Direct versus Water-Mediated Protodecarboxylation of Acetic Acid Catalyzed by Group 10 Carboxylates, [(phen)M(O2CCH3)]+

Woolley, Matthew J.; Khairallah, George N.; Silva, Gabriel da; Donnelly, Paul S.; O’Hair, Richard A. J.

doi:10.1021/om500493w

Cited by 29 publications

(26 citation statements)

References 129 publications

(42 reference statements)

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“…The C-H coupling is an expected outcome for the reaction of organometallic compounds and acids such as water and alcohols. 25 Our findings show that the C-C coupling reactions in the gas phase are not strongly affected by the character of the carbon (sp 3 , sp 2 , or aromatic). It also does not seem to matter whether these types of substituents appear at the organometallic side of the equation (carrying a partially negative charge), or as the ester R′ groups (thus carrying a partially positive charge).…”

Section: Ion-molecule Reactions Of Organonickel Complexes With Estersmentioning

confidence: 58%

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Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

et al. 2019

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Gas‐phase C―C coupling reactions mediated by Ni (II) complexes were studied using a linear quadrupole ion trap mass spectrometer. Ternary nickel cationic carboxylate complexes, [(phen)Ni (OOCR1)]+ (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO2 forming the organometallic cation [(phen)Ni(R1)]+, which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH3COOR2 to yield the acetate complex [(phen)Ni (OOCCH3)]+ and a C―C coupling product R1‐R2. These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R1 and R2 (sp3, sp2, or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp3‐sp3 or sp2‐sp2 coupling reactions proceed rapidly. Experimental results are supported by density functional theory calculations, which provide insights into the energetics associated with the C―C bond coupling step.

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Section: Ion-molecule Reactions Of Organonickel Complexes With Estersmentioning

confidence: 58%

“…The identity of these ions is discussed below. The C―H coupling is an expected outcome for the reaction of organometallic compounds and acids such as water and alcohols …”

Section: Resultsmentioning

confidence: 99%

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

et al. 2019

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“…(5)], thereby closing a catalytic cycle for the protodecarboxylation of acetic acid [Eq. (6)] [22,23]

true [(normalL) M (normalO_{2} CR)]^{+} \to CO_{2} + [(normalL) M (normalR)]^{+}

true [(normalL) M (CH_{3})]^{+} + CH_{3} CO_{2} normalH \to [(normalL) M (normalO_{2} CCH_{3})]^{+} + CH_{4}

true CH_{3} CO_{2} normalH \to CO_{2} + CH_{4}

…”

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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“…Utilizing transition-metal catalysts, the groups of Gooßen, [11] Kozlowski, [12] Larrosa, [13] Nolan, [14] and others have successfully developed the protodecaboxylation of substitutedb enzoica nd aliphatic acids. [15] Photoinducedp rotodecaboxylation was also reported. [16] These methods have been furthera pplied to the deuteration of aromatic and aliphatic compounds.…”

Section: Resultsmentioning

confidence: 92%

Triphenylphosphine/Triethylamine‐Mediated Decarboxylation of α‐Oxocarboxylic Acids and Application in a One‐Pot Synthesis of Deuterated Aldehydes.

2015

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As imple method for synthesizing aldehydes from a-oxocarboxylic acidsv ia decarboxylation in the presence of PPh 3 and Et 3 Ni sr eported.T he decarboxylation can be performed on awide range of a-oxocarboxylic acids;e lectron-rich/electron-deficient aryl, heteroaryl, as well as alkyl a-oxocarboxylic acids. This method also provides ac onvenient procedure for the synthesis of deuterated aldehydes using D 2 Oa sd euterium source in af acile one-pot process.Aryl aldehydes are important synthetic intermediates that are used for numerous transformationsb ecause of the active nature of the formyl group. In addition, aryl aldehydes are also known for playing one of the central roles in pharmaceutical and agricultural chemistry. [1] While the construction of the formal group on an arene couldb ee asily done by the oxidation [2] of analogousb enzyl alcohols or from ozonolysis [3] of as tyrene moiety,t he redox nature of theset ransformations could be ap otential concern for other functional groups in the target molecules. Thus, it is of great importance to develop new methods for the synthesis of aryl aldehydes, [2] especially ones that do not require reduction/oxidation or harsh acid/ base conditions. In recent studies, a-oxocarboxylic acids have been shownt ob ee ffective coupling partners in decarboxylative coupling reactions, [5] and in these reports, the corresponding aryl aldehydes were found to be one of the side products from the decarboxylative event. [6] Thus, we envisage the potential of developing ap ractical procedure for the conversion of a-oxocarboxylic acids into aryl aldehydes. Herein, we report as imple method for the synthesis of aldehydes from a-oxocarboxylic acids mediated by PPh 3 /Et 3 N( Scheme 1). Results and DiscussionWith the inspiration fromC ohen's and Gooßen's work, [6] our initial investigations were carried out using the commercial avail-able phenylglyoxylica cid (1)a st he model substrate. Using [D 6 ]DMSO as solvent, the solutionw as heated to 120 8Cf or 12 h. In the presence of Et 3 N( 5equiv), benzaldehyde( 1a)w as the major product in 73 %y ield (determined by 1 HNMR spectroscopy, Ta ble 1, entry 1). The combination of Et 3 Na nd PPh 3 in the reactions ignificantly improved the reaction yield, and Scheme1.Decarboxylation of a-oxocarboxylic acids. Table 1. Optimization of the reaction conditions. [a] Entry Base (equiv)P hosphine (mol %) Yield [%] [b] T/t [8C/h] 1E t 3 N( 5.0)none 73 120/12 2n oneP Ph 3 (20) 0120/12 3E t 3 N( 5.0)PPh 3 (20) 93 120/12 4E t 3 N( 5.0)PPh 3 (20) 34 120/12 5E t 3 N( 5.0)PPh 3 (20) < 1120/12 6E t 3 N( 5.0)P(p-tol) 3 (20) 90 (0) [c] 120/12 7E t 3 N( 5.0)OPPh 3 (20) 65 (71) [d] 120/12 8 iPr 2 NEt (5.0)P Ph 3 (20) 20 120/12 9p yridine (5.0) PPh 3 (20) 0120/12 10 DBU (5.0)PPh 3 (20) 0120/12 [a] Reactionc onditions:P henylglyoxylica cid (0.1 mmol), base (0.5 mmol), phosphine (20 mol %), [D 6 ]DMSO( 1mL), 120 8C, 12 hi nt he 4mLv ial with Te flon cap.[ b] 1 HNMR yield of the crude mixturew ith 3,5-dinitrobenzoic acid as an internal standard. [c] Without additio...

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Direct versus Water-Mediated Protodecarboxylation of Acetic Acid Catalyzed by Group 10 Carboxylates, [(phen)M(O₂CCH₃)]⁺

Cited by 29 publications

References 129 publications

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

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

Triphenylphosphine/Triethylamine‐Mediated Decarboxylation of α‐Oxocarboxylic Acids and Application in a One‐Pot Synthesis of Deuterated Aldehydes.

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