Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic C–H Acetoxylation Catalyzed by Pd(OAc)2/4,5-Diazafluoren-9-one

Jaworski, Jonathan N.; Kozack, Caitlin V.; Tereniak, Stephen J.; Knapp, Spring M.; Landis, Clark R.; Miller, Jeffrey T.; Stahl, Shannon S.

doi:10.1021/jacs.9b04699

Title: Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic C–H Acetoxylation Catalyzed by Pd(OAc)₂/4,5-Diazafluoren-9-one

Journal Article · 11 June 2019 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b04699 · OSTI ID:1604199

Jaworski, Jonathan N. ^[1];

^[1]; Tereniak, Stephen J. ^[1];

^[1];

^[2];

^[1]

Univ. of Wisconsin, Madison, WI (United States)
Purdue Univ., West Lafayette, IN (United States)

Allylic C–H acetoxylations are among the most widely studied palladium(II)-catalyzed C–H oxidation reactions. While the principal reaction steps are well established, key features of the catalytic mechanisms are poorly characterized, including the identity of the turnover-limiting step and the catalyst resting state. In this study, we report a mechanistic study of aerobic allylic acetoxylation of allylbenzene with a catalyst system composed of Pd(OAc)₂ and 4,5-diazafluoren-9-one (DAF). The DAF ligand is unique in its ability to support aerobic catalytic turnover, even in the absence of benzoquinone or other co-catalysts. Herein, we describe operando spectroscopic analysis of the catalytic reaction using X-ray absorption and NMR spectroscopic methods that allow direct observation of the formation and decay of a palladium(I) species during the reaction. Kinetic studies reveal the presence of two distinct kinetic phases: (1) a burst phase, involving rapid formation of the allylic acetoxylation product and formation of the dimeric Pd^I complex [Pd^I(DAF)(OAc)]₂, followed by (2) a post-burst phase that coincides with evolution of the catalyst resting state from the Pd^I dimer into a π-allyl-Pd^II species. The data provide unprecedented insights into the role of ancillary ligands in supporting catalytic turnover with O₂ as the stoichiometric oxidant and establish an important foundation for the development of improved catalysts for allylic oxidation reactions.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH)

Grant/Contract Number:: AC02-06CH11357; CHE-1665120; CHE-1048642; CHE-9709065; DGE-1256259; R01-GM67173; S10-OD012245

OSTI ID:: 1604199

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 26; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Mechanism of Pd(OAc) ₂ /DMSO-Catalyzed Aerobic Alcohol Oxidation: Mass-Transfer-Limitation Effects and Catalyst Decomposition Pathways Steinhoff, Bradley A.; Stahl, Shannon S. Journal of the American Chemical Society, Vol. 128, Issue 13 https://doi.org/10.1021/ja057914b	journal	April 2006
Oxygenation of Nitrogen-Coordinated Palladium(0): Synthetic, Structural, and Mechanistic Studies and Implications for Aerobic Oxidation Catalysis Stahl, Shannon S.; Thorman, Joseph L.; Nelson, Ryan C. Journal of the American Chemical Society, Vol. 123, Issue 29 https://doi.org/10.1021/ja015683c	journal	July 2001
“Oxidatively Induced” Reductive Elimination of Dioxygen from an η ^2- Peroxopalladium(II) Complex Promoted by Electron-Deficient Alkenes Popp, Brian V.; Stahl, Shannon S. Journal of the American Chemical Society, Vol. 128, Issue 9 https://doi.org/10.1021/ja057753b	journal	February 2006
Electronic Structural Comparison of the Reactions of Dioxygen and Alkenes with Nitrogen-Chelated Palladium(0) Popp, Brian V.; Morales, Christine M.; Landis, Clark R. Inorganic Chemistry, Vol. 49, Issue 18 https://doi.org/10.1021/ic100806w	journal	September 2010
Evidence for (π-allyl)palladium(II)(quinone) complexes in the palladium-catalyzed 1,4-diacetoxylation of conjugated dienes Báckvall, Jan-E.; Gogoll, Adolf Tetrahedron Letters, Vol. 29, Issue 18 https://doi.org/10.1016/S0040-4039(00)86722-2	journal	January 1988
Use of sulfoxides as cocatalysts in the palladium-quinone-catalyzed 1,4-diacetoxylation of 1,3-dienes. An example of ligand-accelerated catalysis Grennberg, Helena; Gogoll, Adolf; Baeckvall, Jan E. The Journal of Organic Chemistry, Vol. 56, Issue 20 https://doi.org/10.1021/jo00020a022	journal	September 1991

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Pd-Catalyzed decarboxylative cross-coupling reactions of epoxides with α,β-unsaturated carboxylic acids Lu, Xiao-Yu; Li, Jin-Song; Wang, Shi-Qun Chemical Communications, Vol. 55, Issue 74 https://doi.org/10.1039/c9cc04795f	journal	January 2019
Base‐Assisted C−H Bond Cleavage in Cross‐Coupling: Recent Insights into Mechanism, Speciation, and Cooperativity Carrow, Brad P.; Sampson, Jessica; Wang, Long Israel Journal of Chemistry, Vol. 60, Issue 3-4 https://doi.org/10.1002/ijch.201900095	journal	December 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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catalysts
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Title: Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic C–H Acetoxylation Catalyzed by Pd(OAc)2/4,5-Diazafluoren-9-one

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