We report a redox-neutral method for nucleophilic fluorination of N-hydroxyphthalimide esters using an Ir photocatalyst under visible light irradiation. The method provides access to a broad range of aliphatic fluorides, including primary, secondary, and tertiary benzylic fluorides as well as unactivated tertiary fluorides, that are typically inaccessible by nucleophilic fluorination due to competing elimination. In addition, we show that the decarboxylative fluorination conditions are readily adapted to radiofluorination with [ 18 F]KF. We propose that the reactions proceed by two electron transfers between the Ir catalyst and redox-active ester substrate to afford a carbocation intermediate that undergoes subsequent trapping by fluoride. Examples of trapping with O-and C-centered nucleophiles and deoxyfluorination via N-hydroxyphthalimidoyl oxalates are also presented, suggesting that this approach may offer a general blueprint for affecting redox-neutral SN1 substitutions under mild conditions. File list (2) download file view on ChemRxiv EWWJBP_JACSManuscript_Final.pdf (1.04 MiB) download file view on ChemRxiv Supporting Information.pdf (23.04 MiB)

Purpose Patients undergoing resection of the external genitalia are often faced with significant deformity and decreased quality of life. Plastic surgeons are tasked with the challenge of reconstructing these defects to minimize morbidity and increase patients' quality of life. The authors have set out to investigate the efficacy of local fasciocutaneous and pedicled perforator flaps in external genital reconstruction. Methods A retrospective review was conducted of all patients undergoing reconstruction of acquired defects of the external genitalia from 2017 to 2021. In total, 24 patients met inclusion criteria for the study. Patients were allocated into 2 cohorts: patients with defects reconstructed using local fasciocutaneous flaps (FF) versus patients with defects reconstructed using pedicled islandized perforator flaps (PF). Comorbid conditions, ablative procedures, operative times, flap size, and complications were compared across all groups. Fisher exact test was used to analyze differences in comorbidities, while independent t tests were used to analyze age, body mass index, operative time, and flap size. Significance was set at P < 0.05. Results Of the 24 patients included in the study, 6 underwent reconstruction with islandized PFs (either profunda artery perforator or anterolateral thigh), and 18 underwent reconstruction with FFs. The most common indication for reconstruction was vulvectomy for vulvar cancer, followed by radical debridement for infection, and lastly penectomy for penile cancer. The PF cohort had a significantly higher percentage of previously irradiated patients (50% vs 11.1%, P = 0.019). Although mean flap size was larger in the PF cohort, this difference did not reach statistical significance (176 vs 143.4 cm2, P = 0.5). Perforator flaps had significantly longer operative times when compared with FFs (237.33 vs 128.99 minutes, P = 0.003). Average length of stay was 6.88 days in FF and 5.33 days in PF (P = 0.624). Complication profile including flap necrosis, wound healing delays, and infection were similar between groups despite a significantly higher rate of prior radiation in the PF cohort. Conclusions Our data suggest that PFs such as profunda artery perforator and anterolateral thigh flaps are associated with longer operative times but may offer a suitable option for reconstruction of acquired defects of the external genital compared with local FFs, especially in the setting of prior radiation.