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Torquoselective ring opening of fused cyclobutenamides: evidence for a cis,trans-cyclooctadienone intermediate.

Wang XN, Krenske EH, Johnston RC, Houk KN, Hsung RP - J. Am. Chem. Soc. (2014)

Bottom Line: Electrocyclic ring opening of 4,6-fused cyclobutenamides 1 under thermal conditions leads to cis,trans-cyclooctadienones 2-E,E as transient intermediates, en route to 5,5-bicyclic products 3.Theoretical calculations predict that 4,5-fused cyclobutenamides should likewise undergo thermal ring opening, giving cis,trans-cycloheptadienones, but in this case conversion to 5,4-bicyclic products is thermodynamically disfavored, and these cyclobutenamides instead rearrange to vinyl cyclopentenones.

View Article: PubMed Central - PubMed

Affiliation: Division of Pharmaceutical Sciences and Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53705, United States.

ABSTRACT
Electrocyclic ring opening of 4,6-fused cyclobutenamides 1 under thermal conditions leads to cis,trans-cyclooctadienones 2-E,E as transient intermediates, en route to 5,5-bicyclic products 3. Theoretical calculations predict that 4,5-fused cyclobutenamides should likewise undergo thermal ring opening, giving cis,trans-cycloheptadienones, but in this case conversion to 5,4-bicyclic products is thermodynamically disfavored, and these cyclobutenamides instead rearrange to vinyl cyclopentenones.

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Ring-FusedCyclobutenamides as Potential Precursors to Small Cis,Trans-Cycloalkadienones
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sch1: Ring-FusedCyclobutenamides as Potential Precursors to Small Cis,Trans-Cycloalkadienones


Torquoselective ring opening of fused cyclobutenamides: evidence for a cis,trans-cyclooctadienone intermediate.

Wang XN, Krenske EH, Johnston RC, Houk KN, Hsung RP - J. Am. Chem. Soc. (2014)

Ring-FusedCyclobutenamides as Potential Precursors to Small Cis,Trans-Cycloalkadienones
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4353010&req=5

sch1: Ring-FusedCyclobutenamides as Potential Precursors to Small Cis,Trans-Cycloalkadienones
Bottom Line: Electrocyclic ring opening of 4,6-fused cyclobutenamides 1 under thermal conditions leads to cis,trans-cyclooctadienones 2-E,E as transient intermediates, en route to 5,5-bicyclic products 3.Theoretical calculations predict that 4,5-fused cyclobutenamides should likewise undergo thermal ring opening, giving cis,trans-cycloheptadienones, but in this case conversion to 5,4-bicyclic products is thermodynamically disfavored, and these cyclobutenamides instead rearrange to vinyl cyclopentenones.

View Article: PubMed Central - PubMed

Affiliation: Division of Pharmaceutical Sciences and Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53705, United States.

ABSTRACT
Electrocyclic ring opening of 4,6-fused cyclobutenamides 1 under thermal conditions leads to cis,trans-cyclooctadienones 2-E,E as transient intermediates, en route to 5,5-bicyclic products 3. Theoretical calculations predict that 4,5-fused cyclobutenamides should likewise undergo thermal ring opening, giving cis,trans-cycloheptadienones, but in this case conversion to 5,4-bicyclic products is thermodynamically disfavored, and these cyclobutenamides instead rearrange to vinyl cyclopentenones.

Show MeSH