A catalytic reductive C1-acylation of 3,4-dihydroisoquinolines is presented that gives direct access to 1,1-disubstituted tetrahydroisoquinolines. The reaction is a titanium(III)-catalyzed reductive umpolung process in which nitriles act as effective acylation agents. The method is highly chemo- and regioselective and is demonstrated in 20 examples. It is well-suited for the large-scale synthesis of functionalized tetrahydroisoquinoline products, which is exemplified in the form of a six-step synthesis of (±)-3-demethoxyerythratidinone.

Chiral ansa-metallocenes are privileged catalysts for a range of stereoselective transformations. Their synthesis, however, has remained a tremendous challenge, which has prevented a broad and systematic exploration for applications in synthesis and catalysis. A modular approach to such ansa-metallocenes that enables a facile modification of the ring substitution and the ligand bridge, as well as the introduction of various core metals, is described. The complexes were formed with good rac-selectivity and could be isolated with high purity. The strength of the approach was demonstrated by the synthesis of several new and previously known complexes, including a unique helical chiral ansa-metallocene. Using a chiral ligand, a moderate central-to-planar chirality transfer was observed.

This minireview provides a survey of the various synthetic approaches to chiral ansa‐metallocenes of Ti, Zr, and Hf containing a carbon‐based bridge. The individual strategies to install substitution patterns at either the cyclopentadienyl framework or the bridging unit are highlighted with focus on the progress made towards a direct preparation of single complex stereoisomers. The review further includes the discussion of potential problems such as the formation of undesired diastereomers, the threat of racemization of enantiopure material, and synthetic challenges originating from the synthesis, purification, and isolation of the target complexes. The review has been written with the goal in mind to facilitate the design and synthesis of new chiral ansa‐metallocene derivatives for emerging research areas in asymmetric catalysis and organometallic chemistry.

Detailed herein are our synthetic studies toward the preparation of the C18- and C19-benzenoid cephalotane-type norditerpenoids. Guided by chemical network analysis, the core structure of this natural product family was constructed in a concise manner using an iterative cross-coupling, followed by a formal inverse-electron-demand [4 + 2] cycloaddition. Initial efforts to functionalize an alkene group in the [4 + 2] cycloadduct using a Mukaiyama hydration and a subsequent olefination led to the complete C18-carbon framework. While effective, this approach proved lengthy and prompted the development of a direct alkene difunctionalization that relies on borocupration to advance the cycloadduct to the natural products. Late-stage peripheral C–H functionalization facilitated access to all of the known cephanolides in 6–10 steps as well as five recently isolated ceforalides in 8–13 steps.

Condensed phosphates are ac ritically important class of molecules in biochemistry.Non-natural analogues are important for various applications,s uch as single-molecule real-time DNAs equencing.O ften, such analogues contain more than three phosphate units in their oligophosphate chain. Consequently,investigations into phosphate reactivity enabling new ways of phosphate functionalization and oligophosphorylation are essential. Here,w es crutinizet he potential of phosphates to act as arynophiles,paving the way for follow-up oligophosphorylation reactions.The aryne phosphate reaction is ap owerful tool to-depending on the perspective-(oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates,t he aryne phosphate reaction enables rapid entry into ab road spectrum of arylated products,l ike monophosphates,d iphosphates,p hosphodiesters and polyphosphates.T he synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.