Nickel‐Catalyzed Hydroheteroarylation of Vinylarenes

Nakao, Yoshiaki; Kashihara, Natsuko; Kanyiva, Kyalo Stephen; Hiyama, Tamejiro

doi:10.1002/ange.201001470

Cited by 74 publications

(24 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…One of the first examples of direct transition‐metal‐catalyzed alkylation of electron‐rich heteroarenes with alkenes was reported in 2004 by Gunnoe for the ethylation of furan and thiophene by using a preformed ruthenium(II) complex . Six years later, Nakao and Hiyama reported the nickel‐catalyzed alkylation of electron‐deficient indoles, as well as of some azoles, with styrenes, as previously described in Section 2.2.1 for N ‐methylbenzimidazole, (benz)oxazole, and benzothiazole . Provided that indoles are activated by electron‐withdrawing groups at the C3‐position, which also allows the control of the regioselectivity to be circumvented, the reaction smoothly provides the corresponding branched isomers in fair to good yields [Scheme , Eq.…”

Section: Alkylation Of Heteroarenesmentioning

confidence: 90%

“…Later on, Nakao and Hiyama reported the use of Ni(cod) 2 and IMes for the direct alkylation (mostly benzylation) of some electron‐poor indoles (see Section 2.3.1 for details) as well as of several azoles such as N ‐methylbenzimidazole, (benz)oxazole, and benzothiazole [Scheme , Eq. (2)] . Here again, branched isomers are obtained from styrenes, whereas alkyl‐substituted olefins afford the linear products (only described with indoles in this case).…”

Section: Alkylation Of Heteroarenesmentioning

confidence: 93%

See 1 more Smart Citation

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

Evano

Theunissen

2019

Angew Chem Int Ed

View full text Add to dashboard Cite

Alkylated arenes are ubiquitous molecules and building blocks commonly utilized in most areas of science where there is a need for small organic molecules. Despite its apparent simplicity, the regioselective alkylation of arenes is still a challenging transformation in a lot of cases. Classical methods for the introduction of alkyl groups on arenes, which include the venerable Friedel-Crafts reaction, radical additions, metallation or pre-functionalization of the arene, as well as alternatives such as the directed alkylation of C-H bonds, still suffer from severe limitations in terms of scope, efficiency and selectivity. This can be addressed by exploiting the innate reactivity of some (hetero)arenes, in which electronic and steric properties, governed (or not) by the presence of one (or multiple) heteroatom(s) ensure high levels of regioselectivity. These innate alkylations of C-H bonds in (hetero)arenes will be overviewed, in a comprehensive manner, in this review article.

show abstract

Section: Alkylation Of Heteroarenesmentioning

confidence: 90%

Section: Alkylation Of Heteroarenesmentioning

confidence: 93%

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

Evano

Theunissen

2019

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

“…[3c] Similarly, our group, [4] as well as those of Nakao and Hiyama [5] and Kanai, [6] have observed the beneficial effect of added AlMe 3 in promoting nickel-mediated CÀH bond activation of heteroarenes. More recently, we reported a switch in the regioselectivity for CÀH functionalization of benzimidazole derivatives with styrene and allylbenzene to afford either linear or branched products when using AlMe 3 .…”

Section: Introductionmentioning

confidence: 90%

Mechanistic Study of a Switch in the Regioselectivity of Hydroheteroarylation of Styrene Catalyzed by Bimetallic Ni–Al through CH Activation

Chen

Lai

Shih

et al. 2014

Chemistry A European J

View full text Add to dashboard Cite

We previously reported a highly efficient protocol for bimetallic Ni-Al-catalyzed hydroheteroarylation of styrene with benzimidazole based on C-H bond activation. We have now delineated the mechanism of this process, providing a rationale for an observed switch in regioselectivity in the presence of the Lewis acid, AlMe3. The present mechanistic study gives insights for the rational development of catalysts that exhibit required linear/branched selectivity.

show abstract

“…During the past decade, remarkable progress has been made for the nickel‐catalyzed C−H bond alkylation of arenes and heteroarenes. At the early stage of indole alkylation, Hiyama and co‐workers reported the alkylation of indoles by hydroarylation strategy wherein activated alkenes led to branched selectivity and unactivated alkenes dominantly produced linear product (Scheme ) …”

Section: Alkylation Reactionsmentioning

confidence: 99%

C−H Functionalization of Indoles by 3d Transition‐Metal Catalysis

Jagtap

Punji

2019

Asian J Org Chem

View full text Add to dashboard Cite

Over the past decade, the use of 3d transition metal for the regioselective C−H bond functionalization of indoles has significantly increased. Particularly, advances in manganese, iron, cobalt, nickel and copper catalysis have demonstrated the selective C(2)−H and C(3)−H arylation, alkenylation, alkynylation and alkylation to a greater extent. Similarly, the C−O and C−N bond‐forming reactions are manifested via direct C−H bond activation by these earth‐abundant metals. The emergence of 3d metals in selective functionalization of the biologically relevant indoles and related heteroarenes would make this protocol more attractive for practical applications. Herein, we provide a brief overview of 3d transition metal‐catalyzed (mostly Mn, Fe, Co, Ni and Cu) C−H functionalization of indoles and related heteroarenes.

show abstract

Nickel‐Catalyzed Hydroheteroarylation of Vinylarenes

Abstract: Mit ausgezeichneter Regioselektivität verläuft die durch einen Nickel‐Carben‐Katalysator ausgelöste Hydroheteroarylierung von Vinylarenen zu 1,1‐Diarylethanen, bei der eine Vielzahl von Heteroarylbausteinen eingebaut werden kann. EWG=elektronenziehende Gruppe.

Cited by 74 publications

References 23 publications

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

Mechanistic Study of a Switch in the Regioselectivity of Hydroheteroarylation of Styrene Catalyzed by Bimetallic Ni–Al through CH Activation

C−H Functionalization of Indoles by 3d Transition‐Metal Catalysis

Contact Info

Product

Resources

About