Formation and characterization of the sulfur-containing distonic radical anion,E.CH2-S-E-CHCN, in the gas phase

The reactions of the atomic oxygen radical anion O−• with CH3SCH2CN in the gas phase have been examined with Fourier transform ion cyclotron resonance in combination with tandem mass spectrometric experiments performed with a double-focusing quadrupole hybrid instrument. Deuterium labeling has revealed that the O−• ion reacts with CH3SCH2CN by proton abstraction from the methylene group as well as by competing 1,1- and 1,3-H2+• abstractions to afford isomeric radical anions. High kinetic energy (8 keV) collision-induced charge reversal experiments indicate that the 1,1-H2+•-abstraction leads to a CH3SC̄CN carbene ion, whereas the 1,3-H2+• abstraction yields a novel sulfur-containing distonic radical anion, which is formulated as CH2SC̄HCN

Chemical ionization of phenyl n-propyl ether and methyl substituted analogs: propene loss initiated by competing proton transfer to the oxygen atom and the aromatic ring.

The mechanism of propene loss from protonated phenyl n-propyl ether and a series of mono-, di-, and trimethylphenyl n-propyl ethers has been examined by chemical ionization (CI) mass spectrometry in combination with tandem mass spectrometry experiments. The role of initial proton transfer to the oxygen atom and the aromatic ring, respectively, has been probed with the use of deuterated CI reagents, D2O, CD3OD, and CD3CN (given in order of increasing proton affinity), in combination with deuterium labeling of the β position of the n-propyl group or the phenyl ring. The metastable [M + D]+ ions of phenyl n-propyl ether—formed with D2O as the CI reagent—eliminate C3H5D and C3H6 in a ratio of 10:90, which indicates that the added deuteron is incorporated to a minor extent in the expelled neutral species. In the experiments with CD3OD as the CI reagent, the ratio between the losses of C3H5D and C3H6 from the metastable [M + D]+ ions of phenyl n-propyl ether is 18:82, whereas the ratio becomes 27:73 with CD3CN as the reagent. A similar trend in the tendency to expel a propene molecule that contains the added deuteron is observed for the metastable [M + D]+ ions of phenyl n-propyl ether labeled at the β position of the alkyl group. Incorporation of a hydrogen atom that originates from the aromatic ring in the expelled propene molecule is of negligible importance as revealed by the minor loss of C3H5D from the metastable [M + H]+ ions of C6D5OCH2CH2CH3 irrespective of whether H2O, CH3OH, or CH3CN is the CI reagent. The combined results for the [M + D]+ ions of phenyl n-propyl ether and deuterium-labeled analogs are suggested to be in line with a model that assumes that propene loss occurs not only from species formed by deuteron transfer to the oxygen atom, but also from ions generated by deuteron transfer to the ring. This is substantiated by the results for the methyl-substituted ethers, which reveal that the position as well as the number of methyl groups bonded to the ring exert a marked effect on the relative importances of the losses of C3H5D and C3H6 from the metastable [M + D]+ ions of the unlabeled methyl-substituted species

Consecutive Pictet-Spengler Condensations toward Bioactive 8-Benzylprotoberberines: Highly Selective Total Syntheses of (+)-Javaberine A, (+)-Javaberine B, and (-)-Latifolian A

Enantiopure 8-benzylprotoberberines were synthesized by two consecutive Pictet-Spengler (PS) condensations with protected 3,4-dihydroxyphenylacetaldehydes. The first PS to (+)-(R)-norprotosinomenine was optimized to 90 % ee with 5 mol-% of (R)-TRIP as chiral Bronsted acid (> 99 % ee after trituration). The second PS did not require any catalyst, and its regioselectivity was strongly dependent on the solvent: 99: 1 para selectivity was obtained in trifluoroethanol leading to (+)javaberine A; 81: 19 ortho selectivity was reached in apolar aprotic solvents for the synthesis of (+)-javaberine B. Complete, natural diastereoselectivity was observed in the second PS. Through selective catechol oxidation the spirocyclic alkaloid (-)-latifolian A was prepared from protected (+)-javaberine A