Hydroarylation of Alkenes Using Anilines in Hexafluoroisopropanol

Colomer, Ignacio

doi:10.1021/acscatal.0c00872

Cited by 77 publications

(62 citation statements)

References 67 publications

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“…However, more recent approaches by the Yao, Patureau, Lebœuf, and Shi groups furnished ortho -hydroarylated products with high regioselectivity SI Section 2.0 Complementary to the above-mentioned processes, the work of Stephan and Colomer elegantly delivered para-selective hydroarylated products SI Section 2.0 From this perspective, the regioselective hydroarylation of conjugated 1,3-dienes remains rarely explored and more challenging with potentially multiple ways of hydroarylation.…”

mentioning

confidence: 99%

Boron-Catalyzed Hydroarylation of 1,3-Dienes with Arylamines

Archana

Grimme

et al. 2021

Org. Lett.

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Catalytic hydroarylation reactions of conjugated dienes are achieved using tris(pentafluorophenyl)borane as a Lewis acid catalyst under mild reaction conditions. This new protocol shows a broad substrate scope for the highly regioselective functionalization of sterically hindered aniline derivatives. Experimental and extensive density functional theory mechanistic studies show that the complex of residual water and B(C6F5)3 plays a crucial role in the aryl-assisted protonation of conjugated dienes, forming allyl cation intermediates that induce the facile electrophilic aromatic substitution of aniline substrates.

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confidence: 99%

Boron-Catalyzed Hydroarylation of 1,3-Dienes with Arylamines

Archana

Grimme

et al. 2021

Org. Lett.

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“…In reductive Meerwein arylations, the aryl radical addition to the alkene is followed by the formation of a C–H bond so that overall, an aryl unit and a hydrogen atom are added to the alkene unit in the sense of a hydroarylation. 9…”

Section: Hydroarylation and Carboarylationmentioning

confidence: 99%

Current Advances in Meerwein-type Radical Alkene Functionalizations

Heinrich¹,

Diesendorf²

2022

Synthesis

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Alkene functionalizations via Meerwein arylations are becoming increasingly attractive, especially since a variety of mild and sustainable methods for aryl radical generation are available today. This entails a broad spectrum of substrates and radical scavengers, as well as convenient synthetic routes to relevant precursors for further transformations. The present review focuses on recent advances in Meerwein-type alkene functionalizations and gives insights into the key mechanistic details of the respective reactions.1 Introduction2 Hydroarylation and Carboarylation3 Carboamination, Carbooxygenation, and Carbothiolation4 Carbohalogenation5 Conclusion and Outlook

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Section: Introductionmentioning

confidence: 99%

“…Interestingly, in 2020, Colomer reported that hexafluoroisopropanol (HFIP) could act as a Brønsted acid catalyst to promote the hydroarylation of styrene-type substrates with aniline derivatives at only 80 °C. 39 In the reported examples, the acidity of HFIP was increased by the addition of 25 mol % of tetrabutylammonium acetate (NBu 4 OAc). Although the HFIP/NBu 4 OAc catalytic system worked well for N-and Csubstituted aniline derivatives, the reaction was much less efficient with aniline because in this specific case, a stoichiometric amount of NBu 4 OAc was required to reach a 60% yield of the hydroarylation product.…”

Section: ■ Introductionmentioning

confidence: 99%

Selective Acid-Catalyzed Hydroarylation of Nonactivated Alkenes with Aniline Assisted by Hexafluoroisopropanol

Peng¹,

Humblot

Wischert³

et al. 2021

J. Org. Chem.

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The catalytic hydroarylation of nonactivated alkenes with aniline is a reaction of high interest, aiming at providing C-functionalized aniline derivatives that are important precursors for the fabrication of polyurethanes. However, this reaction remains a longstanding goal of catalysis, as it requires one to simultaneously address two important goals: (1) the very low reactivity of nonactivated alkenes and (2) control of the hydroarylation/hydroamination selectivity. As a result, the hydroarylation of aniline is mostly restricted to activated alkenes (i.e., featuring ring strain, conjugation, or activation with electron-donating or -withdrawing groups). Here we show that the combination of bismuth triflate and hexafluoroisopropanol (HFIP) leads to the formation of highly active catalytic species capable of promoting the hydroarylation of various nonactivated alkenes, such as 1-octene, 1-heptene, and 1-undecene, among others, with aniline with high selectivity (71–92%). Through a combined experimental and computational investigation, we propose a reaction pathway where HFIP stabilizes the rate-determining transition state through a H-bond interaction with the triflate anion, thus assisting the acid catalyst in the hydroarylation of nonactivated alkenes. From a practical point of view, this work opens a catalytic access to C-functionalized aniline derivatives from two cheap and abundant feedstocks in a 100% atom-economical fashion.

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Hydroarylation of Alkenes Using Anilines in Hexafluoroisopropanol

Cited by 77 publications

References 67 publications

Boron-Catalyzed Hydroarylation of 1,3-Dienes with Arylamines

Boron-Catalyzed Hydroarylation of 1,3-Dienes with Arylamines

Current Advances in Meerwein-type Radical Alkene Functionalizations

Selective Acid-Catalyzed Hydroarylation of Nonactivated Alkenes with Aniline Assisted by Hexafluoroisopropanol

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