The facile insertion of β-keto sulfones to arynes:The direct preparation of polysubstituted ortho-keto benzyl sulfones

One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.

Strain-promoted S-arylation and alkenylation of sulfinamides using arynes and cyclic alkynes

The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction of N-functionalization. Herein, we disclose a novel strain-release strategy to access stereospecific and chemoselective SIV-arylation and alkenylation of sulfinamides using arynes and strained cyclic alkynes. This method tolerates an unprecedented chemical diversity of functional groups attached to the nitrogen center(N-R). The origin of the high SIV-selectivity is elucidated by density functional theory calculations, suggesting a stepwise mechanism for the aryne substrates and a concerted mechanism for the cyclic alkynes.

Highly efficient synthesis of 9-aminoxanthenes via the tandem reaction of arynes with salicyl N-tosylimines

A cascade insertion-nucleophilic annulation reaction of salicyl N-tosylimines with aryne generated in situ from 2-（trimethyl- silyl） aryl triflate and KF-18-crown-6 has been developed, providing 9-aminoxanthenes efficiently in one step.

Synthesis of π-extended dibenzo[d,k]ullazines by a palladium-catalyzed double annulation using arynes

An efficient Pd-catalyzed double annulation reaction of 1-(2,6-dibro mophenyl)-1 H-pyrroles with arynes is developed to synthesizeπ-extended dibenzo[d,k]ullazines in good to excellent yields.For the first time,the parent dibenzo[d,k]ullazine core is obtained and characterized.

Design,Synthesis,and Applications of ortho-Sulfur Substituted Arylphosphanes

Ortho-sulfur substituted arylphosphine oxides and arylphosphonates are the precursors of orthosulfurated arylphosphanes,which are widely utilized as ligands in transition metal-catalyzed reactions.However,efficient synthetic methods to access such compounds are sparse.Herein,highly valuable ortho-sulfur substituted arylphosphine oxides and arylphosphonates were constructed via difunctionalization of aryne precursors with P(O)H and elemental sulfur.This method avoids the use of transition metal catalysts and corrosive phosphorus chloride.The synthetic utility of this reaction is further demonstrated by the reduction of the synthesized products to access monophosphine ligands and their applications in cross-coupling reactions.Moreover,by introducing an alkyne moiety into the P(O)H substrate,cyclic sulfur-containing phosphines could be obtained in a one-pot reaction,which represents a new P,S structure that is inaccessible by known strategies.

Ultralong Organic Phosphorescence Modulation of Aromatic Carbonyls and Multi-Component Systems

Aromatic carbonyls have evoked sustained attention in the field of room-temperature phosphorescence(RTP).The introduction of carbonyl groups is a general way to achieve RTP for their effective intersystem crossing(ISC)by improving spin-orbit coupling(SOC).With further molecular design and processing strategies,aromatic carbonyls materials with multi-functional and high efficiency ultralong organic phosphorescence(UOP)can be obtained.This review summarizes the mechanism of aromatic carbonyls with UOP in pure aromatic carbonyls and their multi-component systems.Some detailed strategies for improving UOP performance are further introduced.The summary and outlook are presented to expound on the advances and lack of aromatic carbonyls.Further development directions and requirements are also put forward.