Studies of the generation and pericyclic behavior of cyclic pentadienyl carbanions. Alkylation reactions as an efficient route to functionalized cis-bicyclo[3.3.0]octenes.
Carbolithiation has been studied with alkyllithium reagents in a series of six- through nine-membered 3-methylene-1,4-cycloalkadienes, efficiently producing the corresponding cyclic pentadienyl carbanions. These pentadienyl anions display unique reactivity, depending on ring size. Cyclooctadienyl anions readily undergo disrotatory electrocyclization to cis-bicyclo[3.3.0]octenyl systems, which are trapped with a variety of electrophiles to stereoselectively provide functionalized cis-bicyclo[3.3.0]octenes. The carbolithiation and electrocyclization processes are examined using low-temperature (1)H NMR experiments. An expedient synthesis of a linear triquinane illustrates this methodology. Electrocyclization of the corresponding cyclononadienyl anion requires unusually high temperatures (120 degrees C), and computational studies provide insights into this change in reactivity. Cycloheptadienyl and cyclohexadienyl anions, generated via carbolithiation, provide functionalized cycloheptadienes and cyclohexadienes upon electrophilic capture. Trapping experiments reveal that the cycloheptadienyl anions are transformed to heptatrienyl anions. A series of experiments have been designed to explore evidence for the feasibility of equilibration of open and closed anionic systems, and these studies report the first isolation of a cis-bicyclo[3.1.0]hexene derived from electrocyclization of a cyclohexadienyl carbanion.
Williams
David R
DR
Department of Chemistry & School of Informatics, Indiana University, Bloomington, Indiana 47405-7102, USA. williamd@indiana.edu
Reeves
Jonathan T
JT
Nag
Partha P
PP
Pitcock
William H
WH
Baik
Mu-Hyun
MH
D000466:Alkadienes / Q000737:chemistry*; D000478:Alkylation; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D003516:Cycloparaffins / Q000138:chemical synthesis* / Q000737:chemistry; D008094:Lithium / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D009795:Octanes / Q000138:chemical synthesis / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D013816:Thermodynamics
D000466:Alkadienes; D001643:Bridged Bicyclo Compounds; D003516:Cycloparaffins; D009795:Octanes; D009942:Organometallic Compounds; D008094:Lithium