RESUMEN
A Rh(III)-catalyzed annulation of 2-arylbenzimidazoles with α-diazo carbonyl compounds via C-H activation/carbene insertion/intramolecular cyclization is explored. The switchable product selectivity is achieved by the use of distinct α-diazo carbonyl compounds. Benzimidazole-fused quinolines are obtained through [4 + 2] annulation exclusively when 2-diazocyclohexane-1,3-diones are used, where they act as a C2 synthon. Alternatively, diazonaphthalen-1(2H)-ones merely function as a one-carbon unit synthon to generate a quaternary center through [4 + 1] cyclization to afford spirocyclic benzimidazole-fused isoindole naphthalen-2-ones. A thorough mechanistic study reveals the course of the reaction.
RESUMEN
A Rh(III)-catalyzed [4 + 1] cyclization of 2-arylbenzimidazoles with alkynoates through C-H activation/ortho-alkenylation/intramolecular annulation cascade to obtain benzimidazole-fused isoindoles is reported. The reaction of the Rh catalyst and internal alkyne ester provides benzo[4,5]imidazo[2,1-a]isoindole acetate exclusively. Conversely, internal alkyne amide participates in the annulation process in the presence of a Ru catalyst to provide benzo[4,5]imidazo[2,1-a]isoindole acetamide. The alkyne acts as a C1 synthon and undergoes [4 + 1] cyclization rather than traditional [4 + 2] annulation.
RESUMEN
A rhodium(III)-catalyzed controllable [4 + 1] and [4 + 2] annulation of N-aryl pyrazolones with maleimides as C1 and C2 synthon has been explored for the synthesis of spiro[pyrazolo[1,2-a]indazole-pyrrolidines] and fused pyrazolopyrrolo cinnolines. The product selectivity was achieved through time-dependent annulation. The [4 + 1] annulation reaction involves sequential Rh(III)-catalyzed C-H alkenylation of N-aryl pyrazolone, followed by an intramolecular spirocyclization via aza-Michael-type addition to afford spiro[pyrazolo[1,2-a]indazole-pyrrolidine]. However, prolonged reaction time converts in situ formed spiro[pyrazolo[1,2-a]indazole-pyrrolidine] into fused pyrazolopyrrolocinnoline. This unique product formation switch proceeds via strain-driven ring expansion through a 1,2-shift of the C-C bond.
RESUMEN
A Rh(III)-catalyzed cascade C-H activation and cyclization of 2-aryl benzimidazoles with maleimides for the synthesis of benzimidazole-fused isoquinolines and benzimidazole-spiro isoindoles is reported. Switchable selectivity towards the formation of these two distinct products can be achieved using unsubstituted and substituted benzimidazoles at the ortho-position of the phenyl ring. Mechanistically, C-H activation followed by migratory insertion of maleimide forms a Heck-type intermediate. Unsubstituted benzimidazole undergoes aza-Michael addition to form a (4 + 2) fused product, whereas ortho-substituted phenyl benzimidazole causes steric clash to deliver a (4 + 1) spiro-adduct favorably via acid-catalyzed intramolecular annulation.
Asunto(s)
Bencimidazoles , Isoquinolinas , Catálisis , CiclizaciónRESUMEN
BACKGROUND: This study was undertaken to determine if expectant management with a longer waiting period is an effective and safe option for women with anembryonic pregnancy. METHODS: Women with an ultrasound diagnosis of anembryonic pregnancy were offered the option of expectant management with a 3-week waiting period or surgical evacuation according to their preference. RESULTS: A total of 121 women with anembryonic pregnancies participated in the study; 45 of them elected expectant management. The overall success rate was 83.3% in the expectant group and 97.3% in the surgical group. No significant complications were noted in either group. CONCLUSION: Expectant management with a 3-week waiting period is an efficacious and safe option with a low risk of infection and hemorrhage. However, it is difficult to predict the exact time period before spontaneous abortion.
Asunto(s)
Aborto Retenido/terapia , Aborto Retenido/diagnóstico , Adulto , Femenino , Edad Gestacional , Humanos , EmbarazoRESUMEN
OBJECTIVE: To report a case of a patient with cervical squamous cell carcinoma stage IIIB who was diagnosed with malignant mixed müllerian tumor (MMMT) 5 years after radiotherapy. CASE REPORT: A 57-year-old female patient with cervical squamous cell carcinoma FIGO stage IIIB received pelvic irradiation for her disease. After radiotherapy, she was followed-up every 6 months. At 60 months, Papanicolaou smear revealed abnormal cancer cells and secondary MMMT was diagnosed. The patient underwent surgical treatment followed by chemotherapy. However, the cancer recurred 8 months after surgery and the patient died 1 month later. CONCLUSION: Patients with cervical cancer administered irradiation many years previously remain at high risk of secondary malignancies. In these cases, long-term follow-up with extreme caution is mandatory. For patients with any types of symptoms, aggressive and immediate investigation is suggested in order to detect possible occult malignancies.