A new palladium-catalyzed annulative allylic alkylation(AAA)reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described,leading to the regiosel...A new palladium-catalyzed annulative allylic alkylation(AAA)reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described,leading to the regioselective synthesis of tetracyclic medium-sized cyclic ethers possessing a bridged aryl-indole scaf-fold,namely,benzo[2,3]oxocino[4,5-b]indoles and benzo[2,3]oxepino[4,5-b]indoles,in good to excellent yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and high regioselectivity,providing a catalytic and flexible method for creating bridged aryl-indole skeletons.展开更多
The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional g...The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.展开更多
Privileged biaryl frameworks,BINOL and NOBIN,were efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions.The judicious selection of palladium-catalytic system plays a pivot...Privileged biaryl frameworks,BINOL and NOBIN,were efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions.The judicious selection of palladium-catalytic system plays a pivotal role in the excellent selectivities.This transformation accommodated fairly broad substrate generality for both 2-naphthol and N-Boc-2-naphthylamine and afforded the structurally diversified BINOLs and NOBIN derivatives in high efficiency.Notably,the bromosubstituents which cannot survive in conventional palladium-catalyzed reactions were well-compatible with this set of conditions,providing an effective handle for further enriching the library of BINOLs and NOBINs.Preliminary attempts on the asymmetric variant of this reaction were also performed with up to 80:20 er for BINOLs synthesis.展开更多
Palladium-catalyzed Suzuki carbonylation with CHCl3 as carbonylative reagent was realized without external ligands. Different substituted benzophenones were explored via the coupling reaction of aryl iodides, arylboro...Palladium-catalyzed Suzuki carbonylation with CHCl3 as carbonylative reagent was realized without external ligands. Different substituted benzophenones were explored via the coupling reaction of aryl iodides, arylboronic acids and CHCl3 as a CO surrogate in moderate to good yields. This method was also successfully applied to the structure modification of α7 nicotinic acetylcholine receptor positive allosteric modulators（α7 nAChR PAMs） based on the preliminary structure-activity relationship.展开更多
基金the National Natural Science Foundation of China(Nos.21971090 and 22271123).
文摘A new palladium-catalyzed annulative allylic alkylation(AAA)reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described,leading to the regioselective synthesis of tetracyclic medium-sized cyclic ethers possessing a bridged aryl-indole scaf-fold,namely,benzo[2,3]oxocino[4,5-b]indoles and benzo[2,3]oxepino[4,5-b]indoles,in good to excellent yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and high regioselectivity,providing a catalytic and flexible method for creating bridged aryl-indole skeletons.
基金the National Natural Science Foundation of China(Nos. 21476074 and 21676088)for financial support
文摘The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.
基金supported by the National Natural Science Foundation of China(21825105)the Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)+2 种基金the Guangdong Innovative Program(2019BT02Y335)the Shenzhen Nobel Prize Scientists Laboratory Project(C17213101)the SUSTech Special Fund for the Construction of High-Level Universities(G02216402)。
文摘Privileged biaryl frameworks,BINOL and NOBIN,were efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions.The judicious selection of palladium-catalytic system plays a pivotal role in the excellent selectivities.This transformation accommodated fairly broad substrate generality for both 2-naphthol and N-Boc-2-naphthylamine and afforded the structurally diversified BINOLs and NOBIN derivatives in high efficiency.Notably,the bromosubstituents which cannot survive in conventional palladium-catalyzed reactions were well-compatible with this set of conditions,providing an effective handle for further enriching the library of BINOLs and NOBINs.Preliminary attempts on the asymmetric variant of this reaction were also performed with up to 80:20 er for BINOLs synthesis.
基金The National Natural Science Foundation of China(Grant No.21572011 and 21272009)
文摘Palladium-catalyzed Suzuki carbonylation with CHCl3 as carbonylative reagent was realized without external ligands. Different substituted benzophenones were explored via the coupling reaction of aryl iodides, arylboronic acids and CHCl3 as a CO surrogate in moderate to good yields. This method was also successfully applied to the structure modification of α7 nicotinic acetylcholine receptor positive allosteric modulators（α7 nAChR PAMs） based on the preliminary structure-activity relationship.
