Síntese régio- e diastereosseletiva de oxazolidinonas via reação de cloroaminociclização promovidas por sais de Pd(II)

• Ano de defesa: 2018
• Autor(a) principal: Papa, Bruna Lacerda [UNIFESP]
• Tipo de documento: Dissertação
• Tipo de acesso: Acesso aberto
• Idioma: por
• Instituição de defesa: Universidade Federal de São Paulo
• Palavras-chave em Português: Chloroaminocyclization; Oxazolidinones; Aminodiols; Palladium; Diastereoseletive; Cloroaminociclização; Oxazolidinonas; Aminodióis; Paládio; Diastereosseletiva
• Link de acesso: https://sucupira.capes.gov.br/sucupira/public/consultas/coleta/trabalhoConclusao/viewTrabalhoConclusao.jsf?popup=true&id_trabalho=7253744; https://repositorio.unifesp.br/handle/11600/52802

Allylic alcohol and especially its structural analogues are organic compounds of great interest to scientific community, since they can suffer a range of chemical transformations. Despite of several advances in reactions involving allylic alcohol derivatives using catalysis. It is possible to affirm that this is a fertile field to develop a variety of new symmetric and asymmetric reaction via metallic complexes as catalysts. A new methodology aiming the synthesis of oxazolidinones has been developed. Reactional time, temperature, Pd(II) source, quantity of CuCl2, solvent, catalyst loading and concentration were evaluated resulting in a optimize condition. The optimize reactional condition is: carbamate (0.2 mmol), PdCl2 (10 mol%), CuCl2 (1.0 mmol), LiCl (1.0 mmol) in ACN (0,10 mol.L-1) during 2,5 hours at 60 ˚C. The scope was explored where fourteen new oxazolidinones were obtain with yields from 50 to 95% and diastereoisomeric ratio up to 99:1. The developed methodology was efficient in a 15 times bigger scale (3.0 mmol) than the optimized one. Besides that, hydrogen NMR and computational studies helped us to propose a trans-catalytic-cycle to the formation of the majority diastereoisomer and a cis-catalytic-cycle to the minor diastereoisomer. In addition, four chemical transformations were done to obtain aminoalcohols, showing the synthetic versatility of the studied oxazolidinones.