Tf2NH-catalyzed,highly regio-and stereo-selective synthesis of trisubstituted alkenes and indane derivatives from benzylic alcohols and alkenes

A reaction of benzylic alcohols with alkenes has been developed in the presence of bis(trifluoromethane)sulfonimide for the synthesis of trisubstituted alkenes and indane derivatives with high stereoselectivity.In general,benzylic alcohols react with 1,1-diaryl alkenes to afford trisubstituted alkenes,and the reaction with 1,2-disubstituted and trisubstituted alkenes affords indane derivatives through a [3 + 2] annulation reaction.     

Theoretical Investigation of the Mechanism of Rh(III)-catalyzed Annulation of 2-Biphenylboronic Acid with Activated Alkene

The mechanism is investigated for Cp^tBuRh(OH)₂-catalyzed annulation of 2-biphenylboronic acid with three activated alkenes using M06-2X functional. The reaction comprises transmetalation via two steps and following C-H activation producing reactive Rh-biphenyl complex with two Rh—C σ bonds. After the coordination/insertion of alkenes, respective fused or bridged cyclic products are yielded depending on different alkenes accompanied by the release of Cp^tBuRh. The promotion of Cp^tBuRh(OH)₂ lies in the barrier decrease of transmetalation and C-H activation ready for coordination/insertion ensuring the smooth progress of common rate-limiting reductive elimination. The stereoselective transfer and ring rotation are specific for benzoquinone and cyclopropenone. The role of Rh(III) catalyst and release of Rh(I) is supported by Multiwfn analysis on frontier molecular orbital(FMO) of specific transiton states(TSs) and Mayer bond order(MBO) value of vital bonding, breaking.     

Annulation-Induced Hidden Reactivity of the 1,2,4-Triazole Backbone

Triazoles are an important class of compounds with widespread applications. Functionalization of the triazole backbone is thus of significant interest. In comparison to 1,2,3-triazoles, C−H activation-functionalization of the congeners 1,2,4-triazoles is surprisingly underdeveloped. Indeed, no such C−H activation-functionalization has been reported for 4-substituted 1,2,4-triazole cores. Furthermore, although denitrogenative ring-opening of 1,2,3-triazoles is well-explored, 1,2,4-triazole/triazolium substrates have not been known to exhibit N−N bond-cleaving ring-opening reactivity so far. In this work, we unveiled an unusual hidden reactivity of the 1,2,4-triazole backbone involving the elusive N−N bond-cleaving ring-opening reaction. This new reactivity was induced by a Satoh-Miura-type C−H activation-annulation at the 1,2,4-triazole motif appended with a pyridine directing group. This unique reaction allowed ready access to a novel class of unsymmetrically substituted 2,2′-dipyridylamines, with one pyridine ring fully-substituted with alkyl groups. The unsymmetrical 2,2′-dipyridylamines were utilized to access unsymmetrical boron-aza-dipyridylmethene fluorescent dyes. Empowered with desirable optical/physical properties such as large Stokes shifts and suitable hydrophobicity arising from optimal alkyl chain length at the fully-substituted pyridine-ring, these dyes were used for intracellular lipid droplet-selective imaging studies, which provided useful information toward designing suitable lipid droplet-selective imaging probes for biomedical applications.     

Total Synthesis of Metaphanine and Oxoepistephamiersine

Herein, we report a concise and divergent synthesis of the complex hasubanan alkaloids metaphanine and oxoepistephamiersine from commercially available and inexpensive cyclohexanedione monoethylene acetal. Our synthesis features a palladium-catalyzed cascade cyclization reaction to set the tricyclic carbon framework of the desired molecules, a regioselective Baeyer–Villiger oxidation followed by a MeNH₂ triggered skeletal reorganization cascade to construct the benzannulated aza[4.4.3]propellane, and a strategically late-stage regio-/diastereoselective oxidative annulation of sp³ C−H bond to form the challenging THF ring system and hemiketal moiety in a single step. In addition, a highly enantioselective alkylation of cyclohexanedione monoethylene acetal paved the way for the asymmetric synthesis of target molecular.     

Unlocking the Chain-Walking Process in Gold Catalysis**

The successful realization of gold-catalyzed chain-walking reactions, facilitated by ligand-enabled Au(I)/Au(III) redox catalysis, has been reported for the first time. This breakthrough has led to the development of gold-catalyzed annulation reaction of alkenes with iodoarenes by leveraging the interplay of chain-walking and π-activation reactivity mode. The reaction mechanism has been elucidated through comprehensive experimental and computational studies.     

Organocatalytic asymmetric [3 + 3] annulation of isatin N,N'-cyclic azomethine imines with enals: Efficient approach to functionalized spiro N-heterocyclic oxindoles

An unprecedented chiral secondary amine-catalyzed [3 + 3] annulation of isatin N,N'-cyclic azomethine imines with α,β-unsaturated aldehydes was developed. This strategy allowed the construction of structurally novel spiro N-heterocyclic oxindole derivatives in good yields (up to 91%) and good to excellent enantioselectivities (up to >99% ee), albeit with modest diastereoselectivities (up to 3.1:1 dr).     

Selective annulation of benzamides with internal alkynes catalyzed by an electron-deficient rhodium catalyst

An electron-deficient [Cp^ERhCl₂]₂ catalyzed annulation of N-pentafluorophenylbenzamides with internal alkynes was successfully established under mild reaction conditions, with the assistance of Lewis acid silver salt. Particularly, electron-deficient benzamide substrates were smoothly transformed into the desired products in this catalytic system. The catalytic system showed a broad tolerance for different substituents on the aromatic rings or aryl, alkyl-substituted alkynes.     

N-Tosylhydrazone as an oxidizing directing group for the redox-neutral access to isoquinolines via Cp1Co(III)-Catalyzed C–H/N–N activation

Herein, an efficient and economic access has been revealed for the synthesis of isoquinolines via C–H bond activation strategy by using comparatively inexpensive and versatile cobalt catalyst. A hardly investigated directing group, N-tosylhydrazone has been effectively applied as an internal oxidant for an annulation reaction with internal alkynes via C–H/N–N bond functionalization. This catalytic protocol works for the extensive variety of substrates in moderate to excellent yields under external oxidant-free conditions. Additionally, the proposed protocol has advantages such as broad substrate coverage with significant product yields, readily synthesized substrates as well as scalability up to the gram quantity which further improves the competency of the methodology.     

Synthesis of 3-aminoindan-1-one derivatives from 2-acetylbenzaldehydes and secondary amines by Mannich annulation

An acid-promoted 2-component Mannich annulation reaction of readily available acetylbenzaldehydes and secondary amines has been reported. The approach provides a simple and efficient method under mild conditions to synthesize 3-aminoindan-1-one derivatives in moderate to good yields.     

BF_3-promoted annulation of azonaphthalenes and ynamides for synthesis of benzo[e]indoles

A novel BF₃-promoted [3+2] annulation of azonaphthalenes and ynamides is described.This protocol provides a modular and efficient entry to functionalized amino benzo[e]indole derivatives smoothly.