We herein describe a highly diastereoselective rhodium(I)-catalyzed C−F bond functionalization of gem-difluoroalkenes with arylboronic acids. In contrast to previously developed Pd(II)-and Pd(0)-catalyzed methods, the Rh(I)/BINAP catalytic system enabled the C−F bond arylation of both trisubstituted β,βdifluorostyrenes and tetrasubstituted β,β-difluoroacrylates in >99:1 dr toward the synthesis of valuable monofluoroalkenes. Experimental and computational studies suggested a plausible migratory insertion/β-F elimination mechanism with the [Rh(I)-Ar] species.

Objective: To evaluate the safety and efficacy of ultrasound (US)-guided percutaneous microwave ablation (UgPMWA) for palliative treatment of advanced head and neck malignancies. Materials and methods: This study includes 18 consecutive patients with advanced head and neck malignancies (n ¼ 24), who have undergone UgPMWA for palliative treatment at our institution from December 2016 to April 2020. The maximum diameter and volume of the tumor were assessed by US, CT or MRI before microwave ablation (MWA), 1, 3 and 6 months after MWA and every 6 months thereafter. The quality of life was clinically assessed by the University of Washington Head and Neck Quality of Life questionnaire (UW-QOl). Results: The success rate of tumor-targeting microwave antenna placement was 100%. No nerve injury and serious complications or death occurred during the perioperative period. The follow-up duration varied from 1 month to 38 months (11.56 ± 10.23 months) among patients. By the last followup before submission, the value of maximum diameter (5.00 ± 2.90 vs 3.28 ± 2.11 cm. p < 0.05) and tumor volume decreased significantly(74.35 ± 46.88 vs 47.45 ± 24.08 cm 3. p < 0.05)respectively after palliative treatment with UgPMWA. UW-QOl of the patients was improved (59.24 ± 11.51 vs 69.84 ± 8.12, p < 0.05). Conclusion: UgPMWA is safe and effective for the palliative treatment of head and neck malignancies. Ultrasonic guidance can indicate an accurate location of the microwave antenna. It can also monitor the ablation area in real-time during the operation to avoid damage to surrounding normal tissues.

A copper-catalyzed bisannulation reaction of malonate-tethered O-acyl oximes with pyridine, pyrazine, pyridazine, and quinoline derivatives has been developed for the concise synthesis of structurally novel dihydroindolizine-fused pyrrolidinones and their analogues. The present reaction shows excellent regioselectivity and stereoselectivity. Theoretical calculations reveal that the coordination effect of the carbonyl group in the nucleophilic substrate determines the excellent regioselectivity. Further functionalization of the generated dihydroindolizine-fused pyrrolidinone could be easily realized through substitution, Michael addition, selective aminolysis, and hydrolysis reactions.

A series of functional platinum­(II) complexes (Pt1–Pt3), which present high activity in four-photon absorption, in vivo imaging, and precise cancer therapy, as previously reported by the experimental work of Zhang et al. (Inorg. Chem. 2021, 60, 2362–2371), are computationally investigated in the article. We find that after the complex goes through four-photon absorption to the S1 state, it undergoes intersystem crossing to the T2 state and eventually reaches the T1 state through internal conversion. On the T1 state, both radiative and nonradiative decay to S0 exit. The radiative decay forms the basis for the phosphorescence imaging in tissues as reported in the original paper. In addition, the nonradiative decay can simultaneously generate cytotoxic singlet oxygen by the excited energy transfer process, also known as triplet oxygen’s quenching of triplet states. We conclude that the phosphorescence property as well as the photosensitizer character jointly bring high activity of in vivo imaging and photodynamic therapy to these complexes.