Regio- and stereospecific synthesis of substituted cyclohexenediols from 7-oxabicyclo[2.2.1]hept-5-en-2-ols and organolithium reagents

Arjona, Odón; Pradilla, Roberto Fernández de la; García, Ernesto Cabezas; Martín‐Domenech, Ángel; Plumet, Joaquı́n

doi:10.1016/s0040-4039(01)93916-4

Cited by 32 publications

(7 citation statements)

References 31 publications

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“…Using cuprates, we were able to achieve the first example of alkylative ring opening of a [3.2.1] oxabicycle, 35 , to give the product 36 in good yield (eq 9) . Plumet and co-workers found that alkyllithium reagents also worked when reactions were carried out in pentane . We were able to use this finding in the development of the first example of an asymmetric ring opening of a [3.2.1] oxabicycle.…”

Section: Palladium-catalyzed Asymmetric Ring Opening With Alkyl Nucle...mentioning

confidence: 88%

“…25 Plumet and coworkers found that alkyllithium reagents also worked when reactions were carried out in pentane. 26 We were able to use this finding in the development of the first example of an asymmetric ring opening of a [3.2.1] oxabicycle. When substoichiometric amounts of sparteine were added to the reaction of BuLi with 37, the product 38 was obtained in 52% ee (eq 10).…”

Section: Palladium-catalyzed Asymmetric Ring Opening With Alkyl Nucle...mentioning

confidence: 92%

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Transition Metal-Catalyzed Enantioselective Ring-Opening Reactions of Oxabicyclic Alkenes

2002

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Over the past five years, several metal-catalyzed asymmetric ring-cleaving reactions have been developed that generate ring-opened products in high yield and enantiomeric excess. These reactions can be carried out with a range of nucleophiles including hydride, stabilized and nonstabilized carbanions, alcohols, amines, and carboxylates. To achieve these results, three different transition metals have been employed, namely nickel, palladium, and rhodium, leading not only to synthetically useful transformations but also to a greater understanding of the reaction manifolds possible with these metals. This Account covers the work by our group and by others toward the development of new metal-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes.

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Section: Palladium-catalyzed Asymmetric Ring Opening With Alkyl Nucle...mentioning

confidence: 88%

Section: Palladium-catalyzed Asymmetric Ring Opening With Alkyl Nucle...mentioning

confidence: 92%

Transition Metal-Catalyzed Enantioselective Ring-Opening Reactions of Oxabicyclic Alkenes

2002

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“…The regioselective cleavage of the oxygen bridge to give functionalized cyclohexanes is central to many synthetic strategies. A regioselective ring opening using organolithium reagents and 7-oxanorbornenes has been investigated by Arjona and Plumet for cases where the olefinic moiety is directly substituted with appropriate Michael acceptor functionalities such as a vinyl sulfone. Similarly, methylthio substitution of the double bond of a 7-oxanorbornene enabled a regioselective ring opening promoted by a Lewis acid catalyst …”

Section: Introductionmentioning

confidence: 99%

Remote Electronic Effects in the Rhodium-Catalyzed Nucleophilic Ring Opening of Oxabenzonorbornadienes

2002

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We report the application of our rhodium-catalyzed nucleophilic ring-opening methodology to unsymmetrically arene-substituted oxabenzonorbornadienes. The regioselectivity of the ring opening was investigated using a variety of nucleophiles that led to a broad selection of dihydronaphthalene products. It was found that good to excellent regioselectivities are obtained using strongly pi-donating substituents, whereas sigma-donating and electron-withdrawing functionalities have a minimal effect. Post ring-opening manipulations of functional groups in the dihydronaphthalene products were shown to give efficient access to mono- and diamine tetrahydronaphthalene building blocks.

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“…61 Arjona and co-workers observed similar reactivities when 7-oxabicyclo[2.2.1]hept-5-en-2-ones were treated with organolithium reagents to yield the corresponding ring-opened products. 62 Reductive ring opening can also be induced by single electron transfer reagents. This method has been applied in various total syntheses 63 with intermediates bearing carbonyl groups alpha to bridging oxygen atoms.…”

Section: Ring-opening Reactions Of Oxabicyclic Substratesmentioning

confidence: 99%

Rapid formation of complexity in the total synthesis of natural products enabled by oxabicyclo[2.2.1]heptene building blocks

Schindler

Carreira

2009

Chem. Soc. Rev.

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This critical review showcases examples of rapid formation of complexity in total syntheses starting from 7-oxabicyclo[2.2.1]hept-5-ene derivatives. An overview of methods allowing synthetic access to these building blocks is provided and their application in recently developed synthetic transformations to structurally complex systems is illustrated. In addition, the facile access to a novel oxabicyclo[2.2.1]heptene derived building block is presented which significantly enlarges the possibilities of previously known chemical transformations and is highlighted in the enantioselective route to the core of the banyaside and suomilide natural products (107 references).

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Regio- and stereospecific synthesis of substituted cyclohexenediols from 7-oxabicyclo[2.2.1]hept-5-en-2-ols and organolithium reagents

Cited by 32 publications

References 31 publications

Transition Metal-Catalyzed Enantioselective Ring-Opening Reactions of Oxabicyclic Alkenes

Transition Metal-Catalyzed Enantioselective Ring-Opening Reactions of Oxabicyclic Alkenes

Remote Electronic Effects in the Rhodium-Catalyzed Nucleophilic Ring Opening of Oxabenzonorbornadienes

Rapid formation of complexity in the total synthesis of natural products enabled by oxabicyclo[2.2.1]heptene building blocks

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