The MAPK signaling cascade is nowadays understood as a network module highly conserved across species. Its main function is to transfer a signal arriving at the plasma membrane to the cellular interior. Current understanding of 'how' this is achieved involves the notions of ultrasensitivity and bistability which relate to the nonlinear dynamics of the biochemical network, ignoring spatial aspec...

An unprecedented cascade reaction of isocyanide and methyleneindolinone has been established, which represents a novel and different reaction mode. This present transformation involves the ring-opening of methyleneindolinone and the construction of two other new rings simultaneously in an atom-economic manner.

Platinum(II) catalyzes the isomerization of camphor sulfonamide diynes in a cascade reaction involving annulation of a five-membered ring to the camphor skeleton, ring-enlargement by C-C bond cleavage, reduction of sulfur(VI) to sulfur(IV), and oxidation of a hydroxy group to a ketone. The reactions of the diynes with other transition metal compounds were also studied. Copper, gold and rhenium ...

The structures of enzymes that collectively modify proteins by covalent addition of ubiquitin-like protein moieties have provided significant insights into the regulatory pathways they compose and have highlighted the importance of protein flexibility for the mechanism and regulation of the ubiquitination reaction.

A general three-component triple cascade reaction through an iminium-enamine-iminium sequential activation initiated by a hetero-Michael addition to α,β-unsaturated aldehydes affords [3.2.0]heterobicycles in high diastereoselectivity. The rate and diastereoselectivity of the reaction depended on the (E)-4-heterocrotonate and size of the secondary amine. The enantiomers of the major diastereoiso...

Bicyclodihydrosiloles were readily prepared from optically active enyne compounds by a radical cascade reaction triggered by tris(trimethylsilyl)silane ((Me3Si)3SiH). The reaction was initiated by the addition of a silyl radical to an α,β-unsaturated ester, forming an α-carbonyl radical that underwent radical cyclization to a terminal alkyne unit. The resulting vinyl radical attacked the silico...

For small cyclic peptides, one electron capture by the [M + 2H](2+) ion generates numerous fragments corresponding to amino acid losses, side-chain losses, and losses of some low molecular weight species such as H(2)O, CH(3)(*), C(3)H(6), and (*)CONH(2). As predicted, the side-chain cleavages are amplified relative to linear peptides of similar size, but the amino acid losses were unexpected be...

Readily available chiral primary 1,2-aminoalcohols and diamines have been explored as organocatalysts for a domino Michael-aldol reaction. Their application in this organocascade process afforded cyclohexanone A with high levels of reactivity (up to 91% yield) and stereoselectivity (>97 : 3 d.r., up to 93% ee). Depending on the acid cocatalyst different chiral species (cyclic secondary amines v...