Formation of benzynes from 2,6-dihaloaryllithiums: mechanistic basis of the regioselectivity.
The key elimination step for the formation of 3-chloro- and 3-fluorobenzyne from 2-chloro-6-fluorophenyllithium displays a pronounced solvent-dependent regioselectivity. 6Li and 13C NMR spectroscopic studies on 2-chloro-6-fluorophenyllithium reveal a single monomeric aryllithium, suggested by DFT computational studies to be a trisolvate. Rate studies indicate that the elimination of LiCl and LiF proceeds via trisolvated and disolvated monomers, respectively.
Ramírez
Antonio
A
Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301, USA.
Candler
John
J
Bashore
Crystal G
CG
Wirtz
Michael C
MC
Coe
Jotham W
JW
Collum
David B
DB
D001555:Benzene Derivatives / Q000138:chemical synthesis* / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis*; D007700:Kinetics; D008094:Lithium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D009942:Organometallic Compounds / Q000737:chemistry
D001555:Benzene Derivatives; D001643:Bridged Bicyclo Compounds; D009942:Organometallic Compounds; D008094:Lithium