TY - JOUR
T1 - Divergent Pd-catalyzed Functionalization of 4-Oxazolin-2-ones and 4-Methylene-2-oxazolidinones and Synthesis of Heterocyclic-Fused Indoles
AU - Yescas-Galicia, Daniel
AU - Restrepo-Osorio, Rodrigo A.
AU - García-González, Ailyn N.
AU - Hernández-Benítez, Roberto I.
AU - Espinoza-Hicks, José C.
AU - Escalante, Carlos H.
AU - Barrera, Edson
AU - Santoyo, Blanca M.
AU - Delgado, Francisco
AU - Tamariz, Joaquín
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/10/7
Y1 - 2022/10/7
N2 - Palladium-catalyzed functionalization was presently performed on two building blocks: 4-oxazolin-2-ones and 4-methylene-2-oxazolidinones. Direct Heck arylation of 4-oxazolin-2-ones led to a series of 5-aryl-4-oxazolin-2-ones, including analogues with N-chiral auxiliary, in an almost quantitative yield. The Pd(II)-catalyzed homocoupling reaction of 4-oxazolin-2-ones provided novel heterocyclic across-ring dienes. Meanwhile, the intramolecular cross-coupling of N-aryl-4-methylene-2-oxazolidinones furnished a series of oxazolo[3,4-a]indol-3-ones. Further functionalization of 4-methylene-2-oxazolidinones afforded substituted indoles and heterocyclic-fused indoles with aryl, bromo, carbinol, formyl, and vinyl groups. A computational study was carried out to account for the behavior of the formylated derivatives. The currently developed methodology was applied to a new formal total synthesis of ellipticine.
AB - Palladium-catalyzed functionalization was presently performed on two building blocks: 4-oxazolin-2-ones and 4-methylene-2-oxazolidinones. Direct Heck arylation of 4-oxazolin-2-ones led to a series of 5-aryl-4-oxazolin-2-ones, including analogues with N-chiral auxiliary, in an almost quantitative yield. The Pd(II)-catalyzed homocoupling reaction of 4-oxazolin-2-ones provided novel heterocyclic across-ring dienes. Meanwhile, the intramolecular cross-coupling of N-aryl-4-methylene-2-oxazolidinones furnished a series of oxazolo[3,4-a]indol-3-ones. Further functionalization of 4-methylene-2-oxazolidinones afforded substituted indoles and heterocyclic-fused indoles with aryl, bromo, carbinol, formyl, and vinyl groups. A computational study was carried out to account for the behavior of the formylated derivatives. The currently developed methodology was applied to a new formal total synthesis of ellipticine.
UR - http://www.scopus.com/inward/record.url?scp=85139240596&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.2c01563
DO - 10.1021/acs.joc.2c01563
M3 - Artículo
C2 - 36153994
AN - SCOPUS:85139240596
SN - 0022-3263
VL - 87
SP - 13034
EP - 13052
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 19
ER -