Conjugate Addition of a Silyl Ketene Acetal to α,β‐Unsaturated Lactones

Abstract

Conjugate addition of a silyl ketene acetal [Me₂C?C (OMe)OSiMe₃] to α,β‐unsaturated lactones (namely, 5,6‐dihydro‐2H‐pyran‐2‐one, 2(5H)‐furanone as Michael acceptor) occurs efficiently at room temperature in the presence of a nucleophilic catalyst, tetra‐n‐butyl ammonium bibenzoate (TBABB), in THF as well as Lewis acid catalysts such as Yb(OTf)₃ and I₂ in CH₂Cl₂, giving the corresponding 1,4‐adducts in excellent yields.     

Bismuth Trichloride–Catalyzed C‐Alkylation of Pyrroles with Electron‐Deficient Olefins

The BiCl₃‐catalyzed reaction of pyrroles with electron‐deficient olefins generated the corresponding Michael adducts in high yields.     

Synthesis of 2,3‐Dihydro‐4H‐furo[3,2‐c] chromen‐4‐ones and 2,3‐Dihydronaphtho[2,3‐b]furan‐4,9‐diones by the Radical Cyclizations of Hydroxyenones with Electron-Rich Alkenes using Manganese(III) Acetate

We have obtained dihydrofurans 3a–j in the radical cyclization of 4‐hydroxycoumarin 1a and 2‐hydroxy‐1,4‐naphtoquinone 1b with electron rich alkenes 2a–i by manganese(III) acetate. Methods A and B, which have different molar ratios were studied comparatively in these reactions, and we observed that method B (molar ratio 2:1:3) gave the best results. Treatment of 4‐hydroxycoumarin 1a and electron rich alkenes 2a–e gave 2,3‐dihydro‐4H‐furo[3,2‐c]chromen‐4‐ones 3a–e in 36–86% yields by the method B. Under the same conditions, the reactions of 2‐hydroxy‐1,4‐naphtaquinone 1b with conjugated alkenes 2b and 2f–i afforded 2,3‐dihydronaphtho[2,3‐b]furan‐4,9‐diones 3f–j in an excellent yields.     

Synthesis of Novel Spiro[indol-2,2′-pyrroles] Using Isocyanide-Based Multicomponent Reaction

An efficient and facile method for the synthesis of novel spiro[indole-2,2′-pyrroles] from N-methyl-3-isatin imines, t-butyl isocyanide, and dialkyl acetylenedicarboxylate has been achieved by [3 + 2] cyclo addition reaction. All the products were purified by column chromatography as yellow solids and confirmed with ¹H NMR, ¹³C NMR, fast atom bombardment, mass, and infrared. Compound 11 was further confirmed with x-ray analysis.     

Formation of Quaternary Stereogenic Centers by Copper‐Catalyzed Asymmetric Conjugate Addition Reactions of Alkenylaluminums to Trisubstituted Enones

Alkenylaluminums undergo asymmetric copper‐catalyzed conjugate addition (ACA) to β‐substituted enones allowing the formation of stereogenic all‐carbon quaternary centers. Phosphinamine–copper complexes proved to be particularly active and selective compared with phosphoramidite ligands. After extensive optimization, high enantioselectivities (up to 96 % ee) were obtained for the addition of alkenylalanes to β‐substituted enones. Two strategies for the generation of the requisite alkenylaluminums were explored allowing for the introduction of aryl‐ and alkyl‐substituted alkenyl nucleophiles. Moreover, alkyl‐substituted phosphinamine (SimplePhos) ligands were identified for the first time as highly efficient ligands for the Cu‐catalyzed ACA.     

Preliminary study on aerosol particle addition calibration method for on-line quantitative analysis of airborne radioactive particles with ICP-MS

An ambient aerosol concentration enrichment system coupled with ICP-MS for real-time monitoring of airborne radioactive particles is now under development. ICP-MS is very sensitive to sample introduction conditions, so it is necessary to develop an easy-use calibration method for on-line quantitative analysis in field application. In this paper, a calibration method using standard solution instead of monodisperse particles was established and validated preliminarily. First of all, four parameters for the method were determined experimentally, including: uptake flow rate and nebulisation efficiency of the Microconcentric nebuliser, nebulisation/transport efficiency of Aridus Desolvating Sample Introduction System, and Relative Sensitivity Factor between ¹⁵⁹?Tb and ¹⁷⁴?Yb. Then, monodisperse terbium nitrate particles were generated by a commercial Vibrating Orifice Aerosol Generator. Continuous aerosols of ytterbium nitrate droplets were nebulised from standard solution. They were mixed together, desolvated through the membrane dryer and introduced into ICP-MS for on-line analysis of terbium nitrate particles. The air sampled from nuclear environment was also introduced into ICP-MS to investigate the effect of flow rate on instrument responses. Finally, atom numbers of ¹⁵⁹?Tb in discrete terbium nitrate particles were determined using the calibration method and compared to the calculated value. Results show that when air flow rate increase from 10?mL?min^?1 to 100?mL?min^?1, the ratio of ¹⁵⁹?Tb ion count to ¹⁷⁴?Yb ion intensity keeps constant although instrument sensitivity decreases by a factor of 25. The relative standard deviation of ¹⁵⁹?Tb atom number measured is better than 18%. The discrepancy with the calculated value could be attributed to the over-estimation of atom number in the particles generated by VOAG because there was some liquid leakage in the VOAG.     

STUDIES OF HETEROCYCLIC COMPOUNDS: VI1 THE MASS SPECTRA OF SOME 2-THIOPHENEMERCURIC DERIVATIVES

Abstract

The mass spectra of some 2-thiophenemercuric derivatives are determined and the fragmentation interpretations are based on mechanistic analogy and supported in some cases by metastable peaks and low energy mass spectra. They all fragment ultimately to the 2-thienyl cation formed either through a two-step process, by cleavage of Hg[sbnd]X bond to give the 2-thienylmercuric cation, followed by extrusion of mercury, or by a one-step process through cleavage of carbon-mercury bond. Their base peaks being the C₃H₃ ⁺ion (m/e 39).