Access to multi-functionalized oxazolines via silver-catalyzed heteroannulation of enamides with sulfoxonium ylides

Disclosed herein is an efficient Ag-catalyzed 4+1 heteroannulation reaction of enamides withα-carbonyl sulfoxonium ylides.The diastereoselective transformation provides a practical access to a diverse range of multi-functionalized oxazoline derivatives.The synthetic utility of the resultant tetrasubstituted oxazolines is further demonstrated by a series of useful manipulations into valuable building blocks of pharmaceutical relevance.

Regulating the dimensionality of diphosphaperylenediimide-based polymers by coordinating the out-of-plane anisotropic π-framework toward Ag^(+)

The development of hetero-π-conjugated molecules is of significance for constructing diverse assembling superstructures based on heteroatom-related bonded or nonbonded interactions.Herein,we developed one-pot P-heteroannulation via palladiumcatalyzed dual P-C bonds formation and subsequent sulfidation to construct two isomeric diphosphaperylenediimides(cis-5 and trans-5).The unique out-of-plane anisotropic π-framework induced a cumulative anisotropy with a dipole moment of up to 8.82 D for cis-5,leading to distinct supramolecular packing arrangements.Optical and electrochemical characterizations demonstrated that they showed the largest redshifts extending to 574 nm and rather low-lying LUMO levels of −4.41 eV.Furthermore,the introduced P=S moieties endowed these diphosphaperylenediimides with prominent coordination ability towards Ag^(+),and thus the first example of perylene diimide(PDI)core-involved metal-organic coordination polymers(MOCPs)with tunable dimensionality varying from 1D,2D,to 3D was tactfully achieved.In view of easy accessibility and 2D layered porous structure,thus 2D(trans-5)·(AgOTf)based MOCP showed high crystallinity and good CO_(2) adsorption capacity with surface area of 112 m^(2)/g.The result opens a span-new avenue for exploring rylene imide-based MOCPs and related properties by integrating P functionality.

Diversity-Oriented Enantioselective Construction of Atropisomeric Heterobiaryls and N-Aryl Indoles via Vinylidene Ortho-Quinone Methides

An atroposelectively diversity-oriented synthetic strategy was developed for the divergent synthesis of axially chiral heterocycles through organocatalytic asymmetric intramolecular annulation of alkyne via vinylidene ortho-quinone methides(VQMs).The methodology reported herein was characterized by rapid reactions(most completed in seconds),high stereocontrol(up to 98%ee),and broad substrate scope(60 examples of different skeletal types,stereogenicelements,andring sizes).