Reactivity of cyclopalladated compounds derived from biphenyl-2-ylamine towards carbon monoxide, tbutyl isocyanide and alkynes

Highly Stereoselective Synthesis of Imine‐Containing Dibenzo[b,d]azepines by a Palladium(II)‐Catalyzed [5+2] Oxidative Annulation of o‐Arylanilines with Alkynes

“…Next, this dimeric palladium complex is broken into its component parts by 2 to form the intermediate I . Notably, it was known from prior work that migratory insertion of the alkyne 2 with 4 favored a regioselective insertion into the PdC bond to afford the eight‐membered intermediate II 15b. Furthermore, CN reductive elimination takes place to deliver the enamine‐containing dibenzo[ b , d ]azepine 6 and concomitantly regenerate Pd(OAc) 2 to complete the cycle.…”

A General and Practical Palladium‐Catalyzed Direct α‐Arylation of Amides with Aryl Halides

“…We, therefore, employed the palladacyclic precursors (Figure 1), which have been demonstrated to readily form active catalysts. 35 As shown in Table 9, in order to identify the optimal reaction conditions, four common solvents [toluene, CPME, dioxane and dimethoxyethane (DME)] were screened using the µ-Cl Pd dimer 35 with Kwong’s indole-based phosphine ( P1 , Figure 1). CPME was found to be the most suitable solvent under the conditions examines, affording a mixture of the mono- and bis-arylated products in a 5:1 ratio.…”

Palladium‐Catalyzed CC Coupling of Aryl Halides with Isocyanides: An Alternative Method for the Stereoselective Synthesis of (3E)‐(Imino)isoindolin‐1‐ones and (3E)‐(Imino)thiaisoindoline 1,1‐Dioxides

“…It is noteworthy that phenanthridines and dibenzooxazepins are important units in numerous biologically active natural products and medicinally significant compounds 18. We presume that the intermediates ( 9′ and 10′ ) were unstable and easily tautomerized8c,18c to the corresponding 6‐aminophenanthridines ( 9 ) and 11‐aminodibenzooxazepines ( 10 ). Next, we examined other isocyanides under the standard reaction conditions.…”

“…N ‐( tert ‐Butyl)phenanthridin‐6‐amine (9a): 18c Light yellow solid; mp 92–94 °C; IR (KBr): ν=3741, 2960, 2359, 1583, 1522, 1425, 1213, 757, 722 cm −1 ; 1 H NMR (400 MHz, CDCl 3 ): δ =8.55 (d, J =8.4 Hz, 1 H), 8.42 (d, J =8.0 Hz, 1 H), 8.00 (d, J =8.0 Hz, 1 H), 7.83 (d, J =8.4 Hz, 1 H), 7.77–7.69 (m, 2 H), 7.60 (t, J =7.6 Hz, 1 H), 7.45 (t, J =7.4 Hz, 1 H), 5.35(br. s, 1 H), 1.85 (s, 9 H); 13 C NMR (100 MHz, CDCl 3 ): δ =152.1, 144.7, 133.7, 129.5, 128.5, 127.3, 126.6, 122.6, 122.1, 121.7, 121.7, 120.1, 119.5, 51.8, 29.3; MS (EI): m / z =77, 110, 140, 151, 166, 178, 194, 235, 250.…”