Rh(iii)-catalyzed regioselective intermolecular N-methylene Csp³–H bond carbenoid insertion

Abstract

A Rh(iii)-catalyzed regioselective intermolecular carbenoid insertion into the N-methylene Csp3–H bond has been achieved via an outer-sphere pathway.

Comparison of the Reactivities and Selectivities of Group 9 [Cp*MIII] Catalysts in C−H Functionalization Reactions

“…[44] Significantly,t he regioselectivity in this carbenoid reaction differed, in that a-CÀH bonds werea lkylated insteado fg-CÀHb onds. [44] Significantly,t he regioselectivity in this carbenoid reaction differed, in that a-CÀH bonds werea lkylated insteado fg-CÀHb onds.…”

“…The same group also investigatedaC(sp 3 )ÀHc arbenoidi nsertion reactiono nt he same type of substrate by using a [Cp*Rh III ]c atalysts ystem (Scheme 33). [44] Significantly,t he regioselectivity in this carbenoid reaction differed, in that a-CÀH bonds werea lkylated insteado fg-CÀHb onds. Surprisingly,t he [Cp*Ir III ]s ystem was not effective at all in this transformation.…”

“…The same group also investigated a C(sp 3 )−H carbenoid insertion reaction on the same type of substrate by using a [Cp*Rh III ] catalyst system (Scheme ) . Significantly, the regioselectivity in this carbenoid reaction differed, in that α‐C−H bonds were alkylated instead of γ‐C−H bonds.…”

Marine Furanocembranoids-Inspired Macrocycles Enabled by Pd-catalyzed Unactivated C(sp3)-H Insertion Reaction of Donor/Donor Carbenes

“…[26][27][28][29] While a few carbene cross-couplings of Csp 3 -H substrates with diazo esters have been developed, they are mainly limited to the activated positions (benzylic, allylic, α-to heteratoms). [30][31][32][33][34][35] Signi cant progress has been made in carbene cross-couplings of unactivated Csp 3 -H bonds from Davies [36][37][38][39][40][41] and Martin. 42 Notably, all of these reported protocols exclusively employed the donor-acceptor metal carbenoid generated from diazo esters.…”

[Cp*RhIII] in an Ionic Liquid as a Highly Efficient and Recyclable Catalytic Medium for Regio‐ and Diastereoselective Csp3–H Carbenoid Insertion

“…Transition‐metal catalyzed heteroatom‐adjacent Csp 3 –H carbenoid insertions recently provide a new, atom‐economic way to construct C–C bonds, while substrate‐specific obstacles prompt scientists to explore more effective approaches. In 2017, Zeng's group firstly reported a bidentate‐assisted Rh III ‐catalyzed N ‐methylene Csp 3 –H bond insertion (Scheme b) . This strategy provides an effective approach to diverse β‐amino esters, but has a limited practicality because of the poor diastereoselectivity and relatively high temperature.…”