Recent progress in transition metal catalysed hydrofunctionalisation of less activated olefins

Yadav, J. S.; Antony, Aneesh; Rao, T. Siva; Reddy, B. V. Subba

doi:10.1016/j.jorganchem.2010.09.052

Cited by 78 publications

(29 citation statements)

References 146 publications

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“…he abundance, low cost and distinct reactivity profiles of alkenes have enabled these feedstock molecules to be widely utilized in olefin functionalization reactions for various chemical synthesis applications [1][2][3] . In this respect, the installation of a hydrogen and carbon-based moiety across πsystems represents an effective strategy for C-C bond construction [4][5][6] . Numerous hydrocarbofunctionalization protocols rely on conjugation (i.e., 1,3-dienes [7][8][9][10][11] , olefins such as styrenes [12][13][14] , alkenyl boronates 15,16 , and Michael acceptors 17 ) to deliver high regioselectivity.…”

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confidence: 99%

Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation

et al. 2020

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Among the plethora of catalytic methods developed for hydrocarbofunctionalization of olefins to date, reactions that regioselectively install a functionalized alkyl unit at the 2-position of a terminal unactivated C=C bond to afford branched products are scarce. Here, we show that a Ni-based catalyst in conjunction with a stoichiometric reducing agent promote Markovnikov-selective hydroalkylation of unactivated alkenes tethered to a recyclable 8-aminoquinaldine directing auxiliary. These mild reductive processes employ readily available primary and secondary haloalkanes as both the hydride and alkyl donor. Reactions of alkenyl amides with ≥ five-carbon chain length regioselectively afforded β-alkylated products through remote hydroalkylation, underscoring the fidelity of the catalytic process and the directing group’s capability in stabilizing five-membered nickelacycle intermediates. The operationally simple protocol exhibits exceptional functional group tolerance and is amenable to the synthesis of bioactive molecules as well as regioconvergent transformations.

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confidence: 99%

Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation

et al. 2020

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“…The relevant literature has been covered from 2012 until early 2019. For early developments, the reader should refer to previously reported reviews . Achievements in the direct addition of electronically biased amines (such as as sulfonamides, carbamates or amides) on unactivated alkenes are beyond the scope of this review as such C−N bond formation reactions are today more appropriately called hydroamidation reactions …”

Section: Introductionmentioning

confidence: 99%

Alkene Hydroamination via Earth‐Abundant Transition Metal (Iron, Cobalt, Copper and Zinc) Catalysis: A Mechanistic Overview

et al. 2020

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This review gives am echanistic overview of the most relevant advancesi nt he area of alkene (formal) hydroamination promoted by earth-abundant transitionm etal catalysts involving iron, cobalt, copper and zinc. Focus will be on catalytic systems for which in depth investigations have been conducted to elucidate the activation pathwaya nd operating mechanism. Ther elevant literature has been covered from 2012u ntil early2 019. 1I ntroduction 2M echanism Overview 3A lkeneA ctivation Pathways 3.1 p-Coordination 3.2 Hydrometalation 3.3 H-Atom Tr ansfer 4A mine Deprotonation Pathway 5C onclusionScheme 5. Proposed mechanism for the DTBM-SEG-PHOS·CuH-catalyzedh ydroamination of styrene and Bn 2 NOCOAr proceeding by alkene hydrometalation [L 1 = (R)-DTBM-SEGPHOS].Scheme 7. Proposed metal hydride H-atom transfer (HAT) mechanism of iron-promoted formal hydroamination of nitro(hetero)arenes and (poly)substituted alkenes.

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“…They are widely used in the production of agrochemicals, pharmaceuticals, organic dyes, detergents, fabric softeners, surfactants, corrosion inhibitors, lubricants, polymers and so on [1,2,3]. Due to the widespread use of these products, a number of synthesis routes have been developed based on classic nucleophilic substitution, like Buchwald-Hartwig [4], Ullmann reactions [5], and hydroamination [6,7,8].…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient and Selective N-Alkylation of Amines with Alcohols Catalyzed by in Situ Rehydrated Titanium Hydroxide

et al. 2020

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Catalytic N-alkylation of amines by alcohols to produce desired amines is an important catalytic reaction in industry. Various noble metal-based homogeneous and heterogeneous catalysts have been reported for this process. Development of cheap non-noble metal heterogeneous catalysts for N-alkylation reaction would be highly desirable. Hereby, we propose the N-alkylation of amines by alcohols over a cheap and efficient heterogeneous catalyst -titanium hydroxide. The catalyst provides the selectivity higher than 90% to secondary amines for functionalized aromatic, aliphatic alcohols and amines at high catalytic activity and stability. Mild Brönsted acidity formed by continuous rehydration of Lewis acidity excludes side reactions and deactivation by adsorbed species. The mechanism of the reaction involves dehydration of alcohols to ethers with subsequent C-O bond cleavage by amine with formation of secondary amine and recovery of alcohol.

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Recent progress in transition metal catalysed hydrofunctionalisation of less activated olefins

Cited by 78 publications

References 146 publications

Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation

Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation

Alkene Hydroamination via Earth‐Abundant Transition Metal (Iron, Cobalt, Copper and Zinc) Catalysis: A Mechanistic Overview

Highly Efficient and Selective N-Alkylation of Amines with Alcohols Catalyzed by in Situ Rehydrated Titanium Hydroxide

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