Synthesis of 4-Heteroaryl-Substituted Coumarins by Suzuki Cross-Coupling Reactions

Abstract

S y n t h e s i s o f 4 -H e t e r o a r y l -S u b s t i t u t e d C o u m a r i n sAbstract: Palladium-catalyzed coupling of 4-trifluoromethylsulfonyloxycoumarins 1a-d with heteroarylboronic acids 2a-d under the Suzuki reaction conditions affords 4-heteroaryl-substituted coumarins in good to excellent yields.

Catalytic methods of creation and functionalization of the coumarin skeleton

“…Thus, the Suzuki-Miyaura [36][37][38][39][40][41][42][43][44][45], Stille [37], Negishi [46], Sonogashira [47][48][49], Heck [50,51], and Buchwald-Hartwig [52][53][54] reactions are used to obtain various aryl-, hetaryl-, alkenyl-, alkynyl-, and also N-hetaryl-and amino-containing coumarins in high yield. [Pd]-cat.…”

Shikimic Acid Pathway

“…Suzuki cross-coupling between 4-trifluoromethylsulfonyloxy-di-and trimethylcoumarins and various heteroarylboronic acids yielded 4-heteroaryl-substituted methoxycoumarins in excellent yields (81-96 %) [55]. They are potential cytotoxic and chemopreventing agents against cancer.…”

“…Thus, these compounds ( Fig. 13.57) potentially constitute a new generation of neoflavonoid tubulin binding agents [55]. 4-Amido-and 4-(N-heteroaryl) coumarins constitute an important class of flavonoids, widely occurring in nature and also are components of the structures of more complex natural products; they exhibit a broad range of biological activities.…”

Plant coumarins: VIII. Suzuki reaction in the synthesis of 3-aryl(hetaryl)furocoumarins

“…In the present work we made an attempt to synthesize furocoumarin derivatives containing an aromatic or heteroaromatic substituent on C 3 by palladium-catalyzed cross-coupling of oreoselone trifluoromethanesulfonate (I) with boronic acid (Suzuki reaction). 4-Halo-and 4-trifluoromethylsulfonyloxycoumarins were successfully involved in Suzuki-Miyaura reaction to synthesize 4-aryl(hetaryl or alkynyl)coumarins [8,9], while analogous reactions with substituted furocoumarins were not reported previously.Cross-coupling of oreoselone trifluoromethanesulfonate (I) with o-tolylboronic acid (II) was used as …”

“…4-Halo-and 4-trifluoromethylsulfonyloxycoumarins were successfully involved in Suzuki-Miyaura reaction to synthesize 4-aryl(hetaryl or alkynyl)coumarins [8,9], while analogous reactions with substituted furocoumarins were not reported previously. [9,10]. We found that the reaction of oreoselone trifluoromethanesulfonate (I) with o-tolylboronic acid (II) in the presence of Bu 4 N + Br -(10%) requires shorter time (4.5 h) and ensures increased yield of compound III (to 75%).…”