Aldimine‐Directed Branched‐Selective Hydroarylation of Styrenes

Lee, Pin‐Sheng; Yoshikai, Naohiko

doi:10.1002/ange.201207958

Cited by 37 publications

(6 citation statements)

References 60 publications

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“…154 In the same year, Yoshikai and co-workers explored an iminedirected alkylation of arenes with aryl olefins. 155,156 Using triarylphosphines as the ligands, only branched products were obtained (Scheme 99), which parallels the results with 1,10phenanthroline as the ligand (vide supra, Scheme 94). 151 In 2014, the same team discovered that linear selectivity can be realized using a bulky triarylphosphine (92) with aryl imine substrates (Scheme 100).…”

Section: Alkylation Via C−h Activation 21 Alkylation Of Aromatic C−h ...supporting

confidence: 75%

Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

et al. 2017

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Alkylation reactions represent an important organic transformation to form C-C bonds. In addition to conventional approaches with alkyl halides or sulfonates as alkylating agents, the use of unactivated olefins for alkylations has become attractive from both cost and sustainability viewpoints. This Review summarizes transition-metal-catalyzed alkylations of various carbon-hydrogen bonds (addition of C-H bonds across olefins) using regular olefins or 1,3-dienes up to May 2016. According to the mode of activation, the Review is divided into two sections: alkylation via C-H activation and alkylation via olefin activation.

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Section: Alkylation Via C−h Activation 21 Alkylation Of Aromatic C−h ...supporting

confidence: 75%

Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

et al. 2017

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“…While previous reports have demonstrated that the CMD under similar conditions is reversible, 39,42 this isotopic labelling study is consistent with accounts of mechanistic variations caused by small changes in substrate. 43 Broadening this result to achieve general, ligand-controlled selectivity requires more experimental study and is ongoing in our lab. In conclusion, we have developed an efficient process for the synthesis of benzocyclobutenes by Pd(II) catalyzed methylene C(sp 3 )-H arylation with a transient directing group.…”

Section: Figure 3 Isotope-incorporation Experiments Indicating An Irr...mentioning

confidence: 99%

“…While previous reports have demonstrated that CMD under similar conditions is reversible, 19,69 calculations and an isotopic labeling study are consistent with accounts of mechanistic variations caused by small changes in the substrate. 70 In this case, the methylene selectivity may be due to two factors: (1) ligand−substrate interactions that promote methylene selectivity and (2) the geometry of Pd at the competing OA transition states. This result is distinct from our earlier publication that described indane cyclizations by reversible CMD.…”

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confidence: 99%

Pd(II)-Catalyzed Synthesis of Benzocyclobutenes by β-Methylene-Selective C(sp³)–H Arylation with a Transient Directing Group

et al. 2021

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Methylene-selective C-H functionalization is a significant hurdle that remains to be addressed in the field of Pd(II) catalysis. In this paper we report a Pd(II) catalyzed synthesis of benzocyclobutenes by methylene-selective C(sp 3 )-H arylation of ketones using a transient directing group. The reaction utilizes glycine as a transient directing group and an electron poor pyridone ligand which is expected to promote concerted metallation deprotonation, but also controls methylene selectivity by intimate interactions with the substrate. These reaction conditions are shown to be highly selective for intramolecular methylene C(sp 3 )-H arylation, and thus enable sequential C(sp 3 )-H functionalization.

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“…802 The low-valent cobalt-catalyzed hydroarylation of alkenes was not restricted to N-aryl ketimines (see Schemes 213b and 215). Hence, recent studies by the Yoshikai group proved that N-aryl aldimines 803 139 as well as NH-free ketimines 804,805 199 also served as directing group for the cobalt-catalyzed C− H activation regime (Scheme 217). These findings enabled the synthesis of ortho-alkylated aldehydes 474 as well as fourfold ortho-alkylations of benzophenones 475.…”

Section: Stoichiometric C−h Activationmentioning

confidence: 99%

3d Transition Metals for C–H Activation

et al. 2018

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C−H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C−H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C−H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C−H activation until summer 2018.

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Aldimine‐Directed Branched‐Selective Hydroarylation of Styrenes

Cited by 37 publications

References 60 publications

Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

Pd(II)-Catalyzed Synthesis of Benzocyclobutenes by β-Methylene-Selective C(sp³)–H Arylation with a Transient Directing Group

3d Transition Metals for C–H Activation

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Aldimine‐Directed Branched‐Selective Hydroarylation of Styrenes

Cited by 37 publications

References 60 publications

Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

Transition-Metal-Catalyzed C–H Alkylation Using Alkenes

Pd(II)-Catalyzed Synthesis of Benzocyclobutenes by β-Methylene-Selective C(sp3)–H Arylation with a Transient Directing Group

3d Transition Metals for C–H Activation

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Pd(II)-Catalyzed Synthesis of Benzocyclobutenes by β-Methylene-Selective C(sp³)–H Arylation with a Transient Directing Group