Synthetic Applications of the Titanium-Catalyzed Exchange of Olefins with Grignard Reagents<sup>1a</sup>

Finkbeiner, Herman; Cooper, Glenn D.

doi:10.1021/jo01057a003

Cited by 73 publications

(13 citation statements)

References 2 publications

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“…[143] It was also reported that FeCl 3 would catalyse the hydromagnesiation of styrene (105), albeit in only 15 % yield (Scheme 60 A, 51 % yield using TiCl 4 ).…”

Section: Hydromagnesiationmentioning

confidence: 98%

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

2014

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The metal‐catalysed hydrofunctionalisation of alkenes and alkynes provides a convenient and atom‐economic route to diversely functionalised products with control of regio‐, chemo‐ and stereoselectivity. As one of the most abundant elements on earth, iron offers a level of sustainable and long‐term availability that is uncommon for most transition metals. Although iron is commonly found in the oxidation states of +2 and +3, the use of redox‐active ligands has allowed the synthesis and application of low oxidation state iron complexes in catalysis. A broad range of hydrofunctionalisation reactions have been developed by using iron catalysts in a wide variety of oxidation states. Intense development over the past decade has resulted in the development of iron‐catalysed hydroamination, hydroalkoxylation, hydrocarboxylation, hydrothiolation, hydrovinylation, hydrosilylation, hydroboration, hydrophosphination, hydromagnesiation and carbonylation reactions, amongst others. With the field still in its infancy, there is great potential for further developments in the mechanistic understanding and synthetic and industrial applicability of these processes.

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“…[143] It was also reported that FeCl 3 would catalyse the hydromagnesiation of styrene (105), albeit in only 15 % yield (Scheme 60 A, 51 % yield using TiCl 4 ).…”

Section: Hydromagnesiationmentioning

confidence: 98%

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

2014

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“…Later this reaction was also shown to be catalyzed by nickel, vanadium, zirconium, and iron complexes. [15] In 2008, Shirakawa and Hayashi and co-workers reported an iron-copper co-catalyzed preparation of primary alkyl Grignard reagentsf rom secondary reagents. [16] Isomerization likely occurs by a b-hydride elimination/transmetallation cascade.…”

Section: Transfer Of Reactive Functionalitymentioning

confidence: 99%

Shuttle Catalysis—New Strategies in Organic Synthesis

Bhawal

Morandi

2017

Chemistry A European J

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Shuttle catalysis has recently emerged as a powerful new concept that provides a platform for performing both functionalization and defunctionalization reactions. In this concept article, applications of shuttle catalysis as a novel strategy in organic synthesis are discussed. This includes using forward shuttle catalysis reactions for challenging bond-forming processes that avoid the use of hazardous chemicals. Shuttle catalysis also facilitates the transfer of reactive functionality as a route to procure a broad range of compounds using one simple procedure. Reverse shuttle catalysis reactions are also discussed as a method for the valorization of biomass and waste materials. Another area of interest, shuttle-catalysis-assisted reactions, wherein the transfer of a small molecule is utilized in a catalytic cycle, is also described. Possible future directions in this exciting new field are also suggested.

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“…In addition to TiCl 4 , compounds such as Ti(O -i -Pr) 4 , Cp 2 TiCl 2 , ZrCl 4 and VCl 4 can also be used as catalysts for this reaction [177,178] . In contrast to TiScheme 18.63 First report of hydromagnesiation of α -alkenes with n -PrMgBr.…”

Section: Alkenesmentioning

confidence: 99%

“…Catalytic hydromagnesiation of α -alkenes and subsequent functionalization of the resulting OMC involving the reactive Mg − C bond has been used successfully in the synthesis of alcohols [176,178,181] , steroids [193] , γ -and δ -lactones [194] , ketones, carboxylic acids [176,191] and other classes of organic compounds (Scheme 18.71 ).…”

Section: Catalytic Hydromagnesiation 473mentioning

confidence: 99%

Hydrometallation of Unsaturated Compounds

Джемилев

Ибрагимов

2008

Modern Reduction Methods

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18 IntroductionTo the number of signifi cant hydrometallating reagents that have been introduced into organic synthesis should be added the stable hydrides of transition metals (Zr) and nontransition metals (B, Al, Mg).Today, hydrides of the these metals and their derivatives are widely used in the reduction of alkenes, dienes, alkynes, allenes, heteroolefi ns and carbonyl compounds as well as for the production of the corresponding organometallic compounds and selective alkene functionalization via the synthesis of compounds containing polar metal -carbon (M − C) bonds. These may be involved in reactions with electrophilic or nucleophilic reagents affording functional derivatives.Generally, the thermal additions of the above hydrides to alkenes proceed via the four -center transition state (1) , with subsequent cleavage of the M − H bond and metal addition. In this case the corresponding organometallic compounds are formed according to Scheme 18.1 .The use of metal complex catalysts in organic and metalloorganic chemistry allows the chemo -, regio -and stereoselective hydroalumination of unsaturated compounds under mild conditions with high yields.The role of a transition metal catalyst in these reactions is determined by its ability to activate the starting substrate by coordination to the metal center forming the intermediate hydride complex (2) . The latter, being a more active hydrometallating reagent, attacks alkenes under mild conditions with subsequent transmetallation of the starting hydride affording the target organic compound (3) according to Scheme 18.2 .To date, a large number of reports have appeared in the literature on the application of hydride reagents in both thermal and catalytic hydrometallation of unsaturated compounds. Hydroboration, hydroalumination, hydrozirconation and hydromagnesiation of unsaturated compounds such as alkenes, dienes or alkynes are considered the most effective reactions for producing the related metalloorganic compounds. It is not possible to consider all these reactions within the

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Synthetic Applications of the Titanium-Catalyzed Exchange of Olefins with Grignard Reagents^1a

Cited by 73 publications

References 2 publications

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

Shuttle Catalysis—New Strategies in Organic Synthesis

Hydrometallation of Unsaturated Compounds

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Synthetic Applications of the Titanium-Catalyzed Exchange of Olefins with Grignard Reagents1a

Cited by 73 publications

References 2 publications

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

Shuttle Catalysis—New Strategies in Organic Synthesis

Hydrometallation of Unsaturated Compounds

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Product

Resources

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Synthetic Applications of the Titanium-Catalyzed Exchange of Olefins with Grignard Reagents^1a