Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran.
The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC(4)) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C(4) fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.
Mulvey
Robert E
RE
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK. r.e.mulvey@strath.ac.uk
Blair
Victoria L
VL
Clegg
William
W
Kennedy
Alan R
AR
Klett
Jan
J
Russo
Luca
L
D043844:Crown Ethers / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D005663:Furans / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry
D043844:Crown Ethers; D005663:Furans; D009942:Organometallic Compounds; C018674:tetrahydrofuran