Perspectives of Mental Health Nurses About Sexual Safety in Acute Inpatient Mental Health Units.

The overall aim of this study is to explore the views of mental health nurses (MHNs) about the sexual safety of consumers receiving care in acute inpatient units. In Australia, people accessing mental health inpatient units have reported feeling unsafe while receiving care including experiences of sexual harassment and abuse from other patients. There has been no study to date that has explored the views of the MHNs providing care.

Total Synthesis of Lissodendoric Acid A.

We describe a full account of our synthetic strategy leading to the first total synthesis of the manzamine alkaloid lissodendoric acid A . These efforts demonstrate that strained cyclic allenes are valuable synthetic building blocks and can be employed efficiently in total synthesis.

Total synthesis of lissodendoric acid A via stereospecific trapping of a strained cyclic allene.

Small rings that contain allenes are unconventional transient compounds that have been known since the 1960s. Despite being discovered around the same time as benzyne and offering a number of synthetically advantageous features, strained cyclic allenes have seen relatively little use in chemical synthesis. We report a concise total synthesis of the manzamine alkaloid lissodendoric acid A, which hinges on the development of a regioselective, diastereoselective, and stereospecific trapping of a fleeting cyclic allene intermediate.

Enantioselective Construction of Quaternary Stereogenic Centers by the Addition of an Acyl Anion Equivalent to 1,3-Dienes.

We report the enantioselective formation of quaternary stereogenic centers by the intermolecular addition of malononitrile, an acyl anion equivalent, and related pronucleophiles to several 1,3-disubstituted acyclic 1,3-dienes in the presence of a Pd-PHOX catalyst. Products are obtained in up to 88% yield and 99:1 er and in most cases are formed as a single regioisomer. The products' malononitrile unit undergoes oxidative functionalization to afford β,γ-unsaturated carbonyls bearing internal olefins and α-quaternary stereogenic centers.

Brønsted acid and Pd-PHOX dual-catalysed enantioselective addition of activated C-pronucleophiles to internal dienes.

We describe the development of Pd-PHOX-catalysed enantioselective couplings of internal dienes with malononitrile and other activated C-pronucleophiles. Reactions are dramatically accelerated by the addition of EtN·HBAr as a Brønsted acid co-catalyst, enabling a suite of products bearing a variety of alkyl substituents at the stereogenic carbon to be prepared. A series of mechanism-oriented experiments reveal key aspects of the catalytic cycle and the importance of the non-coordinating BAr counterion in not only promoting reactions of internal dienes but also additions of previously unreactive nucleophiles towards terminal dienes.

Preparation of Chiral Allenes through Pd-Catalyzed Intermolecular Hydroamination of Conjugated Enynes: Enantioselective Synthesis Enabled by Catalyst Design.

In this study, we establish that conjugated enynes undergo selective 1,4-hydroamination under Pd catalysis to deliver chiral allenes with pendant allylic amines. Several primary and secondary aliphatic and aryl-substituted amines couple with a wide range of mono- and disubstituted enynes in a nonenantioselective reaction where DPEphos serves as the ligand for Pd. Benzophenone imine acts as an ammonia surrogate to afford primary amines in a two-step/one-pot process.

Enantioselective Intermolecular Pd-Catalyzed Hydroalkylation of Acyclic 1,3-Dienes with Activated Pronucleophiles.

We report a highly enantioselective Pd-PHOX-catalyzed intermolecular hydroalkylation of acyclic 1,3-dienes. Meldrum's acid derivatives and other activated C-pronucleophiles, such as β-diketones and malononitriles, react with a variety of aryl- and alkyl-substituted dienes in ≤20 h at room temperature. The coupled products, obtained in up to 96% yield and 97.

Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst.

We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.