Ru‐Catalyzed Anti‐Markovnikov Addition of Amides to Alkynes: A Regio‐ and Stereoselective Synthesis of Enamides

Gooßen, Lukas J.; Rauhaus, Jan E.; Deng, Guo‐Jun

doi:10.1002/anie.200462844

Cited by 127 publications

(40 citation statements)

References 32 publications

(13 reference statements)

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“…[71] For example, 2-pyrrolidinone (158) reacts with n-hexyne (12) in excellent yield, with complete regioselectivity and good E/Z selectivity (equation 1). Product 160 can be prepared from enyne 24 and amide 58 (equation 2), thus constituting an atom economical synthesis of activated dienes for Diels-Alder reactions.…”

Section: Amine Nucleophilesmentioning

confidence: 99%

Metal Vinylidenes as Catalytic Species in Organic Reactions

Trost

McClory

2008

Chemistry An Asian Journal

187

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Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis.

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Section: Amine Nucleophilesmentioning

confidence: 99%

Metal Vinylidenes as Catalytic Species in Organic Reactions

Trost

McClory

2008

Chemistry An Asian Journal

187

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“…More recently, E enamides were formed regio-and stereoselectively in the presence of a catalytic system based on [Ru(methallyl) 2 (cod)], tributylphosphine, and dimethylaminopyridine (DMAP) in toluene at 100 8C (Scheme 21). [125] This catalytic system is closely related to our system, which allows the addition of carboxylic acids to terminal alkynes (see Section 3.1) and the addition of a variety of N-nucleophiles such as amides, lactams, anilides, ureas, and carbamates. Under similar conditions, [125] but in the presence of Cy 2 PCH 2 PCy 2 and water as additives, instead of PnBu 3 and DMAP, the catalytic anti-Markovnikov addition selectively provides the Z isomers.…”

Section: Catalytic Addition Of N-nucleophiles To Alkynes: Direct Tranmentioning

confidence: 99%

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

2006

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The involvement of a catalytic metal vinylidene species was proposed for the first time in 1986 to explain the regioselective formation of vinyl carbamates directly from terminal alkynes, carbon dioxide, and amines. Since this initial report, various metal vinylidenes and allenylidenes, which are key activation intermediates, have proved extremely useful for many alkyne transformations. They have contributed to the rational design of new catalytic reactions. This 20th anniversary is a suitable occasion to present the advancement of organometallic vinylidenes and allenylidenes in catalysis.

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“…Under catalytic conditions, such acids react with the amine substrate present in situ to generate ammonium salts, which can be an adventitious proton source to push the catalytic reaction forward while simultaneously reducing the propensity for the amines to act as preferred ligands for metal coordination. Indeed, hydroamination frequently cannot be realized by using late transition metal complexes; however, hydroamidation and hydrocarbamation can be carried out efficiently due to the reduced nucleophilicity of these amine substrates [122][123][124][125][126][127]. Many recent advances take advantage of this class of protected amine reagents and will be briefly addressed here; however, this chapter focuses on hydroamination using the more challenging unprotected amine substrates.…”

Section: Introductionmentioning

confidence: 99%