The Anodic Oxidation of 1,1-Diphenyl Ketones in the Presence of Nucleophiles

Sheludko, Boris

doi:10.14418/wes01.2.17

Cited by 1 publication

(4 citation statements)

References 31 publications

(76 reference statements)

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“…In contrast to the preferred enolic pathway through which diphenylacetaldehyde (3) proceeds, 1 is converted to 3 via direct α-cleavage (Scheme 4), at least 86% of the time, and the enol is only minimally involved. 10 3 3a 6 7 Scheme 4. Electrochemical conversion of 1 to benzhydryl ethers (7) via the keto pathway (direct α-cleavage).…”

Section: A 4mentioning

confidence: 99%

“…It is likely that the reason behind this stability in air is that oxidation would proceed via the enol, which Boris Sheludko had shown is only minimally involved in the oxidation of 1. 10 In fact, ketones contain, on average, 10-1000 times less enol content than their corresponding aldehydes. 26 The observed conversion of 1 to 2, therefore, does not occur aerobically but primarily through electrochemical means.…”

Section: A Mechanism For the Cathodic Conversion Of 11-diphenylacetone To Benzophenonementioning

confidence: 99%

“…In addition, Evan Baum of the Fry group showed that αcyclohexoxydiphenylacetaldehyde (10) was rapidly converted to 9 when placed in the cathode compartment of a divided cell, but neither 8 nor 10 experienced any conversion to 9 when they were placed in the anode compartment. 12 Scheme 5.…”

mentioning

confidence: 99%

“…As stated earlier, Sheludko demonstrated that the preferred pathway for the conversion of 1,1-diphenylacetone (1) to the corresponding benzhydryl ethers (7) involves direct α-cleavage of the carbon-carbonyl bond, rather than oxidation of the enol tautomer. 10 Because this pathway bypasses formation of an α-alkoxyketone intermediate, 1 is expected to be cleaved at the anode and then attacked by the nucleophile in solution. Therefore, the conversion of 1 to the ethers is still expected to 3 3a 6 7 be an anodic transformation.…”

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Superoxide-Facilitated Cathodic Cleavage of 1,1-Diphenyl Ketones

Tsui¹

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The cathodic conversion of 1,1-diphenylacetone (1) to benzophenone (2) was investigated. Through divided-cell electrolyses, cyclic voltammetry, and reactions with authentic superoxide, it was demonstrated that molecular oxygen is likely reduced to the superoxide anion at the cathode, where it proceeds to react with 1 to form an α-hydroperoxy ketone intermediate. Nucleophilic attack at the carbonyl by a second molecule of superoxide facilitates cleavage of the carbon-carbonyl bond to afford 2. Analogously, it was determined through mechanistic studies that αsubstituted 1,1-diphenyl ketones undergo α-cleavage of the acyl group in a remarkably mild cathodic reaction. This transformation is postulated to occur via reduction of oxygen to superoxide, which forms a hydroperoxy anion that then attacks the carbonyl to give a tetrahedral intermediate. As the intermediate collapses to reform the carbonyl, the carbon-carbonyl bond is cleaved to yield the hydrocarbon product. Observed superoxide-facilitated α-cleavage offers an explanation for the previously-described cathodic cleavage of α-alkoxyaldehydes to benzhydryl alkyl ethers. The significant structural changes that are afforded by the mild cathodic reactions discussed here demonstrate the synthetic capabilities of organic electrochemistry.First and foremost, thank you, Professor Albert J. Fry, for the past two and a half years of guidance, support, patience, and good humor. I can never thank you enough for giving me the opportunity to work in your lab and for teaching me all the necessary skills to succeed. You have dealt with all my questions about electrochemistry, frantic knocks on your door, and constant emails with grace over the years, and I sincerely appreciate all that you have done for me.To the members of the Fry lab: Thank you for making Club Fry one of the best places to spend my summers. To Filmon: Thank you for our many discussions about chemistry and the merits of mass spectrometry. I cannot tell you enough how much I appreciate your patience and willingness to help me whenever I faced a roadblock in my project. To Emily: Thank you for constantly making me laugh. To Will and Haley: Thank you for believing in me, especially during those moments when I doubted myself. I wish all of you the best.To the Wesleyan Chemistry faculty: Thank you for your teaching over the past four years, whether inside or outside of the classroom. Thank you, Professor Northrop and Professor Roberts, for your invaluable advice about chemistry, graduate school, and the future. Thank you, Professor Calter, for introducing me to organic chemistry. I would also like to thank the staff, especially Roslyn, Doug, Don, and Horace, for making sure everything in the department runs smoothly.To Shalisa and Yael: I cannot express how lucky I am to call you my housemates.Thank you for your amazing cooking and baking and for the endless laughs this past year.To Rohit: Thank you for all our conversations about life and helping me realize that we really are the same person. Thank you for listen...

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Section: A 4mentioning

confidence: 99%

Section: A Mechanism For the Cathodic Conversion Of 11-diphenylacetone To Benzophenonementioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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