Enantioconvergent Cu-catalysed N-alkylation of aliphatic amines.

Chiral amines are commonly used in the pharmaceutical and agrochemical industries1. The strong demand for unnatural chiral amines has driven the development of catalytic asymmetric methods1,2. Although the N-alkylation of aliphatic amines with alkyl halides has been widely adopted for over 100 years, catalyst poisoning and unfettered reactivity have been preventing the development of a catalyst-controlled enantioselective version3-5. Here we report the use of chiral tridentate anionic ligands to enable the copper-catalysed chemoselective and enantioconvergent N-alkylation of aliphatic amines with α-carbonyl alkyl chlorides. This method can directly convert feedstock chemicals, including ammonia and pharmaceutically relevant amines, into unnatural chiral α-amino amides under mild and robust conditions. Excellent enantioselectivity and functional-group tolerance were observed. The power of the method is demonstrated in a number of complex settings, including late-stage functionalization and in the expedited synthesis of diverse amine drug molecules. The current method indicates that multidentate anionic ligands are a general solution for overcoming transition-metal-catalyst poisoning.

Copper-Catalyzed Enantioconvergent Radical N-Alkylation of Diverse (Hetero)aromatic Amines.

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, the bond formation relies on the interaction between nucleophile-sequestered metal complexes and radicals, limiting the nucleophile scope to sterically uncongested ones. The coupling of sterically congested nucleophiles poses a significant challenge due to difficulties in transmetalation, restricting the reaction generality. Here, we describe a probable outer-sphere nucleophilic attack mechanism that circumvents the challenging transmetalation associated with sterically congested nucleophiles. This strategy enables a general copper-catalyzed enantioconvergent radical N-alkylation of aromatic amines with secondary/tertiary alkyl halides and exhibits catalyst-controlled stereoselectivity. It accommodates diverse aromatic amines, especially bulky secondary and primary ones to deliver value-added chiral amines (>110 examples). It is expected to inspire the coupling of more nucleophiles, particularly challenging sterically congested ones, and accelerate reaction generality.

Vertical Scar Reduction Mammaplasty Using the Superomedial-Based Pedicle Technique in Gigantomastia.

BACKGROUND: Breast reduction surgery has witnessed significant advancements in recent years; however, it continues to pose challenges for both surgeons and patients when dealing with cases involving excessive breast volume and severe breast ptosis. This study aimed to assess the aesthetic outcomes and the impact on the quality of life, as measured by the BREAST-Q questionnaire, in patients with gigantomastia and severe breast ptosis who underwent reduction mammaplasty using the superomedial-based pedicle technique. METHODS: We present a retrospective series comprising 84 patients who underwent reduction mammoplasty utilizing the superomedial pedicle technique. The surgical resections exceeded 1 kg per breast, with a mean resection weight of 1506.58 g (right breast) and 1500.32 g (left breast). The preoperative mean suprasternal notch to nipple distance measured 40.50 cm (right breast) and 40.38 cm (left breast). Postoperatively, the patients were followed up for a minimum of 6 months. Both preoperative and postoperative BREAST-Q surveys were administered to the participants, and scores were analyzed using descriptive statistics. RESULTS: Complications were observed in 3 patients (3.57%), characterized by partial loss of the areola, which resolved spontaneously over time. Additionally, 2 cases of hematoma and 2 instances of minor delayed wound healing were reported. All patients expressed satisfaction with their aesthetic outcomes, as they achieved a natural breast shape and minimal scarring, along with symptomatic relief. CONCLUSIONS: The superomedial pedicle reduction mammaplasty technique has demonstrated its ability to produce satisfactory aesthetic outcomes and long-term benefits in patients with excessively large breasts. Careful patient selection and postoperative management are vital for achieving optimal results. Further investigations involving larger sample sizes and longer follow-up periods are warranted to validate our findings. LEVEL OF EVIDENCE: IV.

Liposuction Through an Axillary Fold Incision Combined with a Small Areola Incision to Treat Gynecomastia.

BACKGROUND: Gynecomastia is a progressive disease characterized by enlarged breasts, affecting a significant proportion of men. Persistent gynecomastia negatively affects the psychological and emotional development of patients; therefore, surgical intervention is required. In this article, we describe a surgical technique, where liposuction through an axillary incision is used in combination with a single small periareolar incision, to obtain the most minimal scars in the treatment of gynecomastia. METHODS: Between June 2021 and June 2023, 125 patients with different Simon grades of gynecomastia were enrolled. The patients' basic conditions and operation processes were recorded. Following surgery, a score was assigned according to the five main aesthetic aspects of the surgical procedure. RESULTS: In total, 125 patients with gynecomastia were treated with a pre-axillary fold incision combined with a small areolar incision. There were 17 cases of Simon grade I, 46 grade IIA, 42 grade IIB, and 20 grade III. The average operation time was 45.8 min, the average liposuction volume was 250.5 mL, the average glandular tissue volume was 50.5 g, intraoperative blood loss ranged from 15 to 60 mL, and the average hospital stay was 3.2 days. Regarding the postoperative aesthetic effect, doctors scored > 4 points, and the patient satisfaction score was > 7.5, which fully affirmed the aesthetic effect of this method. CONCLUSIONS: Treatment of gynecomastia through an anterior axillary fold incision combined with a small areolar incision is safe and feasible, involving a simple procedure, short operation time, and few complications. Its efficacy and cosmetic effects could lead to its use as a primary surgical method to treat gynecomastia. LEVEL OF EVIDENCE IV: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine Ratings, please refer to Table of Contents or online Instructions to Authors www.springer.com/00266 .

Clinical Application of Long-Pulsed 800-Nm Diode Laser Depilation Technology on Microtia Reconstruction in 965 Patients.

BACKGROUND: The issue of hair growth on reconstructed ears has been a matter of concern for both patients and surgeons, despite the notable progress made in microtia reconstruction technology in recent times. OBJECTIVE: This study aims to present the practical implementation of long-pulsed 800-nm diode laser depilation technology in the field of auricular reconstruction. Furthermore, it seeks to establish a comprehensive and standardized protocol for utilizing lasers in the reconstruction of microtia ears. METHODS: A total of 965 patients (comprising 1021 ears) diagnosed with congenital microtia underwent treatment using 800-nm long-pulsed diode laser depilation. The participants received 1-3 treatment sessions with intervals of 25-30 days. To assess the effectiveness of the treatment, two independent observers compared photographs and measured the reduction in terminal hair count before and after the final session. Clinical outcomes were evaluated using VAS questionnaires, and any adverse events were diligently recorded. RESULTS: The findings indicated that the utilization of the long-pulsed 800-nm diode laser was both safe and efficient in achieving hair removal during microtia ear reconstruction. As additional sessions were conducted, pain scores demonstrated a decline, while adverse reactions remained minimal. LIMITATIONS: This is a retrospective single-institution study. CONCLUSION: The application of a long-pulsed 800-nm diode laser has been proved to be a safe and effective method for removing hair during the process of microtia ear reconstruction, involving the use of a tissue expander and autologous costal cartilage. To achieve satisfactory results in hair removal, it was found necessary to repeat the shots procedure two to three times. LEVEL OF EVIDENCE IV: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors www.springer.com/00266 .

Copper-Catalyzed Enantioselective C(sp3 )-SCF3 Coupling of Carbon-Centered Benzyl Radicals with (Me4 N)SCF3.

In contrast with the well-established C(sp2 )-SCF3 cross-coupling to forge the Ar-SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3 )-SCF3 bond has remained largely unexplored. We herein disclose a copper-catalyzed enantioselective radical C(sp3 )-SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4 N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino-oxazoline-derived anionic N,N,P-ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3 )-SCF3 cross-coupling of racemic benzyl halides and three-component 1,2-carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3 -containing molecules of interest in organic synthesis and medicinal chemistry.

Cu(I)-Catalyzed Chemo- and Enantioselective Desymmetrizing C-O Bond Coupling of Acyl Radicals.

Transition-metal-catalyzed enantioselective functionalization of acyl radicals has so far not been realized, probably due to their relatively high reactivity, which renders the chemo- and stereocontrol challenging. Herein, we describe Cu(I)-catalyzed enantioselective desymmetrizing C-O bond coupling of acyl radicals. This reaction is compatible with (hetero)aryl and alkyl aldehydes and, more importantly, displays a very broad scope of challenging alcohol substrates, such as 2,2-disubstituted 1,3-diols, 2-substituted-2-chloro-1,3-diols, 2-substituted 1,2,3-triols, 2-substituted serinols, and meso primary 1,4-diols, providing enantioenriched esters characterized by challenging acyclic tetrasubstituted carbon stereocenters. Partnered by one- or two-step follow-up transformations, this reaction provides a convenient and practical strategy for the rapid preparation of chiral C3 building blocks from readily available alcohols, particularly the industrially relevant glycerol. Mechanistic studies supported the proposed C-O bond coupling of acyl radicals.

Copper-Catalyzed Enantioconvergent Radical C(sp3)-N Cross-Coupling of Activated Racemic Alkyl Halides with (Hetero)aromatic Amines under Ambient Conditions.

The enantioconvergent C(sp3)-N cross-coupling of racemic alkyl halides with (hetero)aromatic amines represents an ideal means to afford enantioenriched N-alkyl (hetero)aromatic amines yet has remained unexplored due to the catalyst poisoning specifically for strong-coordinating heteroaromatic amines. Here, we demonstrate a copper-catalyzed enantioconvergent radical C(sp3)-N cross-coupling of activated racemic alkyl halides with (hetero)aromatic amines under ambient conditions. The key to success is the judicious selection of appropriate multidentate anionic ligands through readily fine-tuning both electronic and steric properties for the formation of a stable and rigid chelating Cu complex. Thus, this kind of ligand could not only enhance the reducing capability of a copper catalyst to provide an enantioconvergent radical pathway but also avoid the coordination with other coordinating heteroatoms, thereby overcoming catalyst poisoning and/or chiral ligand displacement. This protocol covers a wide range of coupling partners (89 examples for activated racemic secondary/tertiary alkyl bromides/chlorides and (hetero)aromatic amines) with high functional group compatibility. When allied with follow-up transformations, it provides a highly flexible platform to access synthetically useful enantioenriched amine building blocks.

Exploring the motivations for pursuing operative labiaplasty in Chinese patients.

This study aimed to investigate the motivations for Chinese patients seeking operative labiaplasty. Data was collected from January 2018 to December 2019 using a standardized questionnaire, which examined factors influencing patients' motivations, including aesthetic and functional reasons, as well as psychological factors. Of the 216 patients who responded to the questionnaire within 24 months, 22.2% cited cosmetic reasons, while 38.4% reported functional discomfort. Both functional and aesthetic reasons were cited by 35.2% of patients, while 4.2% reported psychological troubles. It is noteworthy that patients who sought surgical intervention for physical complaints did so as a personal decision, and only 6.3% of patients seeking labiaplasty for cosmetic reasons were influenced by their sexual partner. Additionally, 7.9% and 66.7% of patients with other motivations were influenced by their male spouse, while 2.6% and 33.3% were influenced by the media. In conclusion, this study suggests that most Chinese patients seek labiaplasty for functional reasons, with few being influenced by sexual partners or media.Impact statementWhat is already known on this subject? The growing demand and interest in labiaplasty surgery has been widely acknowledged. Existing reports from western countries have highlighted that aesthetic concerns are the primary motivations behind patients' requests for this surgical intervention. However, there is limited information available regarding the factors influencing Chinese patients' decisions to undergo labiaplasty, as China has a large population. Therefore, the specific reasons behind Chinese patients' requests for labiaplasty are not well understood.What do the results of this study add? This clinical study focuses on the perspectives of eastern women regarding labia reduction surgery, contributing to the existing literature on this topic. Notably, this study is one of the few that examines the request for surgical reduction of hypertrophy of the labia minora and highlights that not all patients undergo surgical intervention purely for personal reasons.What are the implications of these findings for clinical practice and/or further research? The implications of these findings for clinical practice and further research are significant. Given the increasing demand for labiaplasty, gynecologists in Australia, Western Europe, the United States, and New Zealand are likely to encounter a rising number of women seeking labial reduction surgery. Similarly, labiaplasty has become an increasingly popular cosmetic surgery procedure in China. This study's results differ from previous research, which suggested that functional concerns were the primary motivation for women seeking to undergo labiaplasty. The request for pursuing labiaplasty is influenced not only by personal preferences but also by external factors. Therefore, a comprehensive evaluation before considering the procedure is crucial, and if practitioners are unsure, multidisciplinary specialized evaluation should be considered.

Copper-Catalyzed Chemo- and Enantioselective Radical 1,2-Carbophosphonylation of Styrenes.

The copper-catalyzed enantioselective radical difunctionalization of alkenes from readily available alkyl halides and organophosphorus reagents possessing a P-H bond provides an appealing approach for the synthesis of α-chiral alkyl phosphorus compounds. The major challenge arises from the easy generation of a P-centered radical from the P-H-type reagent and its facile addition to the terminal side of alkenes, leading to reverse chemoselectivity. We herein disclose a radical 1,2-carbophosphonylation of styrenes in a highly chemo- and enantioselective manner. The key to the success lies in not only the implementation of dialkyl phosphites with a strong bond dissociation energy to promote the desired chemoselectivity but also the utilization of an anionic chiral N,N,N-ligand to forge the chiral C(sp3 )-P bond. The developed Cu/N,N,N-ligand catalyst has enriched our library of single-electron transfer catalysts in the enantioselective radical transformations.

Synthesis of α-Quaternary ß-Lactams via Copper-Catalyzed Enantioconvergent Radical C(sp3 )-C(sp2 ) Cross-Coupling with Organoboronate Esters.

The copper-catalyzed enantioconvergent radical C(sp3 )-C(sp2 ) cross-coupling of tertiary α-bromo-ß-lactams with organoboronate esters could provide the synthetically valuable α-quaternary ß-lactams. The challenge arises mainly from the construction of sterically congested quaternary stereocenters between the tertiary alkyl radicals and chiral copper(II) species. Herein, we describe our success in achieving such transformations through the utilization of a copper/hemilabile N,N,N-ligand catalyst to forge the sterically congested chiral C(sp3 )-C(sp2 ) bond via a single-electron reduction/transmetalation/bond formation catalytic cycle. The synthetic potential of this approach is shown in the straightforward conversion of the corresponding products into many valuable building blocks. We hope that the developed catalytic cycle would open up new vistas for more enantioconvergent cross-coupling reactions.

Copper-Catalyzed Enantioconvergent Radical C(sp3 )-N Cross-Coupling: Access to α,α-Disubstituted Amino Acids.

Transition-metal catalyzed enantioconvergent cross-coupling of tertiary alkyl halides with ammonia offers a rapid avenue to chiral unnatural α,α-disubstituted amino acids. However, the construction of chiral C-N bonds between tertiary-carbon electrophiles and nitrogen nucleophiles presented a great challenge owing to steric congestion. We report a copper-catalyzed enantioconvergent radical C-N cross-coupling of alkyl halides with sulfoximines (as ammonia surrogates) under mild conditions by employing a chiral anionic N,N,N-ligand with a long spreading side arm. An array of α,α-disubstituted amino acid derivatives were obtained with good efficiency and enantioselectivity. The synthetic utility of the strategy has been showcased by the elaboration of the coupling products into different chiral α-fully substituted amine building blocks.

Ligand Development for Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Racemic Alkyl Halides.

The enantioconvergent cross-coupling of racemic alkyl halides represents a powerful tool for the synthesis of enantioenriched molecules. In this regard, the first-row transition metal catalysis provides a suitable mechanism for stereoconvergence by converting racemic alkyl halides to prochiral radical intermediates owing to their good single-electron transfer ability. In contrast to the noble development of chiral nickel catalyst, copper-catalyzed enantioconvergent radical cross-coupling of alkyl halides is less studied. Besides the enantiocontrol issue, the major challenge arises from the weak reducing capability of copper that slows the reaction initiation. Recently, significant efforts have been dedicated to basic research aimed at developing chiral ligands for copper-catalyzed enantioconvergent radical cross-coupling of racemic alkyl halides. This perspective will discuss the advances in this burgeoning area with particular emphasis on the strategic chiral anionic ligand design to tune the reducing capability of copper for the reaction initiation under thermal conditions from our research group.

A Counterion/Ligand-Tuned Chemo- and Enantioselective Copper-Catalyzed Intermolecular Radical 1,2-Carboamination of Alkenes.

The copper-catalyzed enantioselective intermolecular radical 1,2-carboamination of alkenes with readily accessible alkyl halides is an appealing strategy for producing chiral amine scaffolds. The challenge arises from the easily occurring atom transfer radical addition between alkyl halides and alkenes and the issue of enantiocontrol. We herein describe a radical alkene 1,2-carboamination with sulfoximines in a highly chemo- and enantioselective manner. The key to the success of this process is the conceptual design of a counterion/highly sterically demanded ligand coeffect to promote the ligand exchange of copper(I) with sulfoximines and forge chiral C-N bonds between alkyl radicals and the chiral copper(II) complex. The reaction covers alkenes bearing distinct electronic properties, such as aryl-, heteroaryl-, carbonyl-, and aminocarbonyl-substituted ones, and various radical precursors, including alkyl chlorides, bromides, iodides, and the CF3 source. Facile transformations deliver many chiral amine building blocks of interest in organic synthesis and related areas.

Design of Hemilabile N,N,N-Ligands in Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Benzyl/Propargyl Halides with Alkenylboronate Esters.

The enantioconvergent radical C(sp3)-C(sp2) cross-coupling of alkyl halides with alkenylboronate esters is an appealing tool in the assembly of synthetically valuable enantioenriched alkenes owing to the ready availability, low toxicity, and air/moisture stability of alkenylboronate esters. Here, we report a copper/chiral N,N,N-ligand catalytic system for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters (>80 examples) with good functional group tolerance. The key to the success is the rational design of hemilabile N,N,N-ligands by mounting steric hindrance at the ortho position of one coordinating quinoline ring. Thus, the newly designed ligand could not only promote the radical cross-coupling process in the tridentate form but also deliver enantiocontrol over highly reactive alkyl radicals in the bidentate form. Facile follow-up transformations highlight its potential utility in the synthesis of various enantioenriched building blocks as well as in the late-stage functionalization for drug discovery.

Long-Term Follow-up in Labiaplasty in 414 Women: A Single-Center Experience in China.

ABSTRACT: Women with labial hypertrophy may opt for labiaplasty. The aim of the study was to analyze the complications, long-term follow-up of clinical outcomes and satisfaction in this population over the past 10 years.All women who underwent labiaplasty with or without clitoral hood reduction at our center between January 2008 and August 2020 were retrospectively identified. Retrospective study was conducted, recording follow-up outcomes, motivations, techniques, postoperative complications, reasons requiring reoperation, and surgical satisfaction concerned different clinical characteristics. A concrete analysis of each specific outcome and a detailed knowledge of these procedures were performed.A total of 52.41% reported functional impairment, 20.25% cited aesthetics complains, and 27.34% were motivated by both the previously mentioned reasons. Women undergoing surgical correction sometimes mixed with various psychological aspects. A total of 91.06% reported that they were moderately (6.04%) or extremely (85.02%) satisfied with the outcomes after surgery, and 37 (8.94%) reported dissatisfied. Revision surgery was needed in a small number of patients (n = 7 of 414 patients, 1.69%) because of undesirable appearance. The most common complication in our patients was asymmetry (6.28%). Women requested labiaplasty in the last 2 reasons or procedures or without psychological distress were more likely feel satisfied with the results (satisfaction rate >90%). There was a significant difference in satisfaction among the 3 concerns as well as between the 2 kinds of psychological conditions ( P < 0.05). Satisfaction of patients with aesthetic complains compared with the other 2 worries was significantly lower ( P < 0.05). There was no significant difference among the 3 procedures in this comparison group ( P > 0.05). In addition, satisfaction in labiaplasty with or without clitoral hoodoplasty, neither of which was statistically different ( P > 0.05). Patients aged 30 to 39 years reported the lowest satisfaction in comparison with the other age groups.Labiaplasty of the labia minora is the most commonly performed genital cosmetic surgery procedure. This study on 414 patients demonstrated that it is associated with a high degree of patient satisfaction and low morbidity and provided evidence of safety and effectiveness preliminary, indicating that the procedure may be regarded as safe.

Enantioselective Hydroxylation of Dihydrosilanes to Si-Chiral Silanols Catalyzed by In Situ Generated Copper(II) Species.

Catalytic enantioselective hydroxylation of prochiral dihydrosilanes with water is expected to be a highly efficient way to access Si-chiral silanols, yet has remained unknown up to date. Herein, we describe a strategy for realizing this reaction: using an alkyl bromide as a single-electron transfer (SET) oxidant for invoking CuII species and chiral multidentate anionic N,N,P-ligands for effective enantiocontrol. The reaction readily provides a broad range of Si-chiral silanols with high enantioselectivity and excellent functional group compatibility. In addition, we manifest the synthetic potential by establishing two synthetic schemes for transforming the obtained products into Si-chiral compounds with high structural diversity. Our preliminary mechanistic studies support a mechanism involving SET for recruiting chiral CuII species as the active catalyst and its subsequent σ-metathesis with dihydrosilanes.

Enantioconvergent Cu-Catalyzed Radical C-N Coupling of Racemic Secondary Alkyl Halides to Access α-Chiral Primary Amines.

α-Chiral alkyl primary amines are virtually universal synthetic precursors for all other α-chiral N-containing compounds ubiquitous in biological, pharmaceutical, and material sciences. The enantioselective amination of common alkyl halides with ammonia is appealing for potential rapid access to α-chiral primary amines, but has hitherto remained rare due to the multifaceted difficulties in using ammonia and the underdeveloped C(sp3)-N coupling. Here we demonstrate sulfoximines as excellent ammonia surrogates for enantioconvergent radical C-N coupling with diverse racemic secondary alkyl halides (>60 examples) by copper catalysis under mild thermal conditions. The reaction efficiently provides highly enantioenriched N-alkyl sulfoximines (up to 99% yield and >99% ee) featuring secondary benzyl, propargyl, α-carbonyl alkyl, and α-cyano alkyl stereocenters. In addition, we have converted the masked α-chiral primary amines thus obtained to various synthetic building blocks, ligands, and drugs possessing α-chiral N-functionalities, such as carbamate, carboxylamide, secondary and tertiary amine, and oxazoline, with commonly seen α-substitution patterns. These results shine light on the potential of enantioconvergent radical cross-coupling as a general chiral carbon-heteroatom formation strategy.

Copper(I)-Catalyzed Asymmetric Reactions Involving Radicals.

Asymmetric functionalization of alkyl radicals represents a robust yet underdeveloped method for efficient construction and decoration of carbon skeletons in chiral organic molecules. In this field, we have been inspired by the excellent redox, alkyl radical trapping, and Lewis acidic properties of copper to develop several catalytic modes for asymmetric reactions involving alkyl radicals. At the beginning, we discovered tandem radical hydrotrifluoromethylation of unactivated alkenes and enantioselective alkoxylation of remote C(sp3)-H bonds by copper/chiral phosphate relay catalysis. This success has stimulated us to develop an asymmetric three-component 1,2-dicarbofunctionalization of 1,1-diarylalkenes using a similar strategy via radical intermediates. Meanwhile, we also discovered a copper/chiral secondary amine cooperative catalyst for asymmetric radical intramolecular cyclopropanation of alkenes using α-aldehyde methylene groups as C1 sources. The trapping of alkyl radical intermediates by CuII species during the reaction was essential for the chemoselectivity toward cyclopropanation. Encouraged by the efficient enantiocontrol with chiral phosphate and the effective trapping of alkyl radicals with CuII species, we then sought to develop copper/chiral phosphate as a single-electron-transfer catalyst for asymmetric reactions involving alkyl radicals. Subsequently, we successfully achieved a series of highly enantioselective 1,2-aminofluoroalkylation, -aminoarylation, -diamination, -aminosilylation, and -oxytrifluoromethylation of unactivated alkenes. The key for high enantioinduction was believed to be the effective trapping of alkyl radicals by CuII/chiral phosphate complexes. Besides, an achiral pyridine ligand was found to be indispensable for achieving high enantioselectivity, presumably via stabilization of CuIII species in the 1,2-alkoxytrifluoromethylation reaction. This discovery reminded us of tuning the redox properties and chemoreactivity of copper centers with an ancillary ligand. As a result, we subsequently identified cinchona alkaloid-derived sulfonamides as novel neutral-anionic hybrid ligands for simultaneous chemo- and enantiocontrol. We thus accomplished highly enantioselective 1,2-iminoxytrifluoromethylation of unactivated alkenes under the catalysis of copper/cinchona alkaloid-derived sulfonamide ligand, affording trifluoromethylated isoxazolines in high enantiomeric excess. Our copper-catalyzed asymmetric reactions with alkyl radicals provide expedient access to a diverse range of valuable chiral molecules with broad application potential in areas of organic synthesis, medicine, agrochemical, and material sciences.

A New Concept for Central Wedge Resection in Labiaplasty.

OBJECTIVE: The aim of the study was to develop a new concept for central wedge resection to improve surgical results. Currently, the most common postoperative complications of the regular central wedge (RV) resection technique are wound dehiscence and scar contracture. METHODS: A case-control study was applied to randomly divide 119 patients with labia minora hypertrophy deformities into 2 groups: new central wedge (NV) (n = 57) and RV (n = 62). All patients underwent the corresponding corrective surgery to repair the deformity. During the NV procedure, we changed the direction of the scalpel to form 2 inclined sections and sutured these sections together to achieve nonparallel closure lines. The patients in the 2 groups were followed up at 1 and 6 months postoperatively. We described the details of this method and evaluated the treatment outcomes of the 2 groups. RESULTS: Patient age, labia minora width, and procedure time were not significantly different between the 2 groups (p > 0.05). However, the visual analog scale (VAS) scores in the 2 groups were significantly different (p < 0.05). Two patients in the NV group were somewhat dissatisfied because of lymphoedema and asymmetry; 6 patients in the RV group expressed dissatisfaction with scarring, healing complications, and asymmetry. A minor corrective operation was performed for asymmetry, and the dehiscence healed spontaneously. The patient with edema is still being followed up. CONCLUSION: The surgical method we introduced was indicated to be a simple and effective procedure that avoided wound dehiscence and scar contracture, which are common with the regular approach.