Palladium-Catalyzed Addition of Aryl Halides to N-Sulfinylamines for the Synthesis of Sulfinamides.

Sulfinamides are versatile, synthetically useful intermediates, and final motifs. Traditional methods to synthesize sulfinamides generally require substrates with preinstalled sulfur centers. However, these precursors have limited commercial availability, and the associated synthetic routes often require harsh reaction conditions and highly reactive reagents, thus severely limiting their application. Herein, we report the synthesis of sulfinamides from aryl and alkenyl (pseudo)halides and N-sulfinylamines, enabled by palladium catalysis. The reactions use mild conditions and are achieved without the use of highly reactive preformed organometallic reagents, resulting in transformations of broad generality and high functional group tolerance. In particular, substrates featuring protic and electrophilic functional groups can be used successfully. The modification of complex aryl cores and natural product derivatives demonstrates the utility of this method.

The Role of Decision-Making Capacity in Gathering Collateral Information.

AbstractPsychiatric disorders usually do not have characteristic physical exam findings, imaging, or lab values. Psychiatrists therefore diagnose and treat patients largely based on reported or observed behavior, which makes collateral information from a patient's close contacts especially pertinent to an accurate diagnosis. The American Psychiatric Association considers communication with patients' supports a best practice when the patient provides informed consent or does not object to the communication. However, situations arise in which a patient's objection to such communication is the product of impaired decision-making and the benefits of obtaining collateral information represent best practice. In this article a framework for addressing these situations is proposed using a full decisional capacity evaluation, followed by an alternate decision-making process by concurrence from a second physician. It is recommended that a patient's refusal to allow the gathering of collateral information should be addressed exactly like refusals for other diagnostic or treatment interventions.

The Fluorination of C-H Bonds: Developments and Perspectives.

This Review summarizes advances in fluorination by C(sp2 )-H and C(sp3 )-H activation. Transition-metal-catalyzed approaches championed by palladium have allowed the installation of a fluorine substituent at C(sp2 ) and C(sp3 ) sites, exploiting the reactivity of high-oxidation-state transition-metal fluoride complexes combined with the use of directing groups (some transient) to control site and stereoselectivity. The large majority of known methods employ electrophilic fluorination reagents, but methods combining a nucleophilic fluoride source with an oxidant have appeared. External ligands have proven to be effective for C(sp3 )-H fluorination directed by weakly coordinating auxiliaries, thereby enabling control over reactivity. Methods relying on the formation of radical intermediates are complementary to transition-metal-catalyzed processes as they allow for undirected C(sp3 )-H fluorination. To date, radical C-H fluorinations mainly employ electrophilic N-F fluorination reagents but a unique MnIII -catalyzed oxidative C-H fluorination using fluoride has been developed. Overall, the field of late-stage nucleophilic C-H fluorination has progressed much more slowly, a state of play explaining why C-H 18 F-fluorination is still in its infancy.

Diverse saturated heterocycles from a hydroacylation/conjugate addition cascade.

Rhodium-catalyzed hydroacylation using alkynes substituted with pendant nucleophiles, delivers linear α,ß-unsaturated enone intermediates with excellent regioselectivity. These adducts are used to construct a broad range of diversely substituted, saturated O-, N- and S-heterocycles in a one-pot process. Judicious choice of cyclisation conditions enabled isolation of O-heterocycles with high levels of diastereoselectivity. A variety of derivatisation reactions are also performed, generating functionalised hydroacylation products. This sequence serves as a general approach for the synthesis of fully saturated heterocycles.

Navigating Care From Afar: Ethical Considerations for Police Welfare Checks.

The clinical practice of contacting law enforcement to perform safety welfare checks for persons who have missed psychiatry appointments is commonly regarded as benign. However, in nonemergency situations, these interventions may carry greater risk than is usually assumed, especially if the person whose welfare is being checked belongs to a racial-ethnic minority group, and there is little evidence on the safety and effectiveness of these interventions. This Open Forum presents a case analysis to examine the central ethical considerations for these situations. Using crisis intervention teams, making repeated phone calls, or using other methods of communication may be clinically and ethically preferable to contacting law enforcement.

Azine-N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation.

Heterocycle-derived aldehydes are challenging substrates in metal-catalysed hydroacylation chemistry. We show that by using azine N-oxide substituted aldehydes, good reactivity can be achieved, and that they are highly effective substrates for the intermolecular hydroacylation of alkynes. Employing a Rh(i)-catalyst, we achieve a mild and scalable aldehyde C-H activation, that permits the coupling with unactivated terminal alkynes, in good yields and with high regioselectivities (up to >20 : 1 l:b). Both substrates can tolerate a broad variety of functional groups. The reaction can also be applied to diazine aldehydes that contain a free N-lone pair. We demonstrate conversion of the hydroacylation products to the corresponding azine, through a one-pot hydroacylation/deoxygenation sequence. A one-pot hydroacylation/cyclisation, using N-Boc propargylamine, additionally leads to the synthesis of a bidentate pyrrolyl ligand.

Gun Violence, Mental Illness, And Laws That Prohibit Gun Possession: Evidence From Two Florida Counties.

Gun violence kills about ninety people every day in the United States, a toll measured in wasted and ruined lives and with an annual economic price tag exceeding $200 billion. Some policy makers suggest that reforming mental health care systems and improving point-of-purchase background checks to keep guns from mentally disturbed people will address the problem. Epidemiological research shows that serious mental illness contributes little to the risk of interpersonal violence but is a strong factor in suicide, which accounts for most firearm fatalities. Meanwhile, the effectiveness of gun restrictions focused on mental illness remains poorly understood. This article examines gun-related suicide and violent crime in people with serious mental illnesses, and whether legal restrictions on firearm sales to people with a history of mental health adjudication are effective in preventing gun violence. Among the study population in two large Florida counties, we found that 62 percent of violent gun crime arrests and 28 percent of gun suicides involved individuals not legally permitted to have a gun at the time. Suggested policy reforms include enacting risk-based gun removal laws and prohibiting guns from people involuntarily detained in short-term psychiatric hospitalizations.