Direct Stereodivergent Olefination of Carbonyl Compounds with Sulfur Ylides.

The reactivity of phosphorus and sulfur ylides toward carbonyl compounds constitutes a well-known dichotomy that is a common educational device in organic chemistry─the former gives olefins, while the latter gives epoxides. Herein, we report a stereodivergent carbonyl olefination that challenges this dichotomy, showcasing thiouronium ylides as valuable olefination reagents. With this method, aldehydes are converted to Z-alkenes with high stereoselectivity and broad substrate scope, while N-tosylimines provide a similarly proficient entry to E-alkenes. In-depth computational and experimental studies clarified the mechanistic details of this unusual reactivity.

As Similar As Possible, As Different As Necessary - On-Site Laboratory Teaching during the COVID-19 Pandemic.

Most of the available information on studying under the challenging conditions brought about by the COVID-19 pandemic emphasizes a variety of aspects on how to digitalize the whole teaching process. Thus, several useful and potentially game-changing strategies have been reported recently. In contrast to the digitalization of teaching, in this article, we focus on the reverse process: transitioning back to offline teaching, which is unavoidable especially for the acquisition of practical skills during chemistry studies. In this work, we describe our own experience acquired during the Organic Chemistry practical course at the University of Vienna, which was held in June 2020 and onwards. The article contains descriptions of precautions and measures that were taken, additional materials, and necessary changes made in order to safely continue on-site course teaching. We anticipate that this set of precautions can be used in an adapted fashion for any type of laboratory course. Further, we offer a critical analysis of students' and instructors' opinions concerning the changes and well-being during the course. Those opinions were collected via a detailed survey. From our experience, with careful planning and responsible behavior, a return to on-site education is possible and warmly welcomed by all involved participants. The detailed description of our course may also be useful for those who need to start a new organic laboratory course or want to improve an existing one.

Enantioselective Redox-Neutral Coupling of Aldehydes and Alkenes by an Iron-Catalyzed "Catch-Release" Tethering Approach.

The reductive coupling of aldehydes and alkenes is an emerging technology that holds the potential to reinvent carbonyl addition chemistry. However, existing enantioselective methods are limited to form "branched" products. Herein, we present a directed enantio- and diastereoselective alkylation of aldehydes with simple olefins to selectively yield linear coupling products. This is achieved by redox-neutral remote functionalization, whereby a tethering "catch-release" strategy decisively solves the key problems of reactivity and selectivity.

Diastereo- and Enantioselective Access to Stereotriads through a Flexible Coupling of Substituted Aldehydes and Alkenes.

A flexible redox-neutral coupling of aldehydes and alkenes enables rapid access to stereotriads starting from a single stereocenter with perfect levels of enantio- and diastereoselectivity under mild conditions. The versatility of the method is highlighted by the installation of heteroatoms along the tether, which enables a route to structurally diverse building blocks. The formal synthesis of (+)-neopeltolide further demonstrates the synthetic utility of this approach.

A Gold(I)-Catalyzed Domino Coupling of Alcohols with Allenes Enables the Synthesis of Highly Substituted Indenes.

The reaction of aryl-substituted allenes with alcohols under gold catalysis led to highly substituted indenes in good yields, with low catalyst loading and under mild conditions. During this domino transformation, two C-C bonds are formed with water as the only byproduct.