Lipshutz-type bis(amido)argentates for directed argentation.

Bis(amido)argentate (TMP)Ag(CN)Li (, TMP-Ag-ate; TMP = 2,2,6,6-tetramethylpiperidido) was designed as a tool for chemoselective aromatic functionalization unprecedented directed argentation (DAg). X-Ray crystallographic analysis showed that takes a structure analogous to that of the corresponding Lipshutz cuprate. DAg with this TMP-Ag-ate afforded multifunctional aromatics in high yields in processes that exhibited high chemoselectivity and compatibility with a wide range of functional groups.

A Direct, Chemo-, and Regioselective Cross-Coupling Reaction of Arenes via Sequential Directed Cuprations and Oxidation.

Direct cross-coupling of Csp-H/Csp-H bonds of two arenes was achieved in 30-76% yield via sequential directed cuprations (DCu) with the cuprate base (TMP)Cu(CN)Li (, TMP = 2,2,6,6-tetramethylpiperidido), followed by oxidation. This methodology offers easy access to unsymmetric biaryls from arenes with a variety of directed metalation groups (DMGs) and ancillary functional groups, taking advantage of the highly chemoselective action of .

A new route for the efficient metalation of unfunctionalized aromatics.

The synthesis and isolation of a novel bimetallic species formed by reacting two equivalents of TMPLi with CuCl in the presence of EtO are reported. X-ray crystallography reveals the EtO-free tetranuclear aggregate (TMPCu)(TMPLi) , which formally results from the catenation of dimers of TMPLi and TMPCu. NMR spectroscopy confirms that, upon dissolution in hydrocarbon media, the crystals fail to form a conventional Gilman cuprate dimer.

Rhodium-Catalyzed (Perfluoroalkyl)olefination of Acetanilides Leading to Perfluoroalkylated Aromatics.

We have developed an efficient Rh-catalyzed (perfluoroalkyl)olefination reaction of acetanilides, which provides a versatile synthetic entry to a range of perfluoroalkylated compounds.

Direct Hydroxylation and Amination of Arenes via Deprotonative Cupration.

Deprotonative directed ortho cupration of aromatic/heteroaromatic C-H bond and subsequent oxidation with t-BuOOH furnished functionalized phenols in high yields with high regio- and chemoselectivity. DFT calculations revealed that this hydroxylation reaction proceeds via a copper (I → III → I) redox mechanism. Application of this reaction to aromatic C-H amination using BnONH2 efficiently afforded the corresponding primary anilines.

"Cation-Stitching Cascade": exquisite control of terpene cyclization in cyclooctatin biosynthesis.

Terpene cyclization is orchestrated by terpene cyclases, which are involved in the biosynthesis of various cyclic natural products, but understanding the origin and mechanism of the selectivity of terpene cyclization is challenging. In this work, we describe an in-depth mechanistic study on cyclooctatin biosynthesis by means of theoretical calculations combined with experimental methods. We show that the main framework of cyclooctatin is formed through domino-type carbocation transportation along the terpene chain, which we call a "cation-stitching cascade", including multiple hydrogen-shifts and a ring rearrangement that elegantly determine the stereoselectivity.