Aniline derivatives are frequently encountered in molecules of industrial relevance such as dyes or antioxidants, which make the development of synthetic methods for the functionalization of these privileged structures highly sought-after. A general protocol for the hydroarylation of electronically diverse alkenes with anilines would be ideal to provide densely functionalized compounds. Yet, this transformation has been underexplored compared to more traditional hydroarylation of unactivated alkenes because of the significant challenges associated with the control of the selectivity and its substrate tolerance. Herein, we describe a selective, versatile and user-friendly ortho-C-alkylation of anilines with alkenes that hinges on the beneficial combination of a Lewis acid (Ca(II)) and hexafluoroisopropanol as a solvent. This protocol allows for the extension of this transformation to highly deactivated styrenes and demonstrates a remarkable improved reactivity regarding aliphatic alkenes, styrene derivatives and dienes. In addition, DFT computations were performed which, combined with experimental observations, suggest a nearly concerted mechanism that impart the ortho-selectivity.

Pyrrolidine and piperidine derivatives bearing halide functional groups are prevalent building blocks in drug discovery as halides can serve as an anchor for postmodifications.I np rinciple,o ne of the simplest ways to build these frameworks is the haloamination of alkenes.W hile progress has been made in this field, notably with the development of enantioselective versions,t his reaction is still fraught with limitations in terms of reactivity.Besides,amajor question remaining is to understand the mechanism at work. The formation of ah aliranium intermediate is typically mentioned, but limited mechanistic evidence supports it. Reported here is an efficient metal-and oxidant-free protocol to achieve the haloamidation of olefins,p romoted by hexafluoroisopropanol, along with aD FT investigation of the mechanism. These findings should guide the future development of more complex transformations in the field of halofunctionalization.

9,10-Dihydroacridines are frequently encountered as key scaffolds in OLEDs. Yet, accessing those compounds from feedstock precursors typically requires multiple steps. Herein, a modular one-pot synthesis of 9,10-dihydroacridine frameworks is achieved through a reaction sequence featuring a selective ortho-C alkenylation of diarylamines with aryl alkynes followed by an intramolecular hydroarylation of the olefin formed as intermediate. This transformation was accomplished by virtue of the combination of hexafluoroisopropanol and triflimide as a catalyst that triggers the whole process.

This manuscript discloses the first use of chiral phosphates based on C2-symmetric paracyclophane scaffolds as chiral counterions in transition metal catalysis, showing that they may compare favorably with other known chiral phosphates, such as the TRIP phosphate. The targeted catalytic reaction is a silver(I) promoted domino heterocyclization of 2-(1-alkynyl)-2-alken-1-one derivatives, in the presence of C-, or Nnucleophiles, which provides an efficient access to substituted bicyclic furans. Results show that high levels of enantioselectivity can be attained with either paracyclophane-based phosphates or TRIP phosphates, when the nucleophilic reactants display N-H functions in appropriate positions, near to the nucleophilic center. Therefore, the involvement of H-bonding between the NH function and the phosphate in the enantiodetermining step is postulated.N-(4-((2-Phenyl-4,5,6,7-tetrahydrobenzofuran-4-yl)amino)phenyl)acetamide (4g)Following the general procedure with AgPF 6 , the crude residue was purified by flash chromatography (eluent: nheptane 100% to n-heptane/EtOAc 50:50) to afford compound 4 g in 28% yield (9.7 mg). 1 H NMR (500.2 MHz, CDCl 3 ), d (ppm) = 7.60 (d, J = 7.6 Hz, 2H), 7.34 (t, J = 7.6 Hz, 2H), 7.28 (d, J = 7.6 Hz, 2H), 7.21 (t, J = 7.6 Hz, 1H), 7.05-

A new and efficient reaction sequence between 2-furylcarbinols, anilines, and α-haloamides has been developed to afford highly functionalized cyclopenta[b]piperazinones. This transformation was accomplished through an aza-Piancatelli cyclization/azaoxyallyl cation trapping with a complete control of the diastereoselectivity.

The aza‐Piancatelli cyclization provides an expedient synthesis of 4‐aminocyclopentenone building blocks that may be converted into aminocyclopentitols, which are heavily represented motifs among natural products. However, its use as a key step in total synthesis was still unprecedented. Here, we disclose our in‐depth investigations regarding this reaction in order to access highly complex structures representing the core of some natural molecules. The applicability of the cyclization was highlighted by the 3‐step total synthesis of bruceolline D. Thus, we anticipate that this work will lay the ground for further applications in total synthesis.

Herein, we describe a hitherto unprecedented trifluoromethylthiolation of N‐acyliminiums promoted by boron trifluoride etherate to enable a convenient access to various α‐amino trifluoromethylthiolate derivatives in good yields. The reaction proceeds under mild conditions, relying on copper(I) trifluoromethylthiolate as a nucleophilic partner.magnified image

For the first time, azaoxyallyl cations were used as cycloaddition partners with tropone derivatives to access nitrogen-containing [7,6]-fused bicycles in a metal-free process under mild reaction conditions. DFT computations have been used to shed light on the selectivities observed during the course of the reaction.