Circularly polarized chemiluminescence from planar chiral bis(adamantylidene-1,2-dioxetane)s.

Bis(adamantylidene-1,2-dioxetane), upon conjugation to a planar chiral scaffold of [2.2]paracyclophane, gave chemical-triggerable circularly polarized chemiluminescence with a dissymmetry factor of 1.1 × 10-3 scale, to which exciton chirality upon chemiexcitation was assigned as the origin.

Aggregation of phosphorescent Pd(II) and Pt(II) complexes with lipophilic counter-anions in non-polar solvents.

Phosphorescent cationic tridentate C^N^N (HC^N^N = 6-(2-R2,4-R1-phenyl)-2,2'-bipyridine; R1 = R2 = H or F, or R1 = OMe, R2 = H) cyclometallated Pd(II) complexes with an N,N-dimethyl-imidazol-allenylidene ancillary ligand (L) and their corresponding Pt(II) congeners have been synthesized and characterized, following the previously reported preparation of the complex [Pd(6-phenyl-2,2'-bipyridine)L]+. For these cationic Pd(II)/Pt(II) complexes with 2,3,4-tris(dodecyloxy)benzenesulfonate (LA-) counter-anions in mixed CH2Cl2/toluene solvents, uniform square flake or fibre-like aggregates were formed. Corresponding multicolour phosphorescence with obvious metal-metal-to-ligand charge transfer (MMLCT) features gradually changed from red to NIR by manipulating the various fractions of Pd/Pt species. Circular dichroism (CD) and circularly polarized luminescence (CPL) derived from the fibre-like Pd aggregates of [Pd(6-(2,4-difluorophenyl)-2,2'-bipyridine)L]+ in chiroptical CH2Cl2/limonene solvents were achieved with an isodesmic aggregation mode. Dispersive metallophilic interactions are claimed to be the driving force for these photo-functional aggregates.

Direct Asymmetric Aza-Vinylogous-Type Michael Additions of Nitrones from Isatins to Nitroalkenes.

Nitrones commonly act as 1,3-dipoles and electrophiles to furnish valuable isoxazolidine and N-hydroxyl products, respectively. They also can be converted to nitrone ylide species and undergo [3+2] formal cycloadditions to access N-hydroxyl pyrrolidines. Here, asymmetric direct aza-vinylogous-type additions of nitrones from isatins to nitroalkenes are presented, catalyzed by a bifunctional thiourea-tertiary amine, affording highly functionalized nitrones with extended carbon skeletons in excellent stereoselectivity. Notably, the nitrone moiety can be easily removed, thus furnishing the formal asymmetric α-functionalization of alkylamine-type substances. Moreover, the remaining electrophilic nitrone motif enables the subsequent annulations to construct spirocyclic products in high molecular complexity and diversity, which might have potential applications for drug discovery.

Asymmetric Inverse-Electron-Demand Oxa-Diels-Alder Reaction of Allylic Ketones through Dienamine Catalysis.

A remote ß,γ-regioselective asymmetric inverse-electron-demand oxa-Diels-Alder reaction between allylic ketones and α-cyano-α,ß-unsaturated ketones has been developed through induced extended dienamine catalysis of a cinchona-derived primary amine. A spectrum of densely substituted dihydropyran frameworks were efficiently produced with excellent enantioselectivity and fair to exclusive diastereoselectivity.

Catalyst-Controlled Switch in Chemo- and Diastereoselectivities: Annulations of Morita-Baylis-Hillman Carbonates from Isatins.

Regulating both the chemo- and diastereoselectivity, divergently, of a reaction is highly attractive but extremely challenging. Presented herein is a catalyst-controlled switch in the chemo- and diastereodivergent annulation reactions of Morita-Baylis-Hillman carbonates, derived from isatins and 2-alkylidene-1H-indene-1,3(2H)-diones, in exclusive α-regioselectivity. α-Isocupreine efficiently catalyzed [2+1] reactions to access cyclopropane derivatives, and the diastereodivergent [3+2] annulations were accomplished by employing either a chiral phosphine or a DMAP-type molecule. All reactions exhibited excellent chemoselectivities, and good to remarkable stereoselectivities were furnished, thus leading to a collection of compounds with skeletal and stereogenic diversity. Moreover, DFT computational calculations elucidated the catalyst-based switch in mechanism.

[4 + 3] Cycloadditions with Bromo-Substituted Morita-Baylis-Hillman Adducts of Isatins and N-(ortho-Chloromethyl)aryl Amides.

Efficient construction of a challenging aza-spirocycloheptane oxindole scaffold is reported through an unprecedented [4 + 3] cycloaddition reaction with bromo-substituted Morita-Baylis-Hillman adducts of isatins and N-(ortho-chloromethyl)aryl amides. Both reactive intermediates, the allylic phosphonium ylides and aza-o-quinone methides, were in situ generated, chemoselectively facilitated by a Lewis base and Brønsted base, respectively.