Palladium‐Catalyzed Divergent Cyclopropanation by Regioselective Solvent‐Driven C(sp<sup>3</sup>)−H Bond Activation

Chung, Da Sol; Lee, Jae Sung; Ryu, Ho Jin; Park, Jiyong; Kim, Hyun‐Joong; Lee, Juhyun; Kim, U. Bin; Lee, Won Koo; Baik, Mu Hyun; Lee, Sang Gi

doi:10.1002/anie.201809133

Cited by 29 publications

(13 citation statements)

References 63 publications

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“…Alternatively, protonation of C 1 with pivalic acid , furnishes alkylpalladium complex D 1 . The sequence B 1 → C 1 → D 1 results in an overall 1,4-Pd shift. , A second base-induced C(sp 3 )–H activation from D 1 leads to the rare four-membered palladacycle E 1 , ,, already suggested by Martin, which reductively eliminates to generate cyclopropane 3b .…”

Section: Results and Discussionmentioning

confidence: 84%

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Direct Synthesis of Cyclopropanes from gem-Dialkyl Groups through Double C–H Activation

Clemenceau

Thesmar

Gicquel³

et al. 2020

J. Am. Chem. Soc.

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Cyclopropanes are important structural motifs found in numerous bioactive molecules, and a number of methods are available for their synthesis. However, one of the simplest cyclopropanation reactions involving the intramolecular coupling of two C-H bonds on gem-dialkyl groups has remained an elusive transformation. We demonstrate herein that this reaction is accessible using aryl bromide or triflate precursors and the 1,4-Pd shift mechanism. The use of pivalate as the base was found to be crucial to divert the mechanistic pathway toward the cyclopropane instead of the previously obtained benzocyclobutene product. Stoichiometric mechanistic studies allowed the identification of aryl-and alkylpalladium pivalates, which are in equilibrium via a five-membered palladacycle. With pivalate, a second C(sp 3)-H activation leading to the four-membered palladacycle intermediate and the cyclopropane product is favored. A catalytic reaction was developed and showed a broad scope for the generation of diverse arylcyclopropanes, including valuable bicyclo[3.1.0] systems. File list (2) download file view on ChemRxiv Baudoin.pdf (847.45 KiB) download file view on ChemRxiv SupportingInformation.pdf (11.66 MiB)

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Section: Results and Discussionmentioning

confidence: 84%

“…(Scheme b) . Besides, cyclopropanes have been generated through domino reactions including olefin carbopalladation and C(sp 3 )–H activation, leading to putative 4-membered palladacyclic intermediates (Scheme c). , …”

Section: Introductionmentioning

confidence: 99%

Direct Synthesis of Cyclopropanes from gem-Dialkyl Groups through Double C–H Activation

Clemenceau

Thesmar

Gicquel³

et al. 2020

J. Am. Chem. Soc.

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“…First, a nitro-aldol reaction of aldehyde 21 gave 22 in good yield. [20] Then conjugate addition of diethyl Hphosphonate, promoted by DBU, followed by elimination under the reaction conditions produced unsaturated phosphonate 23 in moderate yield. [21] Next a Corey-Chaykovsky cyclopropanation [22] proceeded uneventfully to cyclopropane 24.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Carbon‐ and Nitrogen‐Substituted 5‐ and 6‐Membered Benzophostams

et al. 2022

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Previously, the synthesis of the novel 6-membered and a series of P-substituted 5-membered benzophostams was accomplished. Here, the synthesis of N-and C-substituted benzophostams is presented. For N-substitution, alkylation was accomplished using the heterocycle, LiHMDS and an alkyl halide, or alternatively by copper-catalyzed cyclization of the N-alkyl phosphonamide. N-Arylation could similarly be accomplished on the preformed heterocycle or on the phosphonamide precursor via copper-catalyzed cross-coupling. Dimethylation at the benzylic position could be conducted with LiHMDS and methyl iodide. However, due to the significant cost of LiHMDS, a much less expensive and more efficient alternative approach was developed relying on a palladium-catalyzed reductive Heck reaction.

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“…Various metals and its composite was use for catalytic activities such as Co-N doped carbon [14], Ruthenium supported on ZIF-67 [15], cobalt [16,17], Fe-doped CoP [1], and Pd [19][20][21]. While Pd nanoparticles used as catalyst in heck reaction [22] represents multistep synthesis root, requires massive energy, such as vacuum, pressure and toxic chemicals [3]. As well as palladium is well known for its catalytic activity as oxidative convertor of glycerol [23], as automotive catalyst [24], oil re ning process [25], polyester manufacturing [26] and bacterial reduction of graphene oxide (GO) and Pd (II) salt supported E. coli utilized for production of H 2 and sodium formate [27].…”

Section: Introductionmentioning

confidence: 99%

One Pot Bio-Synthesis of Palladium Nanoneedles and Its Bioavailability

Kulal

Pansare

Shedge

et al. 2021

Preprint

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Bioinorganic chemistry has achieved great importance by considering environmental and health issues. Here we present anticancer, antioxidant, good protein quencher single pot biosynthesized one dimensional palladium Nanoneedles (PdNNs) as a negative catalyst, where water plays a role of safer solvent. Needle-shaped one-dimensional PdNNs was synthesized using filamentous fungal stain of Aspergillus oryzae (biomass) was successively applied as a suppressant for the growth of human breast, colon and leukemia cancer Cell Lines. Quenching process of bovine serum albumin by PdNNs was spontaneous with hydrogen bonding and hydrophilic interaction. Interaction of protein and PdNNs showed binding constant in the range of 104 M-1 and one binding site. Forster's resonance energy transfer (FRET) theory applied to find out distance between the interaction of PdNNs and protein, where critical distance and energy transfer distance varies with change in concentrations of PdNNs 4.84 x 10−6 M to 9.69 x 10-7 M from 2.9 to 3.7 nm and 3.2 to 5.4 nm respectively. Radical scavenging method was applied to find out an antioxidant activity which of nanoneedles. Needle-shaped palladium nanoparticles and particle size found to be ̴ 3.0 nm using high-resolution transmission electron microscopes.

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Palladium‐Catalyzed Divergent Cyclopropanation by Regioselective Solvent‐Driven C(sp³)−H Bond Activation

Cited by 29 publications

References 63 publications

Direct Synthesis of Cyclopropanes from gem-Dialkyl Groups through Double C–H Activation

Direct Synthesis of Cyclopropanes from gem-Dialkyl Groups through Double C–H Activation

Synthesis of Carbon‐ and Nitrogen‐Substituted 5‐ and 6‐Membered Benzophostams

One Pot Bio-Synthesis of Palladium Nanoneedles and Its Bioavailability

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Palladium‐Catalyzed Divergent Cyclopropanation by Regioselective Solvent‐Driven C(sp3)−H Bond Activation

Cited by 29 publications

References 63 publications

Direct Synthesis of Cyclopropanes from gem-Dialkyl Groups through Double C–H Activation

Direct Synthesis of Cyclopropanes from gem-Dialkyl Groups through Double C–H Activation

Synthesis of Carbon‐ and Nitrogen‐Substituted 5‐ and 6‐Membered Benzophostams

One Pot Bio-Synthesis of Palladium Nanoneedles and Its Bioavailability

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Product

Resources

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Palladium‐Catalyzed Divergent Cyclopropanation by Regioselective Solvent‐Driven C(sp³)−H Bond Activation