Recently, Lewis pairs composed of
organobases and organoboranes
have shown high catalytic activity for the synthesis of polyethers
by ring-opening polymerization of epoxides. Surprisingly, copolymerization
of cyclic anhydride and a large excess of epoxide we conducted at
elevated temperatures were free of polyether formation when catalyzed
by a phosphazene base and triethylborane (Et3B), even after
complete anhydride consumption. As a result, polyesters with (near)
perfect alternating sequence distribution, controlled and narrowly
distributed molar mass were readily obtained. Experimental and calculational
results attributed the unexpected chemoselectivity to the protonolysis
of Et3B and the newly formed oxygenated boron species.
Most importantly, the reversible interchange of acyloxyborane and
borinic ester at the propagating chain ends suppressed the reaction
between hydroxy species and epoxide (formation of ethers) while maintaining
the catalytic activity for the reaction between carboxy species and
epoxide (formation of esters). The polyesters containing catalyst
residues exhibited good cytocompatibility despite these changes. The
in situ structure and activity evolvement of boron species revealed
here will pave new pathways for rational design of metal-free catalysts.