TY - JOUR
AU - Leibfarth, Frank A.
AB - The stereochemistry of polymers has a profound impact
on their
properties. Despite the well-developed stereoselective methods for
prochiral vinyl monomers, current methods for racemic monomers are
limited. Conventional approaches treat sp

3
 chiral centers as immutable, resulting in poor atom-economical
processes and limited control over enantioselectivity. This contrasts
with stereoconvergent catalysis in small molecules, which has revolutionized
synthesis by interrupting the transfer of chiral information from
the substrate to the product, providing a clear platform for catalysts
to access enantiopure compounds from racemic mixtures in up to 100%
yield. Here we designed a catalyst that converges stereochemical information
during polymerization, enabling access to asymmetric, isotactic polymers
with quantitative atom economy from racemic feedstocks. The mechanism
of stereoconvergence is accomplished by the catalyst ablating chiral
information, followed by a stereoselective propagation event to control
both tacticity and enantioselectivity. Using this method, we accessed
both enantiomers of an isotactic polymer from a single enantiomer
of monomer and identified a novel stereocomplex. These results represent
a conceptual framework to expand stereoconvergent polymerization into
additional monomers and mechanisms.
TI - StereoconvergentChain-Growth Polymerization
JO - ACS Central Science
DO - 10.1021/acscentsci.5c00239
DA - 2025-05-05
UR - https://www.deepdyve.com/lp/pubmed-central/stereoconvergentchain-growth-polymerization-H00bL2Mpn1
SP - 797
EP - 804
VL - 11
IS - 5
DP - DeepDyve
ER -