Thermal Rearrangement of 2,5-Dimethyl-2-vinyl-2,3-dihydrofuran to 4-Methyl-4-cycloheptenone

Rhoads, Sara Jane; Brandenburg, C.F.

doi:10.1021/ja00970a056

Cited by 19 publications

(2 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This simple pathway, applied to more elaborated substrates, could easily give access to stereodefined and highly functionalized reduced furan structures30 which abound in nature and have attracted considerable attention 31. Moreover, related vinyl derivatives have been used as powerful reactive intermediates in many interesting stereoselective synthetic transformations such as thermal14a, 32 and palladium33‐catalyzed rearrangements, simple addition reactions34 and tandem addition–fragmentation sequences 14b,14c,15b…”

Section: Resultsmentioning

confidence: 99%

Authors' reply

Sapino

Bongiovanni

Cassoni

et al. 2002

The Journal of Pathology

View full text Add to dashboard Cite

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

Section: Resultsmentioning

confidence: 99%

Authors' reply

Sapino

Bongiovanni

Cassoni

et al. 2002

The Journal of Pathology

View full text Add to dashboard Cite

show abstract

“…After 1963, Rhoads published little. She continued to study thermal rearrangements, [145] wrote a major review in 1975 on the Claisen and Cope rearrangements for Organic Reactions [146] and published on C-versus O-alkylation in cyclic β-keto esters. [128] Fundamentally, Rhoads was not in the mainstream of original research in chemistry.…”

Section: Why and Why Not Rhoads?mentioning

confidence: 99%

The Many Chemists Who Could Have Proposed the Woodward‐Hoffmann Rules But Didn't: The Organic Chemists Who Knew of the Smoking Guns**

Seeman

2022

The Chemical Record

View full text Add to dashboard Cite

show abstract

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

View full text Add to dashboard Cite

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.

show abstract

Thermal Rearrangement of 2,5-Dimethyl-2-vinyl-2,3-dihydrofuran to 4-Methyl-4-cycloheptenone

Cited by 19 publications

References 0 publications

Authors' reply

Authors' reply

The Many Chemists Who Could Have Proposed the Woodward‐Hoffmann Rules But Didn't: The Organic Chemists Who Knew of the Smoking Guns**

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

Contact Info

Product

Resources

About