The Suzuki–Miyaura and Buchwald–Hartwig coupling reactions are widely used to form carbon-carbon (C–C) and carbon-nitrogen (C–N) bonds, respectively. We report the incorporation of a formal nitrene insertion process into the Suzuki–Miyaura reaction, altering the products from C–C–linked biaryls to C–N–C–linked diaryl amines and thereby joining the Suzuki–Miyaura and Buchwald–Hartwig coupling pathways to the same starting-material classes. A combination of a bulky ancillary phosphine ligand on palladium and a commercially available amination reagent enables efficient reactivity across aryl halides and pseudohalides, boronic acids and esters, and many functional groups and heterocycles. Mechanistic insights reveal flexibility on the order of bond-forming events, suggesting potential for expansion of the aminative cross-coupling concept to encompass diverse nucleophiles and electrophiles as well as four-component variants. 

Aminative Suzuki–Miyaura coupling

New trends for transition metal-catalyzed ortho/ipso difunctionalizations of arenes

This study aimed to report our experience with spinal anesthesia (SA) in patients undergoing L5-S1 interlaminar endoscopic lumbar discectomy (IELD) and clarify its advantages and disadvantages.One hundred twelve patients who underwent IELD for an L5-S1 disc herniation under SA were retrospectively analyzed. SA with 0.5% ropivacaine was administered using a 27-gauge fine needle. Intraoperatively, the volume and level of SA, surgical time, blood loss, and cardiopulmonary complications were documented. Postoperative data was collected included the number of patients who ambulated on the day of surgery, incidence of complications and were then statistically analyzed.Analgesia was complete throughout the entire operation in all patients and no other adjuvant intraoperative analgesic drugs were needed. Mean visual analog scale scores for intraoperative and early postoperative (24 h) pain were 0 and 2.43 ± 1.66. SA was administered at the L3-4 interspace in 34 patients (30.4%) and the L2-3 interspace in 78 (69.6%). Administration was successful with the first attempt in all patients. Mean operation time was 70.12 ± 6.52 min. Mean intraoperative blood loss volume was 20.71 ± 5.26 ml. Ninety-eight patients ambulated on the same day as surgery. Mean length of hospital stay was 24.36 ± 3.64 h. Dural injury without damaging the nerve root occurred in one patient. One patient experienced recurrent disc herniation. Intraoperative hypotension and respiratory distress occurred in five (4.5%) and three (2.7%) patients, respectively. Three patients (2.7%) received postoperative analgesia therapy and two (1.8%) experienced nausea. Two patients (1.8%) developed urinary retention. Spinal headache, cauda equina syndrome, and neurotoxicity did not occur.SA can achieve satisfactory pain control for patients undergoing IELD with a low incidence of adverse events. SA may be a useful alternative to local and general anesthesia for IELD surgery. Future randomized controlled trials are warranted to investigate. 

Spinal anesthesia for L5-S1 interlaminar endoscopic lumbar discectomy: a retrospective study

Site-selective ortho/ipso C-H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4-tetrasubstituted ones (62 examples, up to 97% yields). To ensure the excellent regioselectivity of the process while keeping high efficiency, an original strategy based on a "C-H thianthenation/Catellani-type reaction" sequence was developed starting from simple arenes. Non-prefunctionalized arenes were first regioselectively converted into the corresponding thianthrenium salts. Then, a palladium-catalyzed, norbornene (NBE)-mediated process allowed the synthesis of ipso-olefinated/ortho-alkylated polyfunctionalized arenes using a thianthrene as a leaving group (revisited Catellani reaction). Pleasingly, using a commercially available norbornene (NBE) and a unique catalytic system, synthetic challenges known for the Catellani reaction with aryl iodides were smoothly and successfully tackled with the "thianthrenium" approach. The protocol was robust (gram-scale reaction) and was widely applied to the two-fold functionalization of various arenes including bio-active compounds. Moreover, a panel of olefins and alkyl halides as coupling partners was suitable. Pleasingly, the "thianthrenium" strategy was successfully further applied to the incorporation of other groups at the ipso (CN/alkyl/H, aryl) and ortho (alkyl, aryl, amine, thiol) positions, showcasing the generality of the process.

Site-Selective Ortho/Ipso C-H Difunctionalizations of Arenes using Thianthrene as a Leaving Group.

Intraoperative controlled hypotension improves surgical field visibility by reducing blood loss (efficacy) but poses potential risks linked to organ hypoperfusion (safety). The use of controlled hypotension persists despite increasing evidence of associations between intraoperative inadvertent hypotension and adverse outcomes. Therefore, we tested the hypothesis that the focus and results of intraoperative controlled hypertension research differ across anaesthesia and surgery investigators because of differing priorities. 

Efficacy and safety of intraoperative controlled hypotension: a systematic review and meta-analysis of randomised trials

The C-H amination and C-O alkenylation of aryl triflates was achieved through Pd/norbornene (NBE) cooperative catalysis. By this strategy, various ortho-alkenyl tertiary anilines including those bearing functional groups were produced in good to excellent yields. This reaction represents a new conversion model for phenoxides. It expands the scope of Catellani-type reactions and the application of phenoxides in organic synthesis.

Palladium-catalyzed and norbornene-mediated C-H amination and C-O alkenylation of aryl triflates.

Background Controlled hypotension technique was usually used to reduce intraoperative bleeding, and it could improve visualization of the surgical field during total knee arthroplasty (TKA). However, inappropriate controlled hypotension, through reducing cerebral blood flow or cerebral perfusion pressure, may cause postoperative cognitive dysfunction (POCD), so it is important to identify the appropriate level of controlled hypotension. Objective: To investigate the effects of different levels of controlled hypotension on regional cerebral oxygen saturation and postoperative cognitive function in patients undergoing TKA. Methods Patients meeting inclusion criteria were enrolled through preoperative visits and basic information was obtained. The patients were randomly divided into three groups: Group A, MAP was maintained at 90–100% of the baseline; Group B, MAP was maintained at 80–90% of the baseline; Group C, MAP was maintained at 70–80% of the baseline. The MAP, HR, and rSO2 were observed and recorded during the operation. The C-reactive protein (CRP), hemoglobin (Hb) and MMSE score at 1, 3, and 7 days after operation were recorded. SPSS25.0 was used for data analysis. Result When the MAP had a decrease among the three groups, rSO2 did not decrease significantly, and none of the patients experienced POCD which was measured by MMSE. And there was no correlation between the decline in rSO2 and that in MAP. Conclusion No POCD was experienced in the three groups, and we recommend that the controlled hypotensive target indicated by MAP was maintained at 70–80% of the baseline which not only decreases intraoperative bleeding and improve the quality of the surgical field, but also is still within safe levels. Graphical Abstract Study flowchat.

/pdf/effects-of-different-levels-of-controlled-hypotension-on-3oqwz0fy.pdf

Effects of different levels of controlled hypotension on regional cerebral oxygen saturation and postoperative cognitive function in patients undergoing total knee arthroplasty

The ortho C‐H methylation and ipso C‐O alkenylation of aryl triflates is regio‐selectively achieved in one pot by palladium/norbornene (NBE) synergistic catalysis. This work provides an efficient method for preparing poly‐substituted aromatics with (deuterated) methyl and alkenyl groups from the readily available phenoxides.

Ortho‐C‐H Methylation and Ispo‐C‐O Alkenylation of Aryl Triflates via Catellani Strategy

Pd/NBE-Mediated Annulation of Aryl Triflates with Oxiranes: Efficient Synthesis of 2,3-Dihydrobenzofurans

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Palladium-catalyzed and norbornene-mediated C-H amination and C-O alkenylation of aryl triflates.

Effects of different levels of controlled hypotension on regional cerebral oxygen saturation and postoperative cognitive function in patients undergoing total knee arthroplasty

Ortho‐C‐H Methylation and Ispo‐C‐O Alkenylation of Aryl Triflates via Catellani Strategy

Pd/NBE-Mediated Annulation of Aryl Triflates with Oxiranes: Efficient Synthesis of 2,3-Dihydrobenzofurans