A palladium-catalyzed alkoxycarbonylation with two different alcohols for the synthesis of cyclobutanecarboxylates bearing an α-quaternary carbon center is presented. The reaction utilizes readily accessible starting materials, tolerates a broad scope of functional groups, and provides a straightforward and efficient approach for the synthesis of a diverse array of cyclobutanecarboxylates bearing an α-quaternary carbon. Meanwhile, this strategy effectively prevents the transition-metal-catalyzed ring-opening of cyclobutanols, preserves the cyclobutane framework, and affords 1,1-disubstituted cyclobutanecarboxylates in high yields with excellent regioisomeric ratios.
View Article and Find Full Text PDFHerein, we developed a mild and efficient palladium-catalyzed carbonylative Sonogashira coupling of aryl thianthrenium salts with aliphatic alkynes and benzyl acetylene toward alkynones and furanones. Various desired products were prepared in good yields with broad functional group tolerance including the bromide group. In the case of using benzyl acetylene, the corresponding furanones can be obtained in good yields under the same conditions with two molecules of CO inserted.
View Article and Find Full Text PDFFour-membered carbocycles are among the most sought-after backbones which are commonly found in biologically active molecules. However, difficulties on their producing are existing due to its highly strained ring system. On the other hand, cyclobutanols can be straightforwardly prepared and can serves as precursors for synthesizing cyclobutane derivatives.
View Article and Find Full Text PDFAlkynones are valuable compounds with applications in various areas. In this work, we developed an efficient carbonylation procedure for the carbonylative cross-coupling of aryl thianthrenium salts with aromatic alkynes. Various useful alkynones were produced in moderate to excellent yields under mild conditions.
View Article and Find Full Text PDFObjective: Biliary duct management is of great significance after laparoscopic cholecystectomy (LC) combined with laparoscopic common bile duct exploration (LCBDE) in the treatment of cholecystolithiasis accompanied with common bile duct (CBD) stones. This study is to evaluate the safety and effectiveness of primary closure with C-tube drainage through cystic duct after LC + LCBDE.
Methods: Through a retrospective study, 290 patients who underwent LC + LCBDE in our hospital from January 2019 to April 2022 were enrolled and divided into 2 groups.
Background: Mounting evidence in recent years has demonstrated that the number of obese adolescents has continued to rise. Obese adolescents are more likely to be diagnosed with type 2 diabetes, which causes additional harm. This study aimed to compare the clinical outcomes of bariatric surgery and medical treatment.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2022
Herein, we developed a new procedure on 1,2-dicarbonylative cyclization of 4-aryl-1-butenes with alkyl bromides. Using simple copper catalyst, two molecules of carbon monoxide were introduced into the double bond with the formation of four new C-C bonds and a new ring. Various α-tetralones and 2,3-dihydroquinolin-4-ones were formed in moderate to good yields.
View Article and Find Full Text PDFCatalytic asymmetric variants for functional group transformations based on carbon-carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp)-C(sp) σ bond activation and click desymmetrization to form synthetically versatile and value-added oxaspiro products. The operationally straightforward and enantioselective palladium-catalyzed atom-economic annulation process exploits a TADDOL-derived bulky P-ligand bearing a large cavity to control enantioselective spiro-annulation that converts cyclopropenones and cyclic 1,3-diketones into chiral oxaspiro cyclopentenone-lactone scaffolds with good diastereo- and enantio-selectivity.
View Article and Find Full Text PDFHydrosilylation of unsaturated carbon-carbon bonds with hydrosilanes is a very important process to access organosilicon compounds and ranks as one of the most fundamental reactions in organic chemistry. However, catalytic asymmetric hydrosilylation of activated alkenes and internal alkenes has proven elusive, due to competing reduction of carbon-carbon double bond or isomerization processes. Herein, we report a highly enantioselective Si-C coupling by hydrosilylation of carbonyl-activated alkenes using a palladium catalyst with a chiral TADDOL-derived phosphoramidite ligand, which inhibits O-hydrosilylation/olefin reduction.
View Article and Find Full Text PDFA novel and unusual palladium-catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si-C(sp ) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp )-C(sp ) and Si-C(sp ) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.
View Article and Find Full Text PDFAims: miR-181a and miR-181b have been investigated as prognostic biomarkers of colorectal cancer (CRC). However, there is controversy about the role of miR-181a and miR-181b in predicting CRC prognosis. Therefore, we performed this meta-analysis to evaluate prognostic values of miR-181a and miR-181b in CRC patients.
View Article and Find Full Text PDF1,5- and 1,8-bis(bifluorenyl)anthracene were synthesized and converted to their corresponding bis(bifluorenyl)triptycenes and bis(bifluorenyl)-9,10-dihydroanthracenes. Analysis of their optical properties shows no feature of extended conjugation in the triptycene pair. The electronic spectra of the triptycene and dihydroanthracene pairs are in fact superimposable.
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