Hydroselenation of olefins: elucidating the β-selenium effect.

We report a light-promoted hydroselenation of alkenes with high -Markovnikov selectivity. Blue light activates an aryl diselenide to generate a seleno radical with subsequent addition into an alkene to form a β-seleno carbon radical. Hydrogen atom transfer (HAT) from the selenol to the carbon radical generates the linear selenide with high selectivity in preference to the branched isomer.

A General and Scalable Method toward Enantioenriched C2-Substituted Azetidines Using Chiral -Butanesulfinamides.

Diverse ranges of chiral nitrogen-containing heterocycles serve as a molecular toolbox for modulating a wide array of biological processes, but enantioenriched production of smaller chiral heterocycles is a bottleneck. There is a lack of general approaches for the stereoselective preparation of chiral 4-membered monocyclic C2-substituted azetidines, where many routes to different substitution types are possible, but no simple and common approach exists. To bridge this gap, inexpensive and widely available chiral -butanesulfinamides are harnessed for chiral induction with 1,3-bis-electrophilic 3-chloropropanal, providing a three-step approach to C2-substituted azetidines with aryl, vinyl, allyl, branched alkyl, and linear alkyl substituents.

Reverse Intersystem Crossing Dynamics in Vibronically Modulated Inverted Singlet-Triplet Gap System: A Wigner Phase Space Study.

We inspect the origin of the inverted singlet-triplet gap (INVEST) and slow change in the reverse intersystem crossing (rISC) rate with temperature, as recently observed. A Wigner phase space study reveals that, though INVEST is found at equilibrium geometry, variation in the exchange interaction and the doubles-excitation for other geometries in the harmonic region leads to non-INVEST behavior. This highlights the importance of nuclear degrees of freedom for the INVEST phenomenon, and in this case, geometric puckering of the studied molecule determines INVEST and the associated rISC dynamics.

Accidental triplet harvesting in donor-acceptor dyads with low spin-orbit coupling.

We present an accidental mechanism for efficient intersystem crossing (ISC) between singlet and triplet states with low spin-orbit coupling (SOC) in molecules having donor-acceptor (D-A) moieties separated by a Sigma bond. Our study shows that SOC between the lowest singlet excited state and the higher-lying triplet states, together with nuclear motion-driven coupling of this triplet state with lower-lying triplet states during the free rotation about a Sigma bond, is one of the possible ways to achieve the experimentally observed ISC rate for a class of D-A type photoredox catalysts. This mechanism is found to be the dominant contributor to the ISC process with the corresponding rate reaching a maximum at a dihedral angle in the range of 72°-78° between the D-A moieties of 10-(naphthalen-1-yl)-3,7-diphenyl-10-phenoxazine and other molecules included in the study.

Can the absolute configuration of cyclic peptides be determined with vibrational circular dichroism?

Cyclic peptides show a wide range of biological activities, among others as antibacterial agents. These peptides are often large and flexible with multiple chiral centers. The determination of the stereochemistry of molecules with multiple chiral centers is a challenging and important task in drug development.