Pyridinium chlorochromate (PCC) oxidation of bishomoallylic tertiary alcohols. A structure–reactivity study

Beihoffer, Lauren A.; Craven, R. A.; Knight, Kyle S.; Sisson, Charles R.; Waddell, Thomas G.

doi:10.1007/s11243-005-4049-8

Cited by 9 publications

(5 citation statements)

References 13 publications

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“…[47][48][49] It is worth noting that such a cycloaddition step also explains the observed cis relationship between the ring-F spiroketal oxygen and the C-8 hydroxyl group (Figure 1).…”

Section: Methodsmentioning

confidence: 78%

Pyridinium chlorochromate chemistry. New insight into oxidation of tetrahydrofurans

Zaccaria¹,

Borbone²,

Oliviero³

et al. 2017

Arkivoc

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A thorough investigation of the minor oxidation products of two penta-tetrahydrofuran compounds with pyridinium chlorochromate has been carried out. Isolation of ring-B oxygenated spiroketal and degradation products, including polycyclic mono-and bis-lactone compounds, supports the previously postulated involvement of cyclic enolether intermediates in the oxidation of THF and poly-THF substances with PCC. Based on the collected evidence, a new mechanistic route for the PCC-mediated oxidative cleavage of -hydroxy-THF compounds to -lactones has been postulated. The proposed mechanism well agrees with the one reported for the oxidative cleavage of 8-hydroxy-neoisocedranol oxide by RuO4, a fact that further supports our previous observation on the similar oxidizing behaviour shown by PPC and RuO4 towards THFcontaining compounds.

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“…[47][48][49] It is worth noting that such a cycloaddition step also explains the observed cis relationship between the ring-F spiroketal oxygen and the C-8 hydroxyl group (Figure 1).…”

Section: Methodsmentioning

confidence: 78%

Pyridinium chlorochromate chemistry. New insight into oxidation of tetrahydrofurans

Zaccaria¹,

Borbone²,

Oliviero³

et al. 2017

Arkivoc

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“…The cyclization of alkenols to 2-formyl tetrahydrofurans is rare, having only been reported to occur via chromium (PCC) promoted cyclization, and these occur in low yields. 37 Typically, 2-formyl heterocycles are obtained by oxidation of the corresponding heterocyclic alcohol 38 or alkene. 39 The catalytic enantioselective dioxygenation/cyclization of alkenols to give cyclic ethers is also uncommon.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The direct catalytic enantioselective synthesis of 2-formyl tetrahydrofurans and related saturated heterocycles from their corresponding alkenols is unprecedented. The cyclization of alkenols to 2-formyl tetrahydrofurans is rare, having only been reported to occur via chromium (PCC) promoted cyclization, and these occur in low yields . Typically, 2-formyl heterocycles are obtained by oxidation of the corresponding heterocyclic alcohol or alkene .…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Enantioselective Aerobic Alkene Aminooxygenation and Dioxygenation: Access to 2-Formyl Saturated Heterocycles and Unnatural Proline Derivatives

et al. 2023

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Alkene aminooxygenation and dioxygenation reactions that result in carbonyl products are uncommon, and protocols that control absolute stereochemistry are rare. We report herein catalytic enantioselective alkene aminooxygenation and dioxygenation that directly provide enantioenriched 2-formyl saturated heterocycles under aerobic conditions. Cyclization of substituted 4-pentenylsulfonamides, catalyzed by readily available chiral copper complexes and employing molecular oxygen as both oxygen source and stoichiometric oxidant, directly provides chiral 2-formyl pyrrolidines efficiently. Reductive or oxidative workup of these aldehydes provides their respective amino alcohols or amino acids (unnatural prolines). Enantioselective synthesis of an indoline and isoquinolines is also demonstrated. Concurrently, cyclization of various alkenols under similar conditions provides 2-formyl tetrahydrofurans, phthalans, isochromans, and morpholines. The nature of the copper ligands, the concentration of molecular oxygen, and the reaction temperature all impact the product distribution. Chiral nitrogen and oxygen heterocycles are common components of bioactive small molecules, and these enabling technologies provide access to saturated heterocycles functionalized with ready-to-use carbonyl electrophiles.

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“…Pyridinium chlorochromate (PCC) is a mild oxidizing agent. The electron transfer reactions of PCC with various molecules have been studied [1][2][3][4][5][6][7][8][9][10][11] . PCC is a mild oxidizing agent.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Mechanism of Palladium Catalysed Electron Transfer Reaction between Glutathione (Reduced) and Pyridinium Chlorochromate in Acid Medium

2013

Chem Sci Trans

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The palladium [Pd +2 ] catalysed electron transfer reaction between glutathione (reduced) (GSH) and pyridinium chlorochromate (PCC) has been studied spectrophotometrically over the range 2.00 ≤ 10 3 [GSH] ≤ 6.00, 0.01 ≤ [H + ] ≤ 0.03 mol dm-3 , 2.83 ≤ 10 5 [Pd +2 ] ≤ 14.15 and 20 0 C ≤ t ≤ 40 0 C. The rate of reaction was found to increase with the increase in [GSH] T , [H + ] T and [Pd +2 ]. The reaction was found to exhibit first order dependence in [GSH] T , [H + ] T and [Pd +2 ] T. The ∆H ≠ (kJ/mol) and ∆S ≠ (JK-1 mol-1) for the electron transfer reaction were found to be-27.7 and-243.9. The product of the reaction was found to be glutathione disulfide (GSSG) as indicated by infrared spectrum. The negative values of activation parameters favour the formation of the ordered transition state.

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Pyridinium chlorochromate (PCC) oxidation of bishomoallylic tertiary alcohols. A structure–reactivity study

Cited by 9 publications

References 13 publications

Pyridinium chlorochromate chemistry. New insight into oxidation of tetrahydrofurans

Pyridinium chlorochromate chemistry. New insight into oxidation of tetrahydrofurans

Copper-Catalyzed Enantioselective Aerobic Alkene Aminooxygenation and Dioxygenation: Access to 2-Formyl Saturated Heterocycles and Unnatural Proline Derivatives

Kinetics and Mechanism of Palladium Catalysed Electron Transfer Reaction between Glutathione (Reduced) and Pyridinium Chlorochromate in Acid Medium

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