Figure 1. Structures of furan derivatives 1-5 and anhydrides 6-7.Scheme1.Prior work on ROMP of fully bio-based monomers prepared from itaconic anhydride.Scheme2.Synthesis of monomers 13 a-c.Scheme3.ROMP of monomers 13 a-c with Grubbs catalysts 9 and 14.

Saturated heterocycles are found widely in biologically active compounds such as medicinal drugs and agrochemicals. However, boronic acid‐derived building blocks for these structures have limited availability, particularly in comparison to heteroaromatic boronic acids. We report the preparation of boronic ester γ‐lactams through a Cu‐catalysed conjugate borylation‐cyclisation protocol. Using a chiral catalyst, this can be performed in high enantioselectivity. Exploration of the further transformations of these reagents suggest that the boronic esters have much potential as chemical building blocks.

We report a Cu-catalysed oxidative coupling of aliphatic amines with alkylboronic esters to give high value alkyl amines, products found widely in applications from medicinal chemistry to materials science. This operationally simple reaction, which can be performed on gram scale, runs under mild conditions and exhibits excellent functional group tolerance. The terminal oxidant of the reaction is O2 from the air, avoiding the need for additional chemical oxidants. Investigation into the reaction mechanism suggests the intermediacy of an alkyl radical, generated from the boronic ester upon activation through an amino radical transfer process. To demonstrate its utility and potential for late-stage functionalization, we showcase the method as the final step in the total synthesis of a TRPV 1 antagonist.

We report a Cu-catalysed oxidative coupling of aliphatic amines with alkylboronic esters to give high value alkyl amines, products found widely in applications from medicinal chemistry to materials science. This operationally simple reaction, which can be performed on gram scale, runs under mild conditions and exhibits excellent functional group tolerance. The terminal oxidant of the reaction is O2 from the air, avoiding the need for additional chemical oxidants. Investigation into the reaction mechanism suggests the intermediacy of an alkyl radical, generated from the boronic ester upon activation through an amino radical transfer process. To demonstrate its utility and potential for late-stage functionalization, we showcase the method as the final step in the total synthesis of a TRPV 1 antagonist.

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