Alkylthianthrenium salts can be shaken up in a ball mill on a decagram scale

We describe an operationally simple, good-yielding, two-step cascade process to convert biscyclopropanes 1 into high-value benzocyclobutene building blocks 3. This study highlights the novel reactivit...

A facile approach to obtaining densely functionalized cyclopropanes is described. The reaction proceeds under mild conditions via the directed nucleopalladation of nonconjugated alkenes with readily a...

The stereoselective activation of alkanes constitutes a long-standing and grand challenge for chemistry. Although metal-containing enzymes oxidize alkanes with remarkable ease and selectivity, chemica...

General methods for the synthesis of chiral difluoromethyl cyclopropanes are challenging to develop, despite the increasing importance of this motif in pharmaceuticals. Now, a copper-catalysed desymme...

Cyclopropanes play an important role in drug discovery, and synthetic access to variedly substituted systems is an ongoing challenge for chemistry teams. A variety of scalable synthetic routes were de...

Radical route cuts out explosive reagents

The di-π-methane (DPM) rearrangement is an important organic photorearrangement that converts 1,4-diene-containing compounds to vinyl cyclopropanes, often resulting in extensive, synthetically valuabl...

'Unusual stereocontrol element' will help medicinal chemists increase three-dimensionality of drug candidates

The di-π-methane (DPM) rearrangement is an important organic photorearrangement that converts 1,4-diene-containing compounds to vinyl cyclopropanes, often resulting in extensive, synthetically valuable restructuring of the substrate’s carbon framework. We investigated the influence of Lewis and Brønsted acids on the DPM rearrangement of dibenzobarrelenes. These studies have culminated in the identification of a dual chiral Brønsted acid–iridium photosensitizer system that enables the first highly enantioselective catalytic all-carbon DPM rearrangement.

Deuterium labeling is a key tool used in drug development to observe and prevent metabolism. Here, we report a mild and operationally simple protocol for the synthesis of deuterated cyclopropanes with high levels of deuterium incorporation. This Fe-catalyzed strategy uses dichloromethane-d2 for safe, practical, and diazo-free access to carbene reactivity. A sterically and electronically diverse range of alkenes with varying functional groups are tolerated in this deuterated cyclopropanation. This highly air and water tolerant method complements existing strategies and significantly broadens access to valuable deuterated cyclopropanes, including with applications for the late-stage functionalization of pharmaceuticals.