Enantioselective Syntheses of Yohimbine Alkaloids: Proving Grounds for New Catalytic Transformations

The total synthesis of bioactive alkaloids is an enduring challenge and an indication of the state of the art of chemical synthesis. With the explosion of catalytic asymmetric methods over the past three decades, these compelling targets have been fertile proving grounds for enantioselective bond forming transformations. We summarize these activities herein both to highlight the power and versatility of these methods and to instill future inspiration for new syntheses of these privileged natural products.

A Facile Synthesis of 2-Aminobenzoxazines Based on Iodine­Catalyzed Desulfurative Cyclization

A facile and environmentally benign access to N-aryl/alkyl-4H-benzoxazin-2-amines is achieved from 1-[2-(hydroxymethyl)phenyl/alkyl]-3-phenylthioureas under transition-metal-free conditions. The conversions occur smoothly in the presence of a catalytic amount of molecular iodine and hydrogen peroxide as the oxidant in tetrahydrofuran at room temperature to afford moderate to good yields (28–90%) of the desired products within 2 hours. This method reports the first examples of the catalytic transformations of 1-[2-(hydroxymethyl)phenyl/alkyl]-3-phenylthioureas into N-aryl/alkyl-4H-benzoxazin-2-amines based on desulfurative cyclization.

Catalytic transformations with finite-size environments: applications to cooling and thermometry

The laws of thermodynamics are usually formulated under the assumption of infinitely large environments. While this idealization facilitates theoretical treatments, real physical systems are always finite and their interaction range is limited. These constraints have consequences for important tasks such as cooling, not directly captured by the second law of thermodynamics. Here, we study catalytic transformations that cannot be achieved when a system exclusively interacts with a finite environment. Our core result consists of constructive conditions for these transformations, which include the corresponding global unitary operation and the explicit states of all the systems involved. From this result we present various findings regarding the use of catalysts for cooling. First, we show that catalytic cooling is always possible if the dimension of the catalyst is sufficiently large. In particular, the cooling of a qubit using a hot qubit can be maximized with a catalyst as small as a three-level system. We also identify catalytic enhancements for tasks whose implementation is possible without a catalyst. For example, we find that in a multiqubit setup catalytic cooling based on a three-body interaction outperforms standard (non-catalytic) cooling using higher order interactions. Another advantage is illustrated in a thermometry scenario, where a qubit is employed to probe the temperature of the environment. In this case, we show that a catalyst allows to surpass the optimal temperature estimation attained only with the probe.