Chelation-Assisted RhI-Catalyzed ortho-Alkylation of Aromatic Ketimines or Ketones with Olefins

Jun, Chul Ho; Moon, Choong Woon; Hong, Ji Won; Lim, Sung Gon; Chung, Kwan Yong; Kim, Yeon Hee

doi:10.1002/1521-3765(20020118)8:2<485::aid-chem485>3.0.co;2-1

Cited by 156 publications

(26 citation statements)

References 40 publications

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“…In sharp contrast to the procedure developed by Murai and co‐workers, electron‐withdrawing substituents on the aromatic ring gave a much better reactivity than electron‐donating ones. Other advantages are that catalytic amounts of benzylamine could be used when directly starting from the arylketone, performing the reaction under microwave irradiation without solvent enabled a faster reaction, and the rhodium‐catalyzed ortho ‐alkylation of imines could be efficiently implemented for the functionalization of azines and polybutadiene, while a self‐assembled supported catalytic system enabled an easy recovery of the catalyst …”

Section: Carbonyl Derivatives As Directing Groupsmentioning

confidence: 99%

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

2019

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The alkylation of arenes is one of the most fundamental transformations in chemical synthesis leading to privileged scaffolds in many areas of science. Classical methods for the introduction of alkyl groups to arenes are mostly based on the Friedel-Crafts reaction, radical additions, metallation or pre-functionalization of the arene: these methods however suffer from limitations in scope, efficiency and selectivity. Moreover, they are based on the innate reactivity of the starting arene, favoring the alkylation at a certain position and rendering the introduction of alkyl chains at other positions much more challenging. This can be addressed by the use of a directing group facilitating, in the presence of a metal catalyst, the regioselective alkylation of a C-H bond. These directed alkylations of C-H bonds in arenes are overviewed, in a comprehensive manner, in this review article.

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Section: Carbonyl Derivatives As Directing Groupsmentioning

confidence: 99%

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

2019

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“…Indeed, isomerization to a thermodynamically more stable, but less reactive internal alkene is often the cause of less efficient or unsuccessful hydroarylation with terminal alkenes bearing allylic hydrogens 2b. 3a,c, 7 In a few cases, isomerization of an internal alkene to a terminal one is followed by hydroarylation to afford a primary alkylation product, as exemplified by the rhodium‐catalyzed reaction of an aromatic imine by Jun et al 3e,f. and the cobalt‐catalyzed reaction of a benzamide by Nakamura et al.,4b where anti‐Markovnikov selectivity of the catalysts serves as the driving force (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Alkene Isomerization–Hydroarylation Tandem Catalysis: Indole C2‐Alkylation with Aryl‐Substituted Alkenes Leading to 1,1‐Diarylalkanes

Yamakawa

Yoshikai

2014

Chemistry An Asian Journal

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A cobalt-N-heterocyclic carbene catalyst generated from CoBr2 , imidazolium salt, and cyclohexylmagnesium bromide was found to promote the imine-directed C2-alkylation of indoles with nonconjugated arylalkenes through a tandem alkene isomerization-hydroarylation process, affording 1,1-diarylalkanes with exclusive regioselectivity. The feasibility of the tandem catalysis was demonstrated for allyl-, homoallyl-, and bishomoallylbenzene derivatives. The catalytic system is also applicable to a variety of β-substituted styrene derivatives. Mechanistic experiments using deuterium-labeled indole substrate and Grignard reagent provided insight into the cobalt-mediated C-H activation step, which likely involves exchange of the C2-hydrogen atom of the former and the β-hydrogen atoms of the latter.

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“…observed the formation of the ortho ‐C(sp 2 )−H alkylation product along with the expected hydroacylated product . This result prompted the authors to investigate the selective alkylation of ortho ‐C−H bonds . The reaction of the aldimine 50 with 3,3‐dimethyl‐1‐butene in the presence of 2‐amino‐3‐picoline gave the ortho ‐C−H alkylation product 51 as a major product after hydrolysis (Scheme a) .…”

Section: C−h Functionalization Of Carbonyl Groupsmentioning

confidence: 99%

Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups

2019

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In recent years, transition‐metal‐catalyzed C−H activation has become a key strategy in the field of organic synthesis. Rhodium complexes are widely used as catalysts in a variety of C−H functionalization reactions because of their high reactivity and selectivity. The availability of a number of rhodium complexes in various oxidation states enables diverse reaction patterns to be obtained. Regioselectivity, an important issue in C−H activation chemistry, can be accomplished by using a directing group to assist the reaction. However, to obtain the target functionalized compounds, it is also necessary to use a directing group that can be easily removed. A wide range of directed C−H functionalization reactions catalyzed by rhodium complexes have been reported to date. In this Review, we discuss Rh‐catalyzed C−H functionalization reactions that are aided by the use of a removable directing group such as phenol, amine, aldehyde, ketones, ester, acid, sulfonic acid, and N‐heteroaromatic derivatives.

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Chelation-Assisted RhI-Catalyzed ortho-Alkylation of Aromatic Ketimines or Ketones with Olefins

Cited by 156 publications

References 40 publications

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

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

Alkene Isomerization–Hydroarylation Tandem Catalysis: Indole C2‐Alkylation with Aryl‐Substituted Alkenes Leading to 1,1‐Diarylalkanes

Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups

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Chelation-Assisted RhI-Catalyzed ortho-Alkylation of Aromatic Ketimines or Ketones with Olefins

Cited by 156 publications

References 40 publications

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

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

Alkene Isomerization–Hydroarylation Tandem Catalysis: Indole C2‐Alkylation with Aryl‐Substituted Alkenes Leading to 1,1‐Diarylalkanes

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

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Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups