Catalytic Asymmetric Cycloaddition of Olefins with In Situ Generated -Boc-Formaldimine.

Chiral 1,3-amino alcohols are ubiquitous structural motifs in natural products and active pharmaceutical ingredients. We present a highly enantioselective, inverse-electron-demand hetero-Diels-Alder reaction of olefins with in situ generated -Boc-formaldimine catalyzed by strong and confined Bro̷nsted acids. This transformation provides direct access to valuable 1,3-amino alcohols from styrenes and 1,1-disubtituted alkenes.

Catalytic asymmetric fragmentation of cyclopropanes.

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, chemical approaches have largely been limited to transition metal-based catalytic carbon-hydrogen functionalizations. Alkanes can be protonated to form pentacoordinated carbonium ions and fragmented into smaller hydrocarbons in the presence of strong Brønsted acids.

Highly Acidic Electron-Rich Brønsted Acids Accelerate Asymmetric Pictet-Spengler Reactions by Virtue of Stabilizing Cation-π Interactions.

Electron-rich heteroaromatic imidodiphosphorimidates (IDPis) catalyze the asymmetric Pictet-Spengler reaction of -carbamoyl-β-arylethylamines with high stereochemical precision. This particular class of catalysts furthermore provides a vital rate enhancement compared to related Brønsted acids. Here we present experimental studies on the underlying reaction kinetics that shed light on the specific origins of rate acceleration.

A solid noncovalent organic double-helix framework catalyzes asymmetric [6 + 4] cycloaddition.

Whereas [4 + 2] cycloadditions are among the most powerful tools in the chemist's synthetic arsenal, controlling reactivity and selectivity of [6 + 4] cycloadditions has proven to be extremely challenging. Such transformations, especially if compatible with simple hydrocarbon-based substrates, could ultimately provide a general approach to highly valuable and otherwise difficult to access 10-membered rings. We report here that highly acidic and confined imidodiphosphorimidate catalysts do not catalyze this reaction under homogeneous conditions.

The catalytic asymmetric polyene cyclization of homofarnesol to ambrox.

Polyene cyclizations are among the most complex and challenging transformations in biology. In a single reaction step, multiple carbon-carbon bonds, ring systems and stereogenic centres are constituted from simple, acyclic precursors. Simultaneously achieving this kind of precise control over product distribution and stereochemistry poses a formidable task for chemists.