In-Cage Recombination Facilitates the Enantioselective Organocatalytic [1,2]-Rearrangement of Allylic Ammonium Ylides.

The [1,2]-rearrangement of allylic ammonium ylides is traditionally observed as a competitive minor pathway alongside the thermally allowed [2,3]-sigmatropic rearrangement. Concerted [1,2]-rearrangements are formally forbidden, with these processes believed to proceed through homolytic C-N bond fission of the ylide, followed by radical-radical recombination. The challenges associated with developing a catalytic enantioselective [1,2]-rearrangement of allylic ammonium ylides therefore lie in biasing the reaction pathway to favor the [1,2]-reaction product, alongside controlling a stereoselective radical-radical recombination event.

Implementation of a penicillin allergy protocol in open abdominal wall reconstruction: Preoperative optimization program.

Introduction: Beta-lactam prophylaxis is the first-line preoperative antibiotic in open abdominal wall reconstruction. However, of the 11% patients reporting a penicillin allergy (PA), most receive second-line, non-β-lactam prophylaxis. Previously, abdominal wall reconstruction research from our institution demonstrated increased wound complications, readmissions, and reoperations with non-β-lactam prophylaxis.

One-Pot Access to Functionalised Malamides via Organocatalytic Enantioselective Formation of Spirocyclic β-Lactone-Oxindoles and Double Ring-Opening.

Malamides (diamide derivatives of malic acid) are prevalent in nature and of significant biological interest, yet only limited synthetic methods to access functionalised enantiopure derivatives have been established to date. Herein, an effective synthetic method to generate this molecular class is developed through in situ formation of spirocyclic β-lactone-oxindoles (employing a known enantioselective isothiourea-catalysed formal [2+2] cycloaddition of C(1)-ammonium enolates and isatin derivatives) followed by a subsequent dual ring-opening protocol (of the β-lactone and oxindole) with amine nucleophiles. The application of this protocol is demonstrated across twelve examples to give densely functionalised malamide derivatives with high enantio- and diastereo-selectivity (up to >95:5 dr and >99:1 er).

De-epimerizing DyKAT of β-lactones generated by isothiourea-catalysed enantioselective [2 + 2] cycloaddition.

An enantioselective isothiourea-catalysed [2 + 2] cycloaddition of C(1)-ammonium enolates with pyrazol-4,5-diones is used to construct spirocyclic β-lactones in good yields, excellent enantioselectivity (99 : 1 er) but with modest diastereocontrol (typically 70 : 30 dr). Upon ring-opening with morpholine or alternative nucleophilic amines and alcohols β-hydroxyamide and β-hydroxyester products are generated with enhanced diastereocontrol (up to >95 : 5 dr). Control experiments show that stereoconvergence is observed in the ring-opening of diastereoisomeric β-lactones, leading to a single product (>95 : 5 dr, >99 : 1 er).

Enantioselective Synthesis in Continuous Flow: Polymer-Supported Isothiourea-Catalyzed Enantioselective Michael Addition-Cyclization with α-Azol-2-ylacetophenones.

A packed reactor bed incorporating a polymer-supported isothiourea HyperBTM catalyst derivative has been used to promote the enantioselective synthesis of a range of heterocyclic products derived from α-azol-2-ylacetophenones and -acetamides combined with alkyl, aryl, and heterocyclic α,β-unsaturated homoanhydrides in continuous flow via an α,β-unsaturated acyl-ammonium intermediate. The products are generated in good to excellent yields and generally in excellent enantiopurity (up to 97:3 er). Scale-up is demonstrated on a 15 mmol scale, giving the heterocyclic product in 68% overall yield with 98:2 er after recrystallization.

Synthesis of Tetra-Substituted 3-Hydroxyphthalide Esters by Isothiourea-Catalysed Acylative Dynamic Kinetic Resolution.

A general and highly enantioselective method for the preparation of tetra-substituted 3-hydroxyphthalide esters via isothiourea-catalysed acylative dynamic kinetic resolution (DKR) is reported. Using (2S,3R)-HyperBTM (5 mol %) as the catalyst, the scope and limitations of this methodology have been extensively probed, with high enantioselectivity and good to excellent yields observed (>40 examples, up to 99 %, 99 : 1 er). Substitution of the aromatic core within the 3-hydroxyphthalide skeleton, as well as aliphatic and aromatic substitution at C(3), is readily tolerated.

Isothiourea-Catalysed Acylative Dynamic Kinetic Resolution of Tetra-substituted Morpholinone and Benzoxazinone Lactols.

The development of methods to allow the selective acylative dynamic kinetic resolution (DKR) of tetra-substituted lactols is a recognised synthetic challenge. In this manuscript, a highly enantioselective isothiourea-catalysed acylative DKR of tetra-substituted morpholinone and benzoxazinone-derived lactols is reported. The scope and limitations of this methodology have been developed, with high enantioselectivity and good to excellent yields (up to 89 %, 99 : 1 er) observed across a broad range of substrate derivatives incorporating substitution at N(4) and C(2), di- and spirocyclic substitution at C(5) and C(6), as well as benzannulation (>35 examples in total).

Managing incisional wounds with Prevena VAC therapy in lower-extremity vascular surgery: A comparative study.

Background: Vascular surgical site infections have been reported with an overall incidence of 5-10% for patients undergoing arterial interventions and as high as 10-20% for lower-limb bypass grafting procedures. Given that vascular surgery patients are known to be at a higher risk of postoperative wound infections and other complications, our objective was to evaluate a potential method to reduce such complications. This study compares the rate of wound healing complications between incisional negative pressure wound therapy (NPWT) and conventional dressings in vascular surgery patients with infra-inguinal incisions.

Understanding divergent substrate stereoselectivity in the isothiourea-catalysed conjugate addition of cyclic α-substituted β-ketoesters to α,β-unsaturated aryl esters.

The development of enantioselective synthetic methods capable of generating vicinal stereogenic centres, where one is tetrasubstituted (such as either an all-carbon quaternary centre or where one or more substituents are heteroatoms), is a recognised synthetic challenge. Herein, the enantioselective conjugate addition of a range of carbo- and heterocyclic α-substituted β-ketoesters to α,β-unsaturated aryl esters using the isothiourea HyperBTM as a Lewis base catalyst is demonstrated. Notably, divergent diastereoselectivity is observed through the use of either cyclopentanone-derived or indanone-derived substituted β-ketoesters with both generating the desired stereodefined products with high selectivity (>95 : 5 dr, up to 99 : 1 er).

α-Functionalisation of Cyclic Sulfides Enabled by Lithiation Trapping.

A general and straightforward procedure for the lithiation trapping of cyclic sulfides such as tetrahydrothiophene, tetrahydrothiopyran and a thiomorpholine is described. Trapping with a wide range of electrophiles is demonstrated, leading to more than 50 diverse α-substituted saturated sulfur heterocycles. The methodology provides access to a range of α-substituted cyclic sulfides that are not easily synthesised by the currently available methods.

Disparate potential for readmission prevention exists among inpatient and outpatient procedures in a minimally invasive surgery practice.

Background: Administrators have focused on decreasing postoperative readmissions for cost reduction without fully understanding their preventability. This study describes the development and implementation of a surgeon-led readmission review process that assessed preventability.

Methods: A gastrointestinal surgical group at a tertiary referral hospital developed and implemented a template to analyze inpatient and outpatient readmissions.

Poor synchronization yet adequate tempo-keeping in adults with autism.

Sensorimotor synchronization to external events is fundamental to social interactions. Adults with autism spectrum condition (ASC) have difficulty with synchronization, manifested in both social and non-social situations, such as paced finger-tapping tasks, where participants synchronize their taps to metronome beats. What limits ASC's synchronization is a matter of debate, especially whether it stems from reduced online correction of synchronization error (the "slow update" account) or from noisy internal representations (the "elevated internal noise" account).

Barriers to the Initiation of Telecommunicator-CPR during 9-1-1 Out-of-Hospital Cardiac Arrest Calls: A Qualitative Study.

Introduction: Fewer than 10% of individuals who suffer out-of-hospital cardiac arrest (OHCA) survive with good neurologic function. Bystander CPR more than doubles the chance of survival, and telecommunicator-CPR (T-CPR) during a 9-1-1 call substantially improves the frequency of bystander CPR.

Objective: We examined the barriers to initiation of T-CPR.

Isothiourea-Catalyzed [2 + 2] Cycloaddition of C(1)-Ammonium Enolates and -Alkyl Isatins.

Enantioselective [2 + 2] cycloaddition of C(1)-ammonium enolates generated catalytically using the isothiourea HyperBTM with -alkyl isatins gives spirocyclic β-lactones. ring opening with an amine nucleophile generates isolable highly enantioenriched products in up to 92:8 dr and in >99:1 er.

A resident robotic curriculum utilizing self-selection and a web-based feedback tool.

To describe an obstetrics and gynecology residency robotic curriculum, facilitated by a web-based feedback and case-tracking tool, allowing for self-selection into advanced training. Phase I (Basic) was required for all residents and included online training modules, online assessment, and robotic bedside assistant dry lab. Phase II (Advanced) was elective console training.

A core outcome set for damage control laparotomy via modified Delphi method.

Objectives: Damage control laparotomy (DCL) remains an important tool in the trauma surgeon's armamentarium. Inconsistency in reporting standards have hindered careful scrutiny of DCL outcomes. We sought to develop a core outcome set (COS) for DCL clinical studies to facilitate future pooling of data via meta-analysis and Bayesian statistics while minimizing reporting bias.

Unseen Burden of Injury: Post-Hospitalization Mortality in Geriatric Trauma Patients.

Background/objectives: Older adults are at risk for adverse outcomes after trauma, but little is known about post-acute survival as state and national trauma registries collect only inpatient or 30-day outcomes. This study investigates long-term, out-of-hospital mortality in geriatric trauma patients.

Methods: Level I Trauma Center registry data were matched to the US Social Security Death Index (SSDI) to determine long-term and out-of-hospital outcomes of older patients.

Complicated Diverticular Disease.

The modern management of colonic diverticular disease involves grouping patients into uncomplicated or complicated diverticulitis, after which the correct treatment paradigm is instituted. Recent controversies suggest overlap in management strategies between these two groups. While most reports still support surgical intervention for the treatment of complicated diverticular disease, more data are forthcoming suggesting complicated diverticulitis does not merit surgical resection in all scenarios.

Bridging the Communication Gap: A Quality Improvement Project of a Ventricular Assist Device Program.

Background: As of December 31, 2016, in the United States, 22 866 patients received left ventricular assist devices (LVADs) (J Heart Lung Transplant. 2017;36(10):1080-1086). First responders are generally unfamiliar with LVAD equipment functionality (J Heart Lung Transplant.

Twelve years of component separation technique in abdominal wall reconstruction.

Background: Component separation technique involves incision of abdominal muscle and its aponeurosis, which generates a myofascial advancement flap to assist with fascial closure in abdominal wall reconstructions. This tissue mobilization allows for musculo-fascial approximation of much larger abdominal wall defects than would otherwise be possible. With extensive tissue mobilization, however, there is concern for significant wound and systemic complications.

Outcomes of open abdomen versus primary closure following emergent laparotomy for suspected secondary peritonitis: A propensity-matched analysis.

Background: Optimal management following index laparotomy is poorly defined in secondary peritonitis patients. Although "open abdomen" (OA), or temporary abdominal closure with planned relaparotomy, is used to reassess bowel viability or severity of contamination, recent studies demonstrate comparable morbidity and mortality with primary abdominal closure (PC). This study evaluates differences between OA and PC following emergent laparotomy.

Trauma Recidivism and Mortality Following Violent Injuries in Young Adults.

Background: Trauma recidivism accounts for approximately 44% of emergency department admissions and remains a significant health burden with this patient cohort carrying higher rates of morbidity and mortality.

Methods: A level 1 trauma center registry was queried for patients aged 18-25 y presented between 2009 and 2015. Patients with nonaccidental gunshot wounds, stab wounds, or blunt assault-related injuries were categorized as violent injuries.

Diagnosis and Management of Parastomal Hernias.

A 63-year-old woman with history of stage II rectal adenocarcinoma status postneoadjuvant chemoradiation and subsequent abdominoperineal resection presented with worsening bulge and inability to pouch stoma. CT scan revealed a 4-cm parastomal hernia. After discussion with the patient regarding management options, she elected to undergo repair of hernia defect.

MELD-Na score associated with postoperative complications in hernia repair in non-cirrhotic patients.

Purpose: In patients with cirrhosis, the Model for End-Stage Liver Disease Sodium (MELD-Na) score is a validated predictor of outcomes after transplant and non-transplant surgical procedures. This study investigates the association of MELD-Na score with complications following elective ventral hernia repair in non-cirrhotic patients.

Methods: The ACS NSQIP database was queried (2005-2016) for all elective laparoscopic and open ventral hernia procedures in patients without ascites or esophageal varices.