Copper-catalyzed ortho-C–H amination of protected anilines with secondary amines

Abstract

A practical Cu-catalyzed picolinamide-directed o-amination of anilines showing excellent mono-substitution selectivity and high functional group tolerance has been developed.

Rhodium‐Catalyzed Oxidative Benzannulation of N‐Pivaloylanilines with Internal Alkynes through Dual C−H Bond Activation: Synthesis of Highly Substituted Naphthalenes

“…[19] The oxidants were finally screened by using [Cp*RhCl 2 ] 2 as ap recatalyst and DMF as as olvent. Cu(OAc) 2 provedt ob et he best oxidanta mong the tested oxidants (Cu(OAc) 2 ,C u(OTf) 2 , Ag 2 CO 3 ,a nd AgOAc;e ntry 8v s. entries [9][10][11]. The yield of benzannulation product 5aa wasf ound to increasew ith increased [Cp*RhCl 2 ] 2 loading (entry 12, 81 %).…”

“…Among the directing groups employed, acylaminog roups are frequently utilized because they can be easily installed into the substrates and convertedt o other functional groups. [5] For example, the acylamino groups linked on aromatic rings were successfully used as the directing groups for new carbon-carbon( including C aryl -C alkenyl , [6] C aryl -C aryl , [7] C aryl -C alkyl , [8] and C aryl -C carbonyl [9] )a nd carbon-heteroatom (including C aryl -N, [10] C aryl -O, [11] C aryl -B, [12] C aryl -Cl, [13] C aryl -Br, [14] and C aryl -I [15] )bond formation as well as for the carbocycle and heterocycle construction. [16][17][18] It was demonstrated that highly functionalized indoles can be efficiently synthesized throughd irect CÀHb ond functionalization in the presence of ac ationic rhodium(III) catalystb yu sing an acetylamino group as the directing group [Eq.…”

Copper-Mediated Intermolecular C–H/C–H and C–H/N–H Couplings via Aromatic C–H Cleavage

“…By using a picoline-type director, anilides can also couple with alkylamines in a dehydrogenative manner to form the corresponding 1,2-diaminobenzene derivatives (Eqs. 33 and 34) [59,60]. The hypervalent I(III) reagent, PhI(OAc) 2 is a critical oxidant, and the reaction occurs under relatively mild conditions (rt-80 C).…”

Directing‐Group‐Assisted Transition‐Metal‐Catalyzed Direct Intermolecular C−H Amidation and Amination of Arenes

“…Following the success of Daugulis’ work, Rodríguez, Arrayás et al . and Chen's group independently reported the picolinamide (PA)‐assisted copper‐catalyzed amination of anilines with cyclic secondary alkylamines (Scheme ).…”