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A new method to investigate the reaction kinetics of intermediates in solution by electrospray ionization mass spectrometry is presented. The method, referred to as delayed reactant labeling, allows investigation of a reaction mixture containing isotopically labeled and unlabeled reactants with different reaction times. It is shown that we can extract rate constants for the degradation of reaction intermediates and investigate the effects of various reaction conditions on their half-life. This method directly addresses the problem of the relevance of detected gaseous ions toward the investigated reaction solution. It is demonstrated for geminally diaurated intermediates formed in the gold mediated addition of methanol to alkynes. Delayed reactant labeling allows us to directly link the kinetics of the diaurated intermediates with the overall reaction kinetics determined by NMR spectroscopy. It is shown that the kinetics of protodeauration of these intermediates mirrors the kinetics of the addition of methanol demonstrating they are directly involved in the catalytic cycle. Formation as well as decomposition of diaurated intermediates can be drastically slowed down by employing bulky ancillary ligands at the gold catalyst; the catalytic cycle then proceeds via monoaurated intermediates. The reaction is investigated for 1-phenylpropyne (Ph-CC-CH3) using [AuCl(PPh3)]/AgSbF6 and [AuCl(IPr)]/AgSbF6 as model catalysts. Delayed reactant labeling is achieved by using a combination of CH3OH and CD3OH or Ph-CC-CH3 and Ph-CC-CD3.

Metabolites of the wood-rotting fungus Stereum subtomentosum Pouzar (Basidiomycetes, order Russulales, family Stereaceae) occurring on birch (Betula pendula Roth) trees were phytochemically investigated for the first time. Three main metabolite chemotypes present in MeOH extracts of the fruit bodies, viz. steroids, fatty acids, and water-soluble sugars, were fractionated, isolated, and identified by 1D/2D NMR-spectroscopic analyses, NMR data comparisons, and chemical correlations combined with GC/MS experiments. Thirteen compounds including two 5 alpha,8 alpha-epidioxy steroids, alpha,alpha'-trehalose, D-arabinitol, D-mannitol, and saturated/unsaturated fatty acids, were identified. Differences among S. subtomentosum and two other birch-associated fungal species, Trametes versicolor (L.: Fr.) Pilát, and Piptoporus betulinus (Bull.: Fr.) P. Karst (Basidiomycetes, order Polyporales, family Polyporaceae) were evaluated as regards the richness and abundance relationships in metabolite profiling.

SummaryAn efficient synthetic route toward the preparation of a complete series of monosubstituted tetraalkylammonium cyclodextrin (CD) derivatives is presented. Monotosylation of native CDs (α-, β-, γ-) at position 6 gave the starting material. Reaction of monotosylate (mono-Ts-CD) with 45% aqueous trimethylamine gave CDs substituted with one cationic functional group in a single step. Derivatives equipped with a substituent containing two cationic sites separated by an ethylene or a propylene linker were prepared by reacting mono-Ts-CD with neat N,N,N’-trimethylethane-1,2-diamine or N,N,N’-trimethylpropane-1,3-diamine and subsequent methylation by CH3I in good yields. Finally, analogues bearing a moiety with three tetraalkylammonium sites were synthesized by reacting mono-Ts-CD with bis(3-aminopropyl)amine and subsequent methylation. The majority of the presented reactions are very straightforward with a simple work-up, which avoids the need of chromatographic separation. Thus, these reactions are suitable for the multigram-scale production of monosubstituted cationic CDs.

The reaction mechanism of a tandem conjugate addition/α-alkylation of enals leading to functionalized cyclopentanes catalyzed by O-trimethylsilyldiphenylprolinol was investigated by mass spectrometry, NMR spectroscopy, and DFT calculations. We have shown that the high stereoselectivity of the reaction depends on the energy discrimination between the two stereoisomers formed by the condensation of the α,β-unsaturated aldehyde (cinnamaldehyde) and the catalyst. The stereoselectivity of this step depends on the solvent used. The experimental activation barriers were determined to be E(a) = 25 ± 7 kJ mol(-1) (Arrhenius equation), ΔH(‡) = 23 ± 7 kJ mol(-1), and ΔG(‡) = 101 ± 9 kJ mol(-1) (Eyring equation).

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A series of unsymmetrically substituted diastereoisomeric (Ra,R) and (Sa,R) bipyridine N,N′‐dioxides was synthesized by using oxidative coupling of the corresponding metallated tetrahydroisoquinoline N‐oxides in the presence of iodine. The N,N′‐dioxides contained substituted aryl groups with electron‐donating or electron‐accepting groups in the near vicinity of the N,N′‐dioxide moiety. Their catalytic activity was tested in a series of reactions of allyltrichlorosilane with various substituted benzaldehydes, thiophenecarbaldehyde, and cinnamaldehyde. The reactions proceeded with high enantioselectivities (up to 98 % ee) with catalyst loadings as low as 0.5 mol‐%. Furthermore, allylation reactions of (E)‐3‐iodomethacrylaldehyde were also carried out to give chiral (E)‐1‐iodo‐2‐methylpenta‐1,4‐dien‐3‐ol, a convenient building block for the synthesis of natural products. The allylations proceeded with high enantioselectivities (up to ca. 99 % ee) with a catalyst loading of 2.5 mol‐%.

The highly stereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with β-ketoesters catalysed by β-ICD is described. The corresponding products containing two adjacent quaternary and tertiary carbon centers were obtained in good yields with high diastereoselectivity (up to 10 : 1 dr) and enantioselectivity (up to 95% ee).