Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO<sub>2</sub>

Yan, Si‐Shun; Zhu, Lei; Ye, Jian‐Heng; Zhang, Zhen; Huang, He; Zeng, Huiying; Li, Chao‐Jun; Lan, Yu; Yu, Da‐Gang

doi:10.1039/c8sc01299g

Cited by 74 publications

(35 citation statements)

References 107 publications

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“…Although, the exact mechanism still remained unclear at this moment, on the basis of literature reports 6,[47][48][49][50][51][52][53][54][55][56] and our findings, a plausible reaction pathway was proposed in Fig. 5.…”

Section: Resultsmentioning

confidence: 69%

“…1d). Inspiration of this project stemsfrom our recent studies on hydrazone chemistry, in which umpolung aldehydes act as carbanion equivalents in the catalytic nucleophilic addition [47][48][49][50][51][52] and cross-coupling reactions [53][54][55][56] . Highlighted features of this strategy are (a) no oxidant needed; (b) H 2 , N 2 and H 2 O as innocuous side products; (c) naturally rich aldehydes as environmentally benign alkyl nucleophiles; (d) excellent regioselectivity achieved via vicinal oxygen atom chelation; (e) first-row abundant nickel as catalyst; (f) broad substrate scope and great functional group compatibility; and (g) modification of pharmaceutical candidates and biological molecules.…”

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confidence: 99%

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Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Zhu

2019

Nat Commun

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Alkenes are fundamental functionalities in nature and highly useful intermediates in organic synthesis, medicinal chemistry and material sciences. Transition-metal-catalyzed Heck couplings with organic halides as electrophiles have been established as a powerful protocol for the synthesis of this valuable building block. However, the requirement of organic halides and the generation of stoichiometric hazardous halide wastes may cause significant sustainable concerns. The halide-free oxidative Heck alkenylations involving organometallics or arenes as the coupling partners provide a facile and alternative pathway. Nonetheless, stoichiometric amounts of extra oxidant are essential in most cases. Herein, we present a direct dehydrogenative alkyl Heck-coupling reaction under oxidant-free conditions, liberating hydrogen, nitrogen and water as the side products. Excellent regioselectivity is achieved via neighboring oxygen atom coordination. Broad substrate scope, great functional group (ketone, ester, phenol, free amine, amide etc) tolerance and modification of pharmaceutical candidates and biological molecules exemplified its generality and practicability.

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Section: Resultsmentioning

confidence: 69%

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confidence: 99%

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Zhu

2019

Nat Commun

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“…The lower potential of chloride-based nucleophiles in epoxide/CO2 coupling reactions follows general trends typically noted in this area. 56 The selectivity was neither perturbed by the CO2 pressure (Table 1, entries 19-22), and was only affected slightly by the choice of solvent (entries [14][15][16][17][18]. In these cases, a lower selectivity goes accompanied by a lower conversion, and therefore MEK was selected as the solvent for further studies.…”

Section: Resultsmentioning

confidence: 99%

“…A fourth product was produced in minor amounts and was assigned by NMR spectroscopy (see SI) as the last remaining possible syn-isomer 3A. (14).…”

Section: Resultsmentioning

confidence: 99%

Effect of an Al(III) Complex on the Regio- and Stereoisomeric Formation of Bicyclic Organic Carbonates

Maquilón¹,

Limburg²,

Laserna³

et al. 2020

Preprint

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Valorization of carbon dioxide into organic molecules using catalytic approaches has witnessed an upsurge in recent years. Here, the influence of an Al(III) aminotriphenolate complex on the regio- and stereo-chemical features of the coupling between carbon dioxide and a cyclic epoxy alcohol has been studied. Three distinct bicyclic carbonate products were produced from a single starting material depending on the catalytic conditions. The proposed carbonate configurations were examined by solution and solid phase techniques including NMR spectroscopic and X-ray crystallographic analyses. Control experiments combined with DFT calculations provide a rationale for the distinct catalytic manifolds observed in the presence and absence of the Al(III) complex.

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“…This compound has been previously reported. 37 N-Tosyl-indol-3-ylacetic Acid 15c. Yield: 58% (93 mg, 0.28 mmol).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Pd(OH)₂/C, a Practical and Efficient Catalyst for the Carboxylation of Benzylic Bromides with Carbon Monoxide

Wakuluk-Machado

Dewez

Baguia

et al. 2019

Org. Process Res. Dev.

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A simple, efficient, cheap, and broadly applicable system for the carboxylation of benzylic bromides with carbon monoxide and water is reported. Upon simple reaction with only 2.5 wt % of Pearlman's catalyst and 10 mol % of tetrabutylammonium bromide in tetrahydrofuran at 110°C for 4 h, a range of benzylic bromides can be smoothly converted to the corresponding arylacetic acids in good to excellent yields after simple extraction and acid−base wash. The reaction was found to be broadly applicable, scalable, and could be successfully extended to the use of ex situ-generated carbon monoxide and applied to the synthesis of the nonsteroidal anti-inflammatory drug diclofenac.

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Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO₂

Abstract: The first ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2 to generate important aryl acetic acids is reported.

Cited by 74 publications

References 107 publications

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Effect of an Al(III) Complex on the Regio- and Stereoisomeric Formation of Bicyclic Organic Carbonates

Pd(OH)₂/C, a Practical and Efficient Catalyst for the Carboxylation of Benzylic Bromides with Carbon Monoxide

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Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2

Abstract: The first ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2 to generate important aryl acetic acids is reported.

Cited by 74 publications

References 107 publications

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Direct dehydrogenative alkyl Heck-couplings of vinylarenes with umpolung aldehydes catalyzed by nickel

Effect of an Al(III) Complex on the Regio- and Stereoisomeric Formation of Bicyclic Organic Carbonates

Pd(OH)2/C, a Practical and Efficient Catalyst for the Carboxylation of Benzylic Bromides with Carbon Monoxide

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Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO₂

Pd(OH)₂/C, a Practical and Efficient Catalyst for the Carboxylation of Benzylic Bromides with Carbon Monoxide