Ligand-induced decarbonylation in diphosphine-ligated palladium acetates [CH3CO2Pd((PR2)2CH2)]+ (R = Me and Ph)

Lesslie, Michael; Yang, Yang; Canty, Allan J.; Piacentino, Elettra L.; Berthias, Francis; Maître, Philippe; Ryzhov, Victor; O’Hair, Richard A. J.

doi:10.1039/c7cc08944a

Cited by 17 publications

(14 citation statements)

References 29 publications

(4 reference statements)

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“…The C−O bond activations of carboxylic acid anhydride via TS5 and TS16 are facile and reversible, leading to two acylpalladium species 6 and 17 in equilibrium . Subsequent decarbonylation via TS7 is significantly more favorable than the decarboxylation via TS18 , which corroborates the proposed decarbonylative strategy to activate carboxylic acid . The arylpalladium intermediate 9 then undergoes the transmetallation and reductive elimination to produce the decarbonylative borylation product 15 .…”

Section: Figuresupporting

confidence: 77%

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Liu

Hong

et al. 2018

Angewandte Chemie

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Decarbonylative borylation of carboxylic acids is reported. Carbon electrophiles are generated directly after reagent‐enabled decarbonylation of the in situ accessible sterically‐hindered acyl derivative of a carboxylic acid under catalyst controlled conditions. The scope and the potential impact of this method are demonstrated in the selective borylation of a variety of aromatics (>50 examples). This strategy was used in the late‐stage derivatization of pharmaceuticals and natural products. Computations reveal the mechanistic details of the unprecedented C−O bond activation of carboxylic acids. By circumventing the challenging decarboxylation, this strategy provides a general synthetic platform to access arylpalladium species for a wide array of bond formations from abundant carboxylic acids. The study shows a powerful combination of experiment and computation to predict decarbonylation selectivity.

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Section: Figuresupporting

confidence: 77%

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Liu

Hong

et al. 2018

Angewandte Chemie

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“…9. Thus, alkenes must be extruded from the organometallic species via a “chain‐walking”‐type mechanism common for Ni(II) and Pd(II) catalysts used for alkene polymerization/depolymerization [24,41] . Detailed investigation of this mechanism in related gas‐phase systems is currently under investigation and will be published separately.…”

Section: Resultsmentioning

confidence: 99%

“…(7)], and the resulting organometallic product ion can lose styrene upon another stage of collisional activation [Eq. (8)] [24]

true [(normalL) Pd (normalO_{2} CCH_{2} CH_{2} normalC_{6} normalH_{5})]^{+} \to CO + [(LO) Pd (CH_{2} CH_{2} normalC_{6} normalH_{5})]^{+}

true [(LO) Pd (CH_{2} CH_{2} normalC_{6} normalH_{5})]^{+} \to [(LO) Pd (normalH)]^{+} + normalC_{6} normalH_{5} CH = CH_{2}

…”

Section: Introductionmentioning

confidence: 99%

Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

et al. 2020

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Using fatty acids as renewable sources of biofuels requires deoxygenation. While a number of promising catalysts have been developed to achieve this, their operating mechanisms are poorly understood. Here, model molecular systems are studied in the gas phase using mass spectrometry experiments and DFT calculations. The coordinated metal complexes [(phen)M(O2CR)]+ (where phen=1,10‐phenanthroline; M=Ni or Pd; R=CnH2n+1, n≥2) are formed via electrospray ionization. Their collision‐induced dissociation (CID) initiates deoxygenation via loss of CO2 and [C,H2,O2]. The CID spectrum of the stearate complexes (R=C17H35) also shows a series of cations [(phen)M(R’)]+ (where R’ < C17) separated by 14 Da (CH2) corresponding to losses of C2H4‐C16H32 (cracking products). Sequential CID of [(phen)M(R’)]+ ultimately leads to [(phen)M(H)]+ and [(phen)M(CH3)]+, both of which react with volatile carboxylic acids, RCO2H, (acetic, propionic, and butyric) to reform the coordinated carboxylate complexes [(phen)M(O2CR)]+. In contrast, cracking products with longer carbon chains, [(phen)M(R)]+ (R>C2), were unreactive towards these carboxylic acids. DFT calculations are consistent with these results and reveal that the approach of the carboxylic acid to the “free” coordination site is blocked by agostic interactions for R > CH3.

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“…[23] Subsequent decarbonylation via TS7 is significantly more favorable than the decarboxylation via TS18,w hich corroborates the proposed decarbonylative strategy to activate carboxylic acid. [24] The arylpalladium intermediate 9 then undergoes the transmetallation [25] and reductive elimination [26] to produce the decarbonylative borylation product 15.T he computations suggest that the acylpalladium intermediate 6 is the resting state of the catalytic cycle,and that the transmetallation step via TS11 is the rate-determining step with an overall barrier of 32.0 kcal mol À1 (6 to TS11). [27] We also attempted to locate the four-membered ring transmetallation transition state.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…The computed free energy profile of the overall catalytic cycle of decarbonylative borylation is shown in Figure 3A.The C À Obond activations of carboxylic acid anhydride via TS5 and TS16 are facile and reversible,l eading to two acylpalladium species 6 and 17 in equilibrium. [24] The arylpalladium intermediate 9 then undergoes the transmetallation [25] and reductive elimination [26] to produce the decarbonylative borylation product 15.T he computations suggest that the acylpalladium intermediate 6 is the resting state of the catalytic cycle,and that the transmetallation step via TS11 is the rate-determining step with an overall barrier of 32.0 kcal mol À1 (6 to TS11). [24] The arylpalladium intermediate 9 then undergoes the transmetallation [25] and reductive elimination [26] to produce the decarbonylative borylation product 15.T he computations suggest that the acylpalladium intermediate 6 is the resting state of the catalytic cycle,and that the transmetallation step via TS11 is the rate-determining step with an overall barrier of 32.0 kcal mol À1 (6 to TS11).…”

mentioning

confidence: 99%

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Liu,

Ji,

Hong

et al. 2018

Angew Chem Int Ed

106

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Decarbonylative borylation of carboxylic acids is reported. Carbon electrophiles are generated directly after reagent-enabled decarbonylation of the in situ accessible sterically-hindered acyl derivative of ac arboxylic acid under catalyst controlled conditions.T he scope and the potential impact of this method are demonstrated in the selective borylation of av ariety of aromatics (> 50 examples). This strategy was used in the late-stage derivatization of pharmaceuticals and natural products.C omputations reveal the mechanistic details of the unprecedented CÀObond activation of carboxylic acids.B ycircumventing the challenging decarboxylation, this strategy provides ag eneral synthetic platform to access arylpalladium species for aw ide arrayo fb ond formations from abundant carboxylica cids.T he study shows ap owerfulc ombination of experiment and computation to predict decarbonylation selectivity.

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Ligand-induced decarbonylation in diphosphine-ligated palladium acetates [CH₃CO₂Pd((PR₂)₂CH₂)]⁺ (R = Me and Ph)

Cited by 17 publications

References 29 publications

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation

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