The first example of alpha-thiomagnesiums generated from dithioacetal monoxides with Grignard reagent; their properties and some synthetic applications

Dithioacetal monoxides were synthesized from aldehydes and cyclohexanone, and reaction of the dithioacetal monoxides with Grignard reagents was investigated. The dithioacetal monoxide synthesized from alkylaldehyde and 4-chlorobenzenethiol reacted with i-PrMgCl to afford the desired alpha-thiomagnesium in high yield. The generated alpha-thiomagnesium was found to be stable at room temperature and to be useful in organic synthesis. In contrast to this, the dithioacetal monoxides derived from benzaldehyde and cyclohexanone did not give satisfactory results.     

Synthesis of block and end‐functionalized polyesters by triflimide‐catalyzed ring‐opening polymerization of ε‐caprolactone, 1,5‐dioxepan‐2‐one,and rac‐lactide

The ring‐opening polymerization (ROP) of cyclic esters, such as ε‐caprolactone, 1,5‐dioxepan‐2‐one, and racemic lactide using the combination of 3‐phenyl‐1‐propanol as the initiator and triflimide (HNTf₂) as the catalyst at room temperature with the [monomer]₀/[initiator]₀ ratio of 50/1 was investigated. The polymerizations homogeneously proceeded to afford poly(ε‐caprolactone) (PCL), poly(1,5‐dioxepan‐2‐one) (PDXO), and polylactide (PLA) with controlled molecular weights and narrow polydispersity indices. The molecular weight determined from an ¹H NMR analysis (PCL, M_n,NMR = 5380; PDXO, M_n,NMR = 5820; PLA, M_n,NMR = 6490) showed good agreement with the calculated values. The ¹H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry analyses strongly indicated that the obtained compounds were the desired polyesters. The kinetic measurements confirmed the controlled/living nature for the HNTf₂‐catalyzed ROP of cyclic esters. A series of functional alcohols, such as propargyl alcohol, 6‐azido‐1‐hexanol, N‐(2‐hydroxyethyl)maleimide, 5‐hexen‐1‐ol, and 2‐hydroxyethyl methacrylate, successfully produced end‐functionalized polyesters. In addition, poly(ethylene glycol)‐block‐polyester, poly(δ‐valerolactone)‐block‐poly(ε‐caprolactone), and poly(ε‐caprolactone)‐block‐polylactide were synthesized using the HNTf₂‐catalyzed ROP. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2455–2463     

Synthesis of 2-azabicyclo[2.1.0]pentanes by the intramolecular nucleophilic substitution of cyclopropylmagnesium carbenoids with magnesium anilide

A variety of 2-azabicyclo[2.1.0]pentanes were synthesized by the intramolecular nucleophilic substitution of cyclopropylmagnesium carbenoids with magnesium anilide. The 1-chlorocyclopropyl p-tolyl sulfoxides possessing an N-aryl-substituted aminomethyl group were prepared from dichloromethyl p-tolyl sulfoxide, α,β-unsaturated carboxylic acid esters, and anilines in four steps. The deprotonation of the amine with t-BuMgCl followed by sulfoxide/magnesium exchange of the sulfoxides with i-PrMgCl led to the generation of the cyclopropylmagnesium carbenoids possessing a magnesium anilide moiety. Subsequent intramolecular nucleophilic substitution of the cyclopropylmagnesium carbenoids occurred in a 4-exo-tet manner to give the 2-azabicyclo[2.1.0]pentanes. The optically active 2-azabicyclo[2.1.0]pentane was synthesized using a p-tolylsulfinyl group as a chiral auxiliary.     

光谱法研究1,3-硫杂杯[4]罗丹明乙二胺酰胺衍生物对Fe3+的探针性能

利用硫杂杯[4]芳烃衍生物与罗丹明乙二胺发生酰化反应,合成了2个具有双罗丹明基团的1,3-硫杂杯[4]罗丹明乙二胺酰胺衍生物.在实验条件下,衍生物与Fe3+均能形成1:1配合物,配合物的形成诱导了衍生物分子中罗丹明基螺环开环,而表现出良好的荧光和比色探针性能.1,3-硫杂杯[4]罗丹明酰胺-2,4-酯对Fe3+的选择性...