Nitrosocarbonyl Hetero-Diels-Alder Cycloaddition: A New Tool for Conjugation

Samoshin, A.V.; Hawker, C.J.; de Alaniz, J.R.
ACS Macro Letters
3, 753-757.

It is demonstrated that nitrosocarbonyl hetero-Diels–Alder chemistry is an efficient and versatile reaction that can be applied in macromolecular synthesis. Polyethylene glycol functionalized with a hydroxamic acid moiety undergoes facile coupling with cyclopentadiene-terminated polystyrene, through a copper-catalyzed as well as thermal hetero-Diels–Alder reaction. The mild and orthogonal methods used to carry out this reaction make it an attractive method for the synthesis of block copolymers. The resulting block copolymers were analyzed and characterized using GPC and NMR. The product materials could be subjected to thermal retro [4 + 2] cycloaddition, allowing for the liberation of the individual polymer chains and subsequent recycling of the diene-terminated polymers.