A Formal 1,2-Stevens Rearrangement of Thioester Ylides as a Single-Atom Molecular Editing Tool.

A rhodium-catalyzed reaction of thioesters with diazo reagents was recognized as a powerful and unprecedented tool for single-atom molecular editing by the insertion of a single carbon atom into the C(O)─S thioester bond, thereby leading to various α-thioketones possessing a quaternary carbon atom. A selective and precise defunctionalization of the polyfunctionalized products further demonstrated the synthetic utility of the reaction for the synthesis of more common structural classes of compounds.

Intramolecular Dearomative Inverse-Electron-Demand Diels Alder Strategy for the Total Synthesis of (+)-Alstonlarsine A.

An evolution of a synthetic route leading to a successful enantioselective total synthesis of monoterpenoid indole alkaloid (+)-alstonlarsine A is represented. The unique 9-azatricyclo[4.3.

Total Synthesis of (+)-Alstonlarsine A.

An enantioselective total synthesis of (+)-alstonlarsine A (1), a monoterpenoid indole alkaloid possessing a unique pentacyclic skeleton as well as a rare biological activity, is achieved. The key step is an efficient domino sequence, comprising enamine formation followed by an inverse-electron-demand intramolecular dearomative Diels-Alder cycloaddition for the construction of 9-azatricyclo[4.3.

Enantioselective Synthesis of the Platensimycin Core by Silver(I)-Promoted Cyclization of Δ -α-Iodoketone.

A chiral-pool-based synthesis of the platensimycin core was achieved using (S)-lactic acid as an inexpensive starting material. The cyclohexenone ring was closed in a Mukaiyama-Michael domino sequence, while the quaternary stereocenter was created by a highly stereoselective decarboxylative allylation. The spirobicyclic skeleton was constructed by a RCM reaction.

Total Synthesis of (±)-Alstoscholarisine A.

The first total synthesis of the neuroactive indole alkaloid (±)-alstoscholarisine A is reported. The key step of the concise synthesis is an efficient domino sequence that was used to assemble the 2,8-diazabicyclo[3.3.

A novel C,D-spirolactone analogue of paclitaxel: autophagy instead of apoptosis as a previously unknown mechanism of cytotoxic action for taxoids.

The design, synthesis and biological evaluation of a novel C,D-spirolactone analogue of paclitaxel is described. This is the first paclitaxel analogue without an oxetane D-ring that shows a significant cytotoxic effect (activity one order of magnitude lower than paclitaxel). More importantly, its cytotoxicity is a result of a different mechanism of action, involving mTOR inhibition-dependent autophagy instead of G(2)/M cell cycle arrest-dependent apoptosis.

An aldol approach to the enantioselective synthesis of (-)-oseltamivir phosphate.

A formal asymmetric synthesis of the antiviral agent (-)-oseltamivir phosphate is achieved using two aldol reactions as key steps.

Radical, one-step approach to o-chlorophenyl thioethers from xanthates. A rapid access to vinylsilanes.

Xanthates have been readily converted into o-chlorophenyl thioethers using a one-step procedure conducted under radical conditions. In some selected cases, these aryl thioethers were successfully oxidized to the corresponding sulfoxides and sulfenic acid elimination afforded the corresponding vinylsilanes.