A new synthesis of 2,3-dihydrofurans: cycloisomerization of alkynyl alcohols to endocyclic enol ethers

McDonald, Frank E.; Connolly, C. B.; Gleason, Mark M.; Towne, Timothy B.; Treiber, K. D.

doi:10.1021/jo00077a006

Cited by 117 publications

(39 citation statements)

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“…[36] The first report of such a transformation dates back almost 15 years (Scheme 21). [37] Although the yields were modest, chromium, tungsten, and molybdenum carbonyl complexes were found to promote the stoichiometric cyclization of homopropargyl alcohol 64 to the corresponding Fischer carbene complexes. In the latter case triethylamine was able to effect in situ demetalation to the corresponding dihydrofuran 67.…”

Section: Intramolecularmentioning

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: Intramolecularmentioning

confidence: 99%

Metal Vinylidenes as Catalytic Species in Organic Reactions

Trost

McClory

2008

Chemistry An Asian Journal

187

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“…[93] The catalytic version, illustrated by the endo cyclization of 3-and 4-alkyn-1-ols to give cyclic five-and six-membered enol ethers has been extensively studied, especially with molybdenum [94] and tungsten [95,96] carbonyl promoters (Scheme 12). [97,98] [Mo(CO) 6 ], [W(CO) 6 ], [W(CO) 5 (thf)], and [W(CO) 5 (Et 3 N)] are the most commonly used catalyst precursors, and photochemical activation is often used to generate the active promoters.…”

Section: Intermolecular Addition Of Alcoholsmentioning

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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“…An example is shown in Scheme 5 [20]. The initial Z 2 -Mo-alkyne complex rearranges to vinylidene-Mo complex intermediate that undergoes an intramolecular nucleophilic attack of the hydroxy oxygen to give cyclic anionic intermediate, protonation of which yields 2,3-dihydrofuran.…”

Section: Mechanism Through Vinylidene Intermediatesmentioning

confidence: 99%

“…(12) and (13)]. Kinetic studies on 20-catalyzed reaction of 1-pentanethiol with 1-hexyne showed the empirical rate low expressed as rate ¼ k obs [20] 1 [1- …”

Section: Organoactinide-and Organolanthanide-catalyzed Hydrothiolationmentioning

confidence: 99%

The Mechanism for Transition-Metal-Catalyzed Hydrochalcogenation of Unsaturated Organic Molecules

Ishii

Nakata

2011

Hydrofunctionalization

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In this chapter, discussions are focused on two types of mechanisms of transition-metal-catalyzed hydrochalcogenation, Type I and Type II, which are classified by the initial behavior of precatalysts. In Type I mechanism, precatalyst M-X (M ¼ Pd, Ni, Zr, Ln, and An) first undergoes protonolysis with REH (E ¼ O, S, and Se) to generate active catalyst M-ER, which then undergoes insertion of alkyne into the M-ER bond (chalcogenometalation) to give 2-chalcogenovinyl complex, followed by protonolysis of M-C vinyl with REH to produce the product and to regenerate active catalyst M-ER. Type II mechanism starts from oxidative addition of REH (E ¼ S and Se) to

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A new synthesis of 2,3-dihydrofurans: cycloisomerization of alkynyl alcohols to endocyclic enol ethers

Cited by 117 publications

References 0 publications

Metal Vinylidenes as Catalytic Species in Organic Reactions

Metal Vinylidenes as Catalytic Species in Organic Reactions

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

The Mechanism for Transition-Metal-Catalyzed Hydrochalcogenation of Unsaturated Organic Molecules

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