Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

Kim, Junghwa; Yi, Chae S.

doi:10.1021/acscatal.6b00856

Cited by 29 publications

(22 citation statements)

References 49 publications

(34 reference statements)

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“…As supporting experimental evidence for the benzene ligand dissociation, we previously observed a facile arene exchange reaction and the formation of free benzene from the coupling reactions mediated by the Ru–H catalyst 1. 14…”

Section: Resultsmentioning

confidence: 99%

Experimental and Computational Study of the (Z)-Selective Formation of Trisubstituted Olefins and Benzo-Fused Oxacycles from the Ruthenium-Catalyzed Dehydrative C–H Coupling of Phenols with Ketones

et al. 2018

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The cationic Ru-H complex was found to be an effective catalyst for the dehydrative C-H coupling of phenols with ketones to form the trisubstituted olefin products. The coupling of phenol with linear ketones led to highly stereoselective formation of the ( Z)-olefin products. The dehydrative coupling of phenol with enones and diones efficiently formed the benzopyrene and related oxacyclic derivatives. The reaction of 3,5-dimethoxyphenol with cyclohexanone-2,2,6,6- d showed a significant H/D exchange to both vinyl and α-CH positions on the olefin product (72-75% D). A significant carbon isotope effect was observed on the ortho-arene carbon of the olefin product. The free energies of intermediate species for the entire catalytic cycle were successfully computed by using the DFT method. The DFT study revealed that the E/ Z stereoselectivity is a result of the energy difference in the insertion step of ortho-metalated phenol to an enol form of the ketone substrate (ΔΔ E = 9.6 kcal/mol). The coupling method provides a direct catalytic C-H olefination method for ketones to form trisubstituted olefins without employing any reactive reagents or forming any wasteful byproducts.

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Section: Resultsmentioning

confidence: 99%

Experimental and Computational Study of the (Z)-Selective Formation of Trisubstituted Olefins and Benzo-Fused Oxacycles from the Ruthenium-Catalyzed Dehydrative C–H Coupling of Phenols with Ketones

et al. 2018

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“…The hydroacylation can be accomplished via metal‐catalyzed C−H bond activation . Transition metals such as Rh,– Ru, Co, and Ni have been widely employed as catalysts in this field. However, most of these metals are expensive and toxic.…”

Section: Methodsmentioning

confidence: 99%

DTBP/TBHP‐Promoted Hydroacylation of Unactivated Alkenes

et al. 2016

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Di-tert-butyl peroxide (DTBP)-promotedi ntermolecular hydroacylation reaction of alkenes with aromatic aldehydes that provides ketonesi sd escribed. In this study,4 -chromanones were formed when 2-(allyloxy)benzaldehydesw ere treated with tert-butyl hydroperoxide (TBHP). The reactions were performed under solvent-and metal-free conditions. Reactions proceeded through the generation of acyl radicals, followed by the reaction with alkenes. Remarkably,n ot only terminal alkenes but also internal alkenes could serve as the starting materials for intramolecular hydroacylationr eaction.Scheme1.Metal-free hydroacylation of alkenes.

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“…Finally, the synergistic Ni/Cu two‐metal catalyst was applied to the derivatization of a complex molecule (Scheme ). Vinylestrone 2 i underwent hydroacylation with 1 a and HSiMe(OMe) 2 at 25 °C, affording 3 p as a 1:1 diastereomeric mixture in 48 % yield without reduction of the cyclopentanone moiety …”

Section: Methodsmentioning

confidence: 99%

“…Vinylestrone 2i underwent hydroacylation with 1a and HSi-Me(OMe) 2 at 25 8C, affording 3p as a1 :1 diastereomeric mixture in 48 %y ield without reduction of the cyclopentanone moiety. [26] In summary,t he hydroacylation of vinylarenes with acyl fluorides and hydrosilanes by synergistic Ni/Cu two-metalc atalysis has been developed. The use of DCYPBz as al igand with its electron-donating, sterically demanding, and rigidp roperties was effective for producing the catalytically active Ni species.…”

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confidence: 99%

Nickel‐Copper‐Catalyzed Hydroacylation of Vinylarenes with Acyl Fluorides and Hydrosilanes

Ueda

Iwai

Sawamura

2019

Chemistry A European J

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The hydroacylation of vinylarenesw ith acyl fluorides and hydrosilanes was enabled by as ynergistic bimetallic Ni/Cu-catalytic system, giving access to the corresponding branched ketone products. The reaction takes place under mild conditions at 25-80 8Ca nd tolerates base-sensitive functional groups such as methoxycarbonyl and acetoxy groups.Acyl fluorides, which are easily preparedf rom carboxylic acids, [1] are less common as acylatingr eagents than the corresponding chlorides and bromides due to their inertness as acylating reagents under conventional conditions. However,t he use of acyl fluoridesa sr eagents in organic synthesis through activation of the CÀFb ond have attracted growing interest in recent years, offering new types of molecular transformations that have not been achieved with acyl chlorideso rb romides. Generally,t he fluorides show better tolerance towards nucleophilic or basic functional groups than the chlorides and bromides.Apioneering work by Rovis described an efficient ketone synthesis through Ni-catalyzed cross-coupling of acyl fluorides with organozincs( Scheme 1a). [2] Later,O giwaraa nd Sakai reported similart ransformationsu sing organosiliconso r organoborons by Pd catalysis. [3] These reactions were initiated by oxidativea ddition of the acyl C(sp 2 )ÀFb onds to low-valent metal complexes,producing acyl metal intermediates. [4,5] Catalytic in situ generation of nucleophilic organometallic speciesb yi nsertiono fu nsaturated CÀCb onds to MÀXb onds followed by trapping with acyl electrophiles affords attractive synthetic methods, which can avoid the use of stoichiometric amountso fp re-formed organometallic reagents. [6] Metal-catalyzed reductivec ouplingo fC ÀCu nsaturated compounds with electrophiles is representative. [7,8] For acylation,c arboxylic anhydrides were used as acylating electrophiles in the reactiono f vinylarenes in the presence of hydrosilanes or H 2 as H sources. [6a, 7a,b] More recently,G agosz and Riant used acyl fluorides as acylating reagents for the Cu-catalyzed boroacylation of alleneswith bis(pinacolato)diboron (Scheme 1b). [9] Our long-standing interest in synergistic bimetallic catalysis prompted us to explore the possibility of enabling the hydroacylation of vinylarenes with acyl fluorides and hydrosilanes by synergistic Ni/Cu two-metal catalysis. [10][11][12][13][14][15] As shown in Scheme 1c,a na cyl fluoridei sa ctivated through oxidative addition to aN i(0) complex (step a). Concurrently,avinylarene is converted into an ucleophilic alkylcopper speciesb yi nsertion into aC u ÀHs pecies( hydrocupration, step d) [16] that is generated in situ from aC u ÀFs peciesw ith ah ydrosilane (step e). [17] The two catalytic speciesm eet and transmetalation occurs to give the corresponding diorganonickel(II) complex with simultaneous regeneration of the CuÀFs pecies (step b). Finally,r e-[a] Prof. Dr.M.S awamura Institute for Chemical Reaction Design and Discovery (WPI-ICReDD)

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Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium–Hydride Complex

Cited by 29 publications

References 49 publications

Experimental and Computational Study of the (Z)-Selective Formation of Trisubstituted Olefins and Benzo-Fused Oxacycles from the Ruthenium-Catalyzed Dehydrative C–H Coupling of Phenols with Ketones

Experimental and Computational Study of the (Z)-Selective Formation of Trisubstituted Olefins and Benzo-Fused Oxacycles from the Ruthenium-Catalyzed Dehydrative C–H Coupling of Phenols with Ketones

DTBP/TBHP‐Promoted Hydroacylation of Unactivated Alkenes

Nickel‐Copper‐Catalyzed Hydroacylation of Vinylarenes with Acyl Fluorides and Hydrosilanes

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