资源环境科技发展态势分析平台

Functionalization of the beta-C-H bonds of aliphatic acids is emerging as a valuable synthetic disconnection that complements a wide range of conjugate addition reactions(1-5). Despite efforts for beta-C-H functionalization in carbon-carbon and carbon-heteroatom bond-forming reactions, these have numerous crucial limitations, especially for industrial-scale applications, including lack of mono-selectivity, use of expensive oxidants and limited scope(6-13). Notably, the majority of these reactions are incompatible with free aliphatic acids without exogenous directing groups. Considering the challenge of developing C-H activation reactions, it is not surprising that achieving different transformations requires independent catalyst design and directing group optimizations in each case. Here we report a Pd-catalysed beta-C(sp(3))-H lactonization of aliphatic acids enabled by a mono-N-protected beta-amino acid ligand. The highly strained and reactive beta-lactone products are versatile linchpins for the mono-selective installation of diverse alkyl, alkenyl, aryl, alkynyl, fluoro, hydroxyl and amino groups at the beta position of the parent acid, thus providing a route to many carboxylic acids. The use of inexpensive tert-butyl hydrogen peroxide as the oxidant to promote the desired selective reductive elimination from the Pd(IV) centre, as well as the ease of product purification without column chromatography, render this reaction amenable to tonne-scale manufacturing.

Charged pions(1) are the lightest and longest-lived mesons. Mesonic atoms are formed when an orbital electron in an atom is replaced by a negatively charged meson. Laser spectroscopy of these atoms should permit the mass and other properties of the meson to be determined with high precision and could place upper limits on exotic forces involving mesons (as has been done in other experiments on antiprotons(2-9)). Determining the mass of the pi(-) meson in particular could help to place direct experimental constraints on the mass of the muon antineutrino(10-13). However, laser excitations of mesonic atoms have not been previously achieved because of the small number of atoms that can be synthesized and their typically short (less than one picosecond) lifetimes against absorption of the mesons into the nuclei(1). Metastable pionic helium (pi He-4(+)) is a hypothetical(14-16) three-body atom composed of a helium-4 nucleus, an electron and a pi(-) occupying a Rydberg state of large principal (n approximate to 16) and orbital angular momentum (l approximate to n - 1) quantum numbers. The pi He-4(+) atom is predicted to have an anomalously long nanosecond-scale lifetime, which could allow laser spectroscopy to be carried out(17). Its atomic structure is unique owing to the absence of hyperfine interactions(18,19) between the spin-0 pi(-) and the He-4 nucleus. Here we synthesize pi He-4(+) in a superfluid-helium target and excite the transition (n, l) = (17, 16) -> (17, 15) of the pi(-)-occupied pi He-4(+) orbital at a near-infrared resonance frequency of 183,760 gigahertz. The laser initiates electromagnetic cascade processes that end with the nucleus absorbing the pi(-) and undergoing fission(20,21). The detection of emerging neutron, proton and deuteron fragments signals the laser-induced resonance in the atom, thereby confirming the presence of pi He-4(+). This work enables the use of the experimental techniques of quantum optics to study a meson.

Long-lived pionic helium atoms (composed of a helium-4 nucleus, an electron and a negatively charged pion) are synthesized in a superfluid-helium target, as confirmed by laser spectroscopy involving the pion-occupied orbitals.