Rh(i)- and Rh(ii)-catalyzed C–H alkylation of benzylamines with alkenes and its application in flow chemistry

Abstract

Rh(i)- and Rh(ii)-catalyzed C–H alkylation of benzylamines with alkenes using a picolinamide derivative as a directing group is reported under both batch and flow.

Transition-metal-catalyzed C–H bond alkylation using olefins: recent advances and mechanistic aspects

“…The same picolinamide directing group was further utilized for the Rh(I) and Rh(II) catalyzed C-H bond alkylation of benzylamine derivatives 20a (Scheme 20). 74 The reaction was compatible with various alkenes, including a,b-unsaturated alkenes and styrene derivatives. Several substituted benzylamines and thiophene derived amines were well tolerated in this reaction.…”

Dirhodium: carbene transformations and beyond

“…Not long ago, the same group found that Rh 2 (OAc) 4 could also be employed in the C–H alkylation of benzylamines with alkenes (Scheme 79). 132 Both picolinamide as well as other heterocycles such as a thiophene-derived amine were amenable for use as the directing group. The conditions of Rh( i ) as the catalyst also worked well, but were inferior in the substrate scope investigation.…”

Rh(II)-Catalyzed C–H Alkylation of Benzylamines with Unactivated Alkenes: The Influence of Acid on Linear and Branch Selectivity

“…On the other hand, C–H alkylation with alkenes offers a much more environmentally friendly reaction because all the molecules of the substrates and alkenes are fully utilized in forming the desired products. Given our ongoing interest in C–H alkylation reactions, we investigated the ortho -alkylation of benzylamines with unactivated alkenes. In our previous work, we reported the Rh-catalyzed linear-selective, picolinamide chelation assisted C–H alkylation of benzylamine derivatives with activated alkenes, such as acrylates, styrenes, and maleimides .…”