Ligand‐Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis

Kuai, Chang‐Sheng; Ji, Ding‐Wei; Zhao, Chaoyang; Liu, Heng; Hu, Yan‐Cheng; Chen, Qing‐An

doi:10.1002/anie.202007930

Cited by 69 publications

(20 citation statements)

References 141 publications

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“…Very recently, Breit's group reported an impressive achievement in metal catalyzed couplings of indazole with allenes (Figure 1 C). [16] In our continued interest towards regiodivergent transformations of isoprene, [6k, 9h,j] it is noteworthy that the exploitation of naturally and industrially abundant isoprene in coupling with indazoles is largely absent in the literature. This is speculated to be attributed to obstacles towards regiocontrol: 1) the competitive nucleophilic sites between the N 1 and N 2 positions of indazole; 2) the four electrophilic sites derived from the electronically unbiased alkenyl carbon atoms of isoprene.…”

Section: Introductionmentioning

confidence: 99%

Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

Jiang

Zhang

et al. 2021

Angew Chem Int Ed

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Depending on the reactant property and reaction mechanism, one major regioisomer can be favored in areaction that involves multiple active sites.H erein, an orthogonal regulation of nucleophilic and electrophilic sites in the regiodivergent hydroamination of isoprene with indazoles is demonstrated. Under Pd-hydride catalysis,t he 1,2-or 4,3insertion pathway with respect to the electrophilic sites on isoprene could be controlled by the choice of ligands.Interms of the nucleophilic sites on indazoles,t he reaction occurs at either the N 1-o rN 2-position of indazoles is governed by the acid co-catalysts.P reliminary experimental studies have been performed to rationalizet he mechanism and regioselectivity. This study not only contributes ap ractical tool for selective functionalization of isoprene,b ut also provides ag uide to manipulate the regioselectivity for the N-functionalization of indazoles.

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Section: Introductionmentioning

confidence: 99%

Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

Jiang

Zhang

et al. 2021

Angew Chem Int Ed

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“…Thus far, only a few examples of hydrosilylation of natural compounds have been reported. [18] Among them, eugenol seems to be an interesting reagent for the synthesis of SCAs due to the possibility to carry out hydrosilylation reactions with the allyl group and substitution of the hydroxyl group with various organic compounds.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bio‐Based Silane Coupling Agents by the Modification of Eugenol

et al. 2021

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A simple method for the synthesis of new bio-based silane coupling agents (SCAs) with a terpene aromatic core by the functionalization of cheap, natural eugenol and its sulfur derivatives using the hydrosilylation of the C=C bonds with HSi(OEt) 3 , followed by nucleophilic substitution reactions of OH/SH groups is presented. The obtained alkoxysilanes possess different polymerreactive functionalities (alkenyl, epoxide, thiirane, thiocarbamoyl, thioester, thioether moieties). This new group of biogenic SCAs was fully characterized using 1 H, 13 C, 29 Si NMR, FT-IR, GC-MS, and HRMS or elemental analysis. Examples of their application as additives to tire rubbers and their influence on several factors are also discussed.

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“…In the course of our study, we came across that the hydrosilylation of conjugated dienes catalyzed by a mono(phosphine)palladium(0) complex gives the 1,2- E and 1,4- Z products depending on the phosphorus ligand used and the nature of silanes (eq ). In this contribution, we disclose regiodivergent hydrosilylation of conjugated diene catalyzed by the mono(phosphine)palladium(0) complexes …”

Section: Introductionmentioning

confidence: 90%

Ligand-Controlled Regiodivergent Hydrosilylation of Conjugated Dienes Catalyzed by Mono(phosphine)palladium(0) Complexes

et al. 2020

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Mono(phosphine)palladium(0) complexes, [Pd(η2:η2-C6H10O)(PR3)] (1), catalyze hydrosilylation of electron-deficient conjugated dienes with HSiPh3. Hydrosilylation of methyl penta-2,4-dienoate with HSiPh3 catalyzed by [Pd(η2:η2-C6H10O)(PR3)] (R = Me (1a), Et (1b), OEt (1d), O i Pr (1e)) proceeds to give the 1,2-E product in quantitative yield with exclusive Markovnikov selectivity. In contrast, their triphenylphosphine and -phosphite analogues, [Pd(η2:η2-C6H10O)(PR3)] (R = Ph (1f), OPh (1g)), mainly produce the 1,4-Z product (1,2-E/1,4-Z = 3/7). The regioselectivity in the hydrosilylation of methyl 2,4-pentadienoate is also controlled by organosilanes. Mechanistic studies suggest that the reaction using a compact and basic mono-phosphorus complex proceeds by the Chalk–Harrod mechanism involving the reductive elimination from an (η3-allyl)(silyl)palladium(II). A poor electron-donating mono-phosphorus ligand such as P(OPh)3 destabilizes a Pd(II) species and promotes direct reductive elimination to give the 1,4-Z product. On the other hand, a compact and electron-donating phosphorus ligand, such as PMe3, PEt3, and P(OMe)3, favors to give the more stable (η3-allyl)(silyl)palladium(II) intermediate by the allyl rotation, followed by reductive elimination to give the 1,2-E product.

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Ligand‐Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis

Cited by 69 publications

References 141 publications

Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

Orthogonal Regulation of Nucleophilic and Electrophilic Sites in Pd‐Catalyzed Regiodivergent Couplings between Indazoles and Isoprene

Synthesis of Bio‐Based Silane Coupling Agents by the Modification of Eugenol

Ligand-Controlled Regiodivergent Hydrosilylation of Conjugated Dienes Catalyzed by Mono(phosphine)palladium(0) Complexes

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