Kyphoplasty of C2 Pathological Fractures Using an Anterior Midline Approach and Steerable Osteotome: Technical Note and Case Series.

Background: Malignant lesions involving the C2 vertebral body (axis) may be challenging to treat, and not all patients with cancer are good candidates for posterior cervical or occipitocervical instrumentation.

Objective: To describe a modified technique of the direct anterolateral C2 kyphoplasty using a steerable osteotome, commonly used for the treatment of thoracolumbar spinal lesions. We also report a case series of 11 patients treated with this technique at our institution.

Case report: bilateral tunneled epidural catheters to prevent unilateral analgesia for cancer-related pain.

Objective: Unilateral analgesia often occurs with epidural analgesia. Traditional methods of troubleshooting this problem can be insufficient in obtaining adequate pain relief in a timely manner for terminal cancer patients. This case report demonstrates a safe and effective solution which can be utilized in these circumstances.

Intrathecal Injection of Gadobutrol: A Tale of Caution.

In the field of interventional pain medicine a radiocontrast agent is commonly used in conjunction with fluoroscopy. Limited work has been published regarding the use of gadolium based contrast agents (GBCA) in the intrathecal space. We report a case of an intrathecal gadobutrol injection resulting in neurotoxic manifestations.

Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation.

Pd-catalyzed enantioselective alkylation in conjunction with further synthetic elaboration enables the formal total syntheses of a number of "classic" natural product target molecules. This publication highlights recent methods for setting quaternary and tetrasubstituted tertiary carbon stereocenters to address the synthetic hurdles encountered over many decades across multiple compound classes spanning carbohydrate derivatives, terpenes, and alkaloids. These enantioselective methods will impact both academic and industrial settings, where the synthesis of stereogenic quaternary carbons is a continuing challenge.

Palladium-catalyzed decarboxylative allylic alkylation of diastereomeric β-ketoesters.

The palladium-catalyzed decarboxylative allylic alkylation of diastereomeric β-ketoesters derived from 4--butylcyclohexanone is described. These experiments were performed to elucidate our understanding of stereoablative enantioconvergent catalysis. A detailed analysis of the product distribution, including stereochemical outcome of the products, is included.

Development of (trimethylsilyl)ethyl ester protected enolates and applications in palladium-catalyzed enantioselective allylic alkylation: intermolecular cross-coupling of functionalized electrophiles.

The development of (trimethylsilyl)ethyl ester protected enolates is reported. The application of this class of compounds in palladium-catalyzed asymmetric allylic alkylation is explored, yielding a variety of α-quaternary six- and seven-membered ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to traditional β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of (trimethylsilyl)ethyl β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.

Enantio-, diastereo-, and regioselective iridium-catalyzed asymmetric allylic alkylation of acyclic β-ketoesters.

The first regio-, diastereo-, and enantioselective allylic alkylation of acyclic β-ketoesters to form vicinal tertiary and all-carbon quaternary stereocenters is reported. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands. Broad functional group tolerance is observed at the keto-, ester-, and α-positions of the nucleophile.

Construction of vicinal tertiary and all-carbon quaternary stereocenters via Ir-catalyzed regio-, diastereo-, and enantioselective allylic alkylation and applications in sequential Pd catalysis.

Highly congested vicinal stereocenters comprised of tertiary and all-carbon quaternary centers were generated via Ir-catalyzed asymmetric allylic alkylation of β-ketoesters. These catalytic reactions proceed in excellent yields with a broad scope on either reaction partner and with outstanding regio-, diastereo-, and enantiocontrol. Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated products with pinpoint stereochemical control of both chiral centers.

Enantioselective construction of α-quaternary cyclobutanones by catalytic asymmetric allylic alkylation.

The first transition metal-catalyzed enantioselective α-alkylation of cyclobutanones is reported. This method employs palladium catalysis and an electron deficient PHOX type ligand to afford all–carbon α-quaternary cyclobutanones in good to excellent yields and enantioselectivities.