Gas-phase facial diastereoselectivity of equatorial and axial 4-chloro-adamant-2-yl cations.

The acid-catalyzed addition of CH3(18)OH to 2-methylene-adamantanes bearing a chlorine atom in the 4-equatorial (1e) or 4-axial (1a) position has been investigated in the gas phase, at 760 Torr, in the 40-120 degrees C temperature range. Two different experimental approaches were employed: (1) by adding neutral CH3(18)OH to the 2-methyl-4-Cl-adamant-2-yl cation, generated by protonation of the corresponding 2-methylene-4-Cl-adamantane (the extracomplex reaction) and (2) by reaction of 2-methylene-4-Cl-adamantane with CH3(18)OH2+, generated by methylation of H2(18)O (the intracomplex reaction). The crucial role of the nature of the noncovalent intermediates involved along the reaction coordinates emerges from the difference between the results obtained in the extracomplex and intracomplex reactions for both substrates investigated. The kinetic and stereochemical results indicate that the 4-Cl substituent plays a different role depending on its equatorial or axial orientation. Examination of the experimental results in the light of MP2/6-31G* theoretical calculations provides important information about the intrinsic factors governing the facial diastereoselectivity of trigonal carbocations. The effects due to differential face solvation phenomena emerge from the comparison of the present gas-phase results with those obtained from strictly related studies in solution.

Gas-phase enantioselectivity of chiral N-linked peptidoresorc[4]arene isomers toward dipeptides.

The gas-phase enantioselectivity of cone N-linked peptidoresorc[4]arenes (generally symbolized as M) toward the homologue dipeptides (generally symbolized as A) has been evaluated by measuring the kinetics of the A release from the diastereomeric [M x H x A](+) complexes induced by (R)-(-)-2-butylamine (B). In most cases investigated, the heterochiral [M x H x A](+) complexes, namely those wherein the configuration of the A guest is opposite to that of the host M pendants, react faster (up to 5 times) than the homochiral analogues, wherein guest A guest has the same configuration of the host M pendants. The kinetic results, discussed in the light of previous MS and NMR evidence, indicate that both the efficiency and the enantioselectivity of the guest exchange reaction depend essentially on the structure and the relative stability of the diastereomeric [M x H x A](+) complexes. These, in turn, depend on the functional groups and the configuration of both the guest and the host pendants. The absence of any significant effects of the B configuration indicates that, in all systems investigated, the dipeptide guest A is predominantly located outside the host chiral cavity.

Interactions of vinca alkaloid subunits with chiral amido[4]resorcinarenes: a dynamic, kinetic, and spectroscopic study.

The stereoselectivity of the reaction between (R)-(-)-2-butylamine and the diastereomeric proton-bound complexes of (+)-catharanthine (C) or (-)-vindoline (V) with some chiral amido[4]resorcinarenes has been investigated in the gas phase by ESI-FT-ICR-MS. The reaction stereoselectivity (0.56 < k(homo)/k(hetero) < 16.9) is found to depend critically on the functional groups present in the chiral pendants of the hosts. Rationalisation of the kinetic results is based on careful computational and spectroscopic studies of the most stable conformations of (+)-catharanthine and its protonated form in the isolated state and in water, as well as in a representative host structure. The emerging picture points to the relevant diastereomeric proton-bound complexes as quasi-degenerate, thus suggesting that their stereoselectivity in the guest exchange reaction is mostly due to kinetic factors. The results of this study may represent a starting point for a deeper comprehension of the intrinsic factors that endow these molecules, and their dimeric forms, with their biochemical properties.

A kinetic study of guest displacement reactions on a host-guest complex with a photoswitchable calixarene.

The displacement processes of several guests, incorporated in a calixarene host system, were investigated in the gas phase by electrospray ionization-Fourier transform-ion cyclotron resonance (ESI-FT-ICR) mass spectrometry. The complexes resulting from a resorcin[4]arene host with ammonia and sec-butylamine guests were isolated in an ICR-cell, separately using both states of the photoswitch as well as two reference systems for the open and closed forms of the photoswitchable host. The isolated complexes were forced to exchange the guest by using methylamine, ethylamine and sec-butylamine, resulting in different reaction rates for all the measured systems. Especially, the reaction rates of both states of the photoswitch are dependent on the provided guest. Potential side effects like proton exchanges were examined by an H/D-exchange experiment. The results were investigated and supported by quantum chemical calculations (DFT).

Generation and reactivity of enantiomeric (BINOLato)Ni+ complexes with chiral secondary alcohols in the gas phase.

In the presence of secondary alcohols, electrospray ionization of dilute methanolic solutions of nickel(II) salts and 1,1'-bis-2-naphthol (BINOL) leads to complexes of the formal composition [(BINOLato)Ni(CH3CH(OH)R)]+ (BINOLato refers to a singly deprotonated (R)- or (S)-1,1'-bis-2-naphthol ligand; R=CH3, C2H5, n-C3H7, n-C4H9, n-C5H11, n-C6H13, c-C6H11, and C6H5). Upon collision-induced dissociation, each mass-selected nickel complex either loses the entire secondary alcohol ligand or undergoes bond activation followed by elimination of the corresponding ketone, as revealed by deuterium labeling. When enantiomeric BINOLato ligands (R or S) are combined with chiral secondary alcohols (R or S), differences in the branching ratios between these channels for the two stereoisomers of the secondary alcohols provide insight into the chiral discrimination operative in the C--H- and O--H-bond activation processes. For saturated alkan-2-ols, the chiral discrimination is low, and if any preference is observed at all, ketone elimination from the homochiral complexes (R,R and S,S) is slightly favored. In contrast, the diastereomeric (BINOLato)Ni+ complexes of 1-phenylethanol exhibit preferential ketone losses for the heterochiral systems (S,R and R,S).

Gaseous iron(II) and iron(III) complexes with BINOLate ligands.

Electrospray ionization (ESI) of dilute solutions of 1,1'-bi-2-naphthol (BINOL) and iron(II) or iron(III) sulfate in methanol/water allows the generation of monocationic complexes of iron and deprotonated BINOL ligands with additional methanol molecules in the coordination sphere, and the types of complexes formed can be controlled by the valence of the iron precursors used in ESI. Thus, iron(II) sulfate leads to [(BINOLate)Fe(CH3OH)n]+ complexes (n=0-3), whereas usage of iron(III) sulfate allows the generation of [(BINOLdiate)-Fe(CH3OH)n]+ cations (n=0-2); here, BINOLate and BINOLdiate stand for singly and doubly deprotonated BINOL, respectively. Upon collision-induced dissociation, the mass-selected ions with n>0 first lose the methanol ligands and then undergo characteristic fragmentations. Bare [(BINOLdiate)Fe]+, a formal iron(III) species, undergoes decarbonylation, which is known as a typical fragmentation of ionized phenols and phenolates either as free species or as the corresponding metal complexes. The bare [(BINOLate)Fe]+ cation, on the other hand, preferentially loses neutral FeOH to afford an organic C20H12O+* cation radical, which most likely corresponds to ionized 1,1'-dinaphthofurane.

Gas-phase diastereoselectivity of secondary 5-substituted (X)-adamant-2-yl (X = F, Si(CH(3))(3)) cations.

Secondary 5-X-adamant-2-yl cations IX (X = F, Si(CH3)3) have been generated in the gas phase (total pressure = 760 Torr) from protonation-induced defluorination of epimeric 2-F-5-X-adamantanes 1X and their kinetic diastereoselectivity toward CH318OH investigated in the 40-160 degrees C range. The experimental results indicate that the facial selectivity of IX is insensitive to the composition of the starting 1X epimers as well as to the presence and the concentration of a powerful base (N(C2H5)3). This kinetic picture, supported by B3LYP/6-31G* calculations, is consistent with a single stable pyramidalized structure for IX, that is, (Z)-5-F-adamant-2-yl (I(Z)F) and (E)-5-Si(CH3)3-adamant-2-yl cations (I(E)Si). The temperature dependence of the IX diastereoselectivity lends support to the intermediacy of noncovalent adducts [IX*CH318OH], characterized by a specific C2-H+...O18(H)CH3 hydrogen bonding interaction. Their conversion to the covalently bonded O-methylated (Z)- (II(Z)X) and (E)-5-X-adamantan-2-ols (II(E)X; X = F, Si(CH3)3) is governed by activation parameters, whose magnitude depends on the specific IX face accommodating CH318OH. The gas-phase diastereoselectivity of IX toward CH318OH is compared to that exhibited in related gas-phase and solution processes. The emerging picture indicates that the factors determining the diastereoselectivity of IX toward simple nucleophiles in the gaseous and condensed media are completely different.