Editing of polymer backbones.

Polymers are at the epicentre of modern technological progress and the associated environmental pollution. Considerations of both polymer functionality and lifecycle are crucial in these contexts, and the polymer backbone - the core of a polymer - is at the root of these considerations. Just as the meaning of a sentence can be altered by editing its words, the function and sustainability of a polymer can also be transformed via the chemical modification of its backbone. Yet, polymer modification has primarily been focused on the polymer periphery. In this Review, we focus on the transformations of the polymer backbone by defining some concepts fundamental to this topic (for example, 'polymer backbone' and 'backbone editing') and by collecting and categorizing examples of backbone editing scattered throughout a century's worth of chemical literature, and outline critical directions for further research. In so doing, we lay the foundation for the field of polymer backbone editing and hope to accelerate its development.

Catalytic intramolecular hydroamination of aminoallenes using titanium and tantalum complexes of sterically encumbered chiral sulfonamides.

Catalysis using earth abundant metals is an important goal due to the relative scarcity and expense of precious metal catalysts. It would be even more beneficial to use earth abundant catalysts for the synthesis of common pharmaceutical structural motifs such as pyrrolidine and pyridine. Thus, developing titanium catalysts for asymmetric ring closing hydroamination is a valuable goal. In this work, four sterically encumbered chiral sulfonamides derived from naturally occurring amino acids were prepared. These compounds undergo protonolysis reactions with Ti(NMe2)4 or Ta(NMe2)5 to give monomeric complexes as determined by both DOSY NMR and X-ray crystallography. The resulting complexes are active for the ring closing hydroamination hepta-4,5-dienylamine to give a mixture of tetrahydropyridine and pyrrolidine products. However, the titanium complexes convert 6-methylhepta-4,5-dienylamine exclusively to 2-(2-methylpropenyl)pyrrolidine in higher enantioselectivity than those previously reported, with enantiomeric excesses ranging from 18-24%. The corresponding tantalum complexes were more selective with enantiomeric excesses ranging from 33-39%.