Aerobic Alcohol Oxidation Coupled to Palladium‐Catalyzed Alkene Hydroarylation with Boronic Esters

Iwai, Yasumasa; Gligorich, Keith M.; Sigman, Matthew S.

doi:10.1002/anie.200705317

Cited by 97 publications

(38 citation statements)

References 33 publications

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“…2 Various methods have been reported to access such compounds including Au- 3 and Ni-catalyzed 4 hydroheteroarylation reactions. In this regard, our laboratory has reported the use of styrenes 5 and dienes 6 as substrates in oxidative Pd(II)-catalyzed hydrofunctionalization reactions with organometallic reagents and either an alcohol 5–7 or alkylzinc reagents 8 as the hydride source. These reactions have generally been limited to the introduction of simple arenes and alkyl groups as the organometallic reaction partner.…”

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confidence: 99%

Palladium-Catalyzed Hydrofunctionalization of Vinyl Phenol Derivatives with Heteroaromatics

Pathak

Sigman

2011

Org. Lett.

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confidence: 99%

Palladium-Catalyzed Hydrofunctionalization of Vinyl Phenol Derivatives with Heteroaromatics

Pathak

Sigman

2011

Org. Lett.

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“…Initially, we evaluated PhB(OH) 2 ( BA ) with the conditions developed for organostannanes ix. This led to the desired product 10a in poor yield xxxiii. During the course of the reaction, a black precipitate was observed, which suggested decomposition of the Pd catalyst.…”

Section: Resultsmentioning

confidence: 99%

A new approach to carbon–carbon bond formation: development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes

Gligorich

Iwai²,

Cummings

et al. 2009

Tetrahedron

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Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed. These results inspired the development of a new Pd-catalyzed reductive coupling reaction of alkenes and organometallic reagents that generates a new carbon-carbon bond. Optimization of the conditions for the coupling of both organostannanes and organoboronic esters is described and the initial scope of the transformation is presented. Additionally, several mechanistic experiments are outlined and support the rationale for the development of the reaction based upon coupling alcohol oxidation to alkene functionalization.

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“…26 To an oven-dried 50 mL round bottom flask equipped with a stir bar, is added 1.0 g of phenyl boronic acid (8.2 mmol, 1.00 equiv. ), 1.07 g of ethylene glycol (8.6 mmol, 1.05 equiv.)…”

Section: Methodsmentioning

confidence: 99%

“…The NMR spectra of PBE (colorless liquid), Figures A1 and A2, is very similar to previously reported spectra. 26 …”

Section: Appendixmentioning

confidence: 99%

Mitigating Performance Degradation of High-Capacity Lithium-Ion Cells with Boronate-Based Electrolyte Additives

Zhu

Abraham

2014

J. Electrochem. Soc.

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Boronate-based electrolyte additives are tested in high-capacity lithium-ion cells containing graphite-based negative and Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 -based positive electrodes. Cells containing small amounts (0.25 wt%) of phenyl boronic acid ethylene glycol ester (PBE) in an EC:EMC (3:7 by wt) + 1.2M LiPF 6 (Gen2) electrolyte show improved capacity retention and reduced impedance rise compared to cells without the additive. Adding a perfluorooctyl chain to PBE creates the phenyl boronic acid perfluorooctyl ethylene glycol ester (PFO-PBE) compound. Cells with 0.25 wt% PFO-PBE additive display the lowest capacity fade (21%) compared to the PBE (34%) and Gen2 (65%) cells after more than 200, 2.2-4.6 V cycles, at 30 • C. These data validate our modular-electrolyte additive concept (PBE head and perfluoroalkyl tail) for high-capacity lithium-ion cells. Impedance rise is reduced further by addition of 2 wt% LiDFOB (LiF 2 BC 2 O 4 ) to cells with 0.25 wt% PFO-PBE, thus demonstrating that additive combinations can enhance performance during extended cycling.Lithium-ion cells are a common feature of everyday life with applications in laptops, cell phones and various devices that require portable energy storage. These cells are also increasingly used in the transportation sector; herein, high energy density cells are needed to reduce the weight and volume of batteries being considered for plug-in hybrid and fully electric vehicles. Cell energy densities can be increased through the use of lithium-and manganese-rich transition metal layered-oxides (LMR-NMC) as active materials in the positive electrode; the theoretical energy densities of these cells can exceed 900 Wh-kg oxide −1 . 1,2 However, to achieve these high energy densities, the cells are cycled at high voltages (>4.5 V vs Li/Li + ), which deteriorates performance and reduces life. 2 This performance degradation is often attributed to undesirable side reactions, especially at the positive electrode. 3,4 Preventing or minimizing these performance-degrading reactions at electrode-electrolyte interfaces is crucial for the commercial success of high-energy cells.In prior articles, we have demonstrated that modification of electrode interfaces by coatings and/or by electrolyte additives can improve long-term performance of high-capacity cells. 5-8 Electrolyte additives are especially important because they offer a viable, relatively inexpensive, and highly practical pathway for in situ modification of interfaces. Several electrolyte additives have been reported for high voltage lithium ion cells. 9 These compounds include lithium chelatoborates, 10,11 lithium chelatophosphates, 12 heterocyclic compounds such as substituted thiophenes, 13 and various phosphorousbearing organic compounds. [14][15][16] In this article we report on boronatebased electrolyte additives that enhance longevity of high-capacity cells.Boronate-based materials, augmented by various electron withdrawing groups such as fluorinated phenyls, have been studied as anion receptors in lithium-ion c...

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Aerobic Alcohol Oxidation Coupled to Palladium‐Catalyzed Alkene Hydroarylation with Boronic Esters

Cited by 97 publications

References 33 publications

Palladium-Catalyzed Hydrofunctionalization of Vinyl Phenol Derivatives with Heteroaromatics

Palladium-Catalyzed Hydrofunctionalization of Vinyl Phenol Derivatives with Heteroaromatics

A new approach to carbon–carbon bond formation: development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes

Mitigating Performance Degradation of High-Capacity Lithium-Ion Cells with Boronate-Based Electrolyte Additives

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