A New Facile Anionic Domino Ring Expansion of Cyclopentanones by Two and Three Carbons for the Flexible Preparation of Functionalized Seven- and Eight-Membered Rings

Lavoisier-Gallo, Tania; Charonnet, Emmanuelle; Rodríguez, Jean

doi:10.1021/jo971811x

Cited by 24 publications

(10 citation statements)

References 13 publications

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“…Compounds 5 a ± d and 5 g ± i have been fully characterized and described by us, previously. [54] Cyclooctane [b]indole-7,10,10(11H)-tricarboxylic methyl ester (5 e General procedure for the preparation of cyclic enol ethers: Powdered K 2 CO 3 (2.5 mmol) was added to a solution of keto dicarboxylate 1 (1 mmol) in dry THF (15 mL) and the mixture was stirred under nitrogen for 15 min at room temperature. The selected 1,4-dihalide 2 (1 mmol) in dry THF (10 mL) was then added through a syringe and the resulting reaction mixture was stirred under reflux for the time indicated in Table 3.…”

Section: Methodsmentioning

confidence: 99%

C−C versus C−O Anionic Domino Cycloalkylation of Stabilized Carbanions: Facile One-Pot Stereoselective Preparation of Functionalized Bridged Bicycloalkanones and Cyclic Enol Ethers

et al. 2001

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alpha,alpha'-Diactivated cyclic- or acyclic ketones undergo a chemoselective base promoted (K2CO3, DBU) one-pot C-C cycloalkylation, with 1,3- and 1,4-dihalides having a cis-like fixed configuration. This reaction gives highly functionalized bicyclo[3.2.1]octan-9-one and bicyclo[4.2.1]nonan-9-one derivatives, which are easily transformed to seven- and eight-membered rings through a high yield retro-Dieckmann cleavage. Starting from trans-1,4-dibromo-2-butenes, the transformation is governed by stereoelectronic factors and leads, through a chemo- and stereoselective C-O cycloalkylation, to synthetically valuable monocyclic or fused polycyclic functionalized enol ethers of high synthetic value. Semiempirical calculations showed a small difference in energy and the late character of the transition states leading to cis and trans isomers of the corresponding fused polycyclic enol ethers. These results, although minimizing the influence of a destabilizing 1,3-interaction on the outcome of the reaction, are qualitatively in agreement with the experimental results.

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Section: Methodsmentioning

confidence: 99%

C−C versus C−O Anionic Domino Cycloalkylation of Stabilized Carbanions: Facile One-Pot Stereoselective Preparation of Functionalized Bridged Bicycloalkanones and Cyclic Enol Ethers

et al. 2001

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“…Two indirect approaches were proposed as alternative routes for the synthesis of eight-membered rings through RCM. The concept is based on the formation of a temporary bridge [75][76][77] in correctly functionalized bridged bicyclic derivatives followed by selective strategic bond fragmentations of these strained intermediates. Mascareaeas and co-workers [78] introduced the selective formation/fragmentation of bicyclo-[3.3.1]nonanones with a hydroxy group at the bridgehead (Scheme 40).…”

Section: Miscellaneous Transformationsmentioning

confidence: 99%

Selective Construction of Carbocyclic Eight‐Membered Rings by Ring‐Closing Metathesis of Acyclic Precursors

2006

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Although the efficient preparation of cyclooctanoids has remained a long-standing objective, a real breakthrough was possible only relatively recently with the development of more specific reagents and by the development of new reactions. The direct construction of carbocyclic eight-membered rings from acyclic precursors is still a challenge, mainly because of unfavorable entropic and enthalpic factors that preclude ring formation. This Minireview describes the utilization of ring-closing metathesis (RCM) as a new approach to synthesize cyclooctanoids.

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“…After completion (TLC), evaporation of the volatiles under reduced pressure gave the corresponding crude seven‐ or eight‐membered rings 5 a – n , which were purified by FC. Compounds 5 a – d and 5 g – i have been fully characterized and described by us, previously 54…”

Section: Methodsmentioning

confidence: 99%

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Sapino

Bongiovanni

Cassoni

et al. 2002

The Journal of Pathology

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α,α′‐Diactivated cyclic‐ or acyclic ketones undergo a chemoselective base promoted (K2CO3, DBU) one‐pot C−C cycloalkylation, with 1,3‐ and 1,4‐dihalides having a cis‐like fixed configuration. This reaction gives highly functionalized bicyclo[3.2.1]octan‐9‐one and bicyclo[4.2.1]nonan‐9‐one derivatives, which are easily transformed to seven‐ and eight‐membered rings through a high yield retro‐Dieckmann cleavage. Starting from trans‐1,4‐dibromo‐2‐butenes, the transformation is governed by stereoelectronic factors and leads, through a chemo‐ and stereoselective C−O cycloalkylation, to synthetically valuable monocyclic or fused polycyclic functionalized enol ethers of high synthetic value. Semiempirical calculations showed a small difference in energy and the late character of the transition states leading to cis and trans isomers of the corresponding fused polycyclic enol ethers. These results, although minimizing the influence of a destabilizing 1,3‐interaction on the outcome of the reaction, are qualitatively in agreement with the experimental results.

show abstract

A New Facile Anionic Domino Ring Expansion of Cyclopentanones by Two and Three Carbons for the Flexible Preparation of Functionalized Seven- and Eight-Membered Rings

Cited by 24 publications

References 13 publications

C−C versus C−O Anionic Domino Cycloalkylation of Stabilized Carbanions: Facile One-Pot Stereoselective Preparation of Functionalized Bridged Bicycloalkanones and Cyclic Enol Ethers

C−C versus C−O Anionic Domino Cycloalkylation of Stabilized Carbanions: Facile One-Pot Stereoselective Preparation of Functionalized Bridged Bicycloalkanones and Cyclic Enol Ethers

Selective Construction of Carbocyclic Eight‐Membered Rings by Ring‐Closing Metathesis of Acyclic Precursors

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