiv) was added over a 5-min period, forming a dark red solution. After quenching with an excess of cold aqueous ammonium chloride, a red-brown organic layer was formed to which 25 ml of benzene was added. The two layers were filtered to remove 0.347 g of an insoluble dark brown solid, and the organic layer was then separated and washed with cold distilled water. The dark brown oily residue left on evaporation was taken up in 100 ml of dry benzene and filtered to remove insoluble material. After drying over sodium sulfate and evaporating, the residual brown oil was dried overnight at 0.004 mm and 18.4 mg of biphenyl distilled over into the trap. Anhydrous ether (20 ml) was added to the oily residue. The red solution was filtered from some insoluble material and cooled in an ice-water bath before adding 100 ml of cold petroleum ether (bp 30-60°). The brown solid which precipitated was collected by filtration, washed with petroleum ether, and then freeze dried from benzene to yield 121.5 mg (14%) of 1 -phenylthiabenzene, softening point 68-73°.1-Phenylthiabenzene (VI) was also prepared2 by treating 1.0 g of VII11 suspended in 50 ml of ether under nitrogen in a separatory funnel capped with a rubber serum cap with 15 ml of 2 M phenyllithium in etherbenzene (Lithium Corp. of America, New York, N. Y.) added by a syringe slowly with shaking. After 15 min additional shaking, it was worked up as above to give 72 mg of a brown solid, softening point 68-72°.

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“…Pertinent to this study, the first explicit mention of radical intermediates in the Fe II ‐mediated degradation of α‐alkoxy hydroperoxides (and the formation of alkyl radical dimers) came from Hawkins in 1955 (Scheme ) . Later, Kumamoto, De La Mare, Rust, and Kochi described the trapping of these alkyl radicals with cupric species to form either alkyl halides or alkenes . Although Criegee had in 1949 reported the formation of α‐alkoxy hydroperoxides through ozonolysis of alkenes in alcoholic solvents, it was not until 1964 that Murai, Sonoda, and Tsutsumi combined this method of hydroperoxide generation with the established iron/copper couple to produce a dimer and halide products from alkenes .…”

Section: Methodsmentioning

confidence: 99%

Oxodealkenylative Cleavage of Alkene C(sp³)−C(sp²) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials

Smaligo

Burton

et al. 2019

Angew Chem Int Ed

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Reported herein is a one‐pot protocol for the oxodealkenylative introduction of carbonyl functionalities into terpenes and terpene‐derived compounds. This transformation proceeds by Criegee ozonolysis of an alkene, reductive cleavage of the resulting α‐alkoxy hydroperoxide, trapping of the generated alkyl radical with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO), and subsequent oxidative fragmentation with MMPP. Using readily available starting materials from chiral pool, a variety of carbonyl‐containing products have been accessed rapidly in good yields.

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The Use of Cupric and Ferric Chlorides in the Trapping of Radical Intermediates and the Synthesis of Alkyl Chlorides

Cited by 30 publications

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Hydrodealkenylative C(sp ³ )–C(sp ² ) bond fragmentation

Hydrodealkenylative C(sp ³ )–C(sp ² ) bond fragmentation

Evidence and hypothesis for a "Taube bridge electron transfer" propagating to a remote site through .sigma. bonding. Formation of ethylene from monoethyl sulfate

Oxodealkenylative Cleavage of Alkene C(sp³)−C(sp²) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials

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The Use of Cupric and Ferric Chlorides in the Trapping of Radical Intermediates and the Synthesis of Alkyl Chlorides

Cited by 30 publications

References 0 publications

Hydrodealkenylative C(sp 3 )–C(sp 2 ) bond fragmentation

Hydrodealkenylative C(sp 3 )–C(sp 2 ) bond fragmentation

Evidence and hypothesis for a "Taube bridge electron transfer" propagating to a remote site through .sigma. bonding. Formation of ethylene from monoethyl sulfate

Oxodealkenylative Cleavage of Alkene C(sp3)−C(sp2) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials

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Hydrodealkenylative C(sp ³ )–C(sp ² ) bond fragmentation

Hydrodealkenylative C(sp ³ )–C(sp ² ) bond fragmentation

Oxodealkenylative Cleavage of Alkene C(sp³)−C(sp²) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials