Catalytic Direct‐Type Addition Reactions of Alkylarenes with Imines and Alkenes

Abstract

Catalytic addition reactions of very weakly acidic nonactivated alkylarenes such as toluene and its derivatives were developed by using a strongly basic mixed catalyst system under mild reaction conditions. The addition reactions with imines and alkenes proceeded smoothly under proton-transfer conditions to afford the desired products in good to high yields, and high levels of regio- and stereoselectivity were achieved. It was also revealed that the asymmetric addition reaction of an alkylarene was possible.

Alkylpotassium-Catalyzed Benzylic C–H Alkylation of Alkylarenes with Alkenes

“…Quite recently, we have developed potassium tert-butoxide/lithium tetramethylpiperidide (KOt-Bu/LiTMP) mixed base-catalyzed addition reactions of alkylarenes with N-alkylimines (Scheme 1b). 12 In this reaction, a highly basic reaction intermediate (N-dialkylamide) functions as a base to deprotonate…”

Synthesis of densely substituted pyridine derivatives from nitriles by a non-classical [4+2] cycloaddition/1,5-hydrogen shift strategy

“…Based on the above investigation and literature reports, [82][83][84][85][86][87][88][89][90] a possible mechanism is proposed in Fig. 5.…”

“…As a strategic fundamental step, our primary task is to identify the balanced conditions for the C(sp 3 )-H bond activation, simultaneously avoiding the intrinsic tendency of intramolecular cyclization under the transition metal catalysis. Alkali metals bearing the weaker coordination ability, as a powerful tool for C − H bond activation, [83][84][85][86][87][88][89][90] might have a broadly bene cial impact on our protocol. We envisioned that the C(sp 3 )-H bond activation should occur primarily triggered by the amenable alkali metal reagents to form the nucleophilic benzyl or allyl − metal species, which could be trapped rapidly by the suitable electrophile-nitrile.…”

Main Group Metal‐Mediated Transformations of Imines

“…[112] Recently,t he catalysed addition of alkylarenes to imines was reported by Kobayashi employing the well-known LiNK system, potassium tert-butoxide (KOtBu) and lithium 2,2,6,6-tetramethylpiperidide (LiTMP). [113] Aw ide range of substituted toluene derivatives were probed with an N-alkylimine as illustrated in Scheme36, resultingi ng ood to excellent yields of the corresponding amine. The scopeo fa ryl (Ar) moietyo nt he imine was also explored including various functional groups, polyand hetero-aromatics.…”