Metal‐Catalyzed Reactions between 2‐Azabicyclo[2.2.1]hept‐5‐en‐3‐ones and Arylboronic Acids

Abstract

Cu‐ and Rh‐catalyzed coupling reactions of 2‐azabicyclo[2.2.1]hept‐5‐en‐3‐ones (1) with arylboronic acids were successful carried out under microwave irradiation conditions and yielded N‐aryl and C‐aryl derivatives of 1, respectively.

Nickel–Copper‐Catalyzed C(sp2)N Cross‐Coupling of Cyclic and Bridged Amides: An Access to Cyclic Enamides and Alkenyl Vince Lactams

“…( 1S,4R )‐2‐(4‐Methoxyphenyl)‐2‐azabicyclo[2.2.1]hept‐5‐en‐3‐one (4a): 13e Yield (X=I, Br): 189 mg (88%), 174 mg (81%); 1 H NMR (300 MHz, CDCl 3 ): δ =2.24–2.27 (m, 1 H), 2.49 (d, J =8.1 Hz, 1 H), 3.48–3.49 (m, 1 H), 3.78 (s, 3 H), 4.67 (d, J =2.1 Hz, 1 H), 6.72 (s, 1 H), 6.86–6.89 (m, 2 H), 6.99–7.01 (m, 1 H), 7.24–7.26 (m, 2 H); 13 C NMR (75 MHz, CDCl 3 ): δ =22.8, 54.7, 55.6, 57.8, 65.5, 114.4 (2 C), 120.9 (2 C), 133.0, 138.6, 139.3, 156.5, 177.7.…”

“…( 1S,4R )‐2‐(Biphenyl‐4‐yl)‐2‐azabicyclo[2.2.1]hept‐5‐en‐3‐one (4c): 13e Yield (X=I, Br): 230 mg (87%), 206 mg (70%); brownish solid; mp 140–145 °C; 1 H NMR (500 MHz, CDCl 3 ): δ =2.29 (d, J =7.5 Hz, 1 H), 2.50 (d, J =8.0 Hz, 1 H), 3.53 (s, 1 H), 4.81 (d, J =1.5 Hz, 1 H), 6.73 (s, 1 H), 7.05 (d, J =4.5 Hz, 1 H), 7.33 (t, J =7.5 Hz, 1 H), 7.43 (t, J =7.5 Hz, 2 H), 7.47 (d, J =8.5 Hz, 2 H), 7.55–7.59 (m, 4 H); 13 C NMR (75 MHz, CDCl 3 ): δ =54.8, 57.3, 64.7, 118.9 (2 C), 126.9 (2 C), 127.2, 127.7 (2 C), 128.9 (2 C), 136.8, 138.7, 138.9, 139.1, 140.6, 177.4.…”

Modern Development in Copper‐ and Nickel‐Catalyzed Cross‐Coupling Reactions: Formation of Carbon‐Carbon and Carbon‐Heteroatom bonds under Microwave Irradiation Conditions

“…The optimized reaction included employment of copper(II) acetate as a catalyst and trimethylamine N ‐oxide as oxidant in basic acetonitrile solution at 80 °C. The reaction of various substrates featuring electron‐withdrawing and electron‐donating groups provided moderate to good yields of the desired products, Scheme 36 [106] …”

Recent Advances in Microwave-Assisted Copper-Catalyzed Cross-Coupling Reactions

“…Using microwave heating technique, Abe, T. et al have reported on the arylation reaction of 2-azabicyclo[2.2.1]hept-5-en-3-ones with arylboronic acids with copper catalyst to produce the related N-aryl compounds [117]. The reaction optimized to the use of a catalytic amount (10 mol %) of copper(II) acetate (Cu(OAc) 2 ), in the presence of arylboronic acids and KOH as base in acetonitrile, the reaction mixture was then heated in a microwave oven at 80 • C for 30-120 min producing the title compounds in moderate to very good yield, Scheme 58.…”