Controlled tautomerism complexation

The tautomerization is induced by cobalt(II) which forms the thermodynamically more stable metalatcd hydroporphyrins from which the cobalt can be removed using trifluoroacctic acid under kinetic control. Experiments with porphyrinogen and hexahydroporphyrin show that the porphyrinogen-hexahydroporphyrin equilibrium can be shifted by complexation of porphyrinogen with metal ions to the more stable metal hexahydroporphyrins and that metal-free hexahydroporphyrins tautomerize back to the more stable metal-free porphyrinogens.29... 

The different ratios of 52/53 produced by cycloadditions performed at atmospheric and high pressure, and the forma tion of the unusual trans adducts 53, have been explained by the facts that (i) Diels-Alder reactions under atmospheric pressure are thermodynamically controlled, and (ii) the anti-endo adducts 52 are converted into the short-lived syn-endo adducts 54 which tautomerize (via a dienol or its aluminum complexes) to 53. The formation of trans compounds 53 by induced post-cycloaddition isomerization makes the method more flexible and therefore more useful in organic synthesis. 

The pH dependence of the hydrolysis of all compounds studied is, in principle, consistent with the mechanism of Scheme 6 that applies to the alkoxyphenylcarbene complexes, and so are the products of the reactions of 68, 66 and 8. However, the products obtained in the hydrolysis of 144 and the fact that in basic solution the hydrolysis of all the compounds is subject to a substantial kinetic solvent isotope effect are inconsistent with Scheme 6, at least at pH >8.5. The mechanism that accounts best for all experimental observations at pH >8.5, including the isotope effect, is shown in Scheme 17 for the example of 68. It involves rapid deprotonation of 68 followed either by slow protonation of 135 with water ( 2 )) or a buffer acid (fe [BH]) and subsequent rapid conversion of 161 to 162, or slow concerted water (fe2c) or buffer acid catalyzed (fe [BH]) conversion of 135 to 162 (more on these two alternatives below). Complexation between (CO)sCr and the enol ether activates the latter toward basic hydrolysis which rapidly leads to the vinyl alcohol and tautomerization to the aldehyde. Control experiments demonstrated that the kind of complexation indicated by 162 indeed promotes rapid hydrolysis of the enol ether. ° In the reactions of 144 complexation of the enol ether ()8-methoxystyrene) appears to be weak, presumably because of steric crowding, and hence the reaction... 

Abstract. Very successful stereo-, regio-, and enantio-controls of the photoreaction of a guest compound were achieved by irradiation of the host-guest complex in the sohd state. In order to discover the reason for the successful control, the X-ray crystal structure of the complex was studied. The complexation method was also effective to freeze the equilibrium in solution and isolate the labile tautomeric isomer as an inclusion complex. 

The control of stereochemistry with chromium carbine complexes has been reviewed. The DBR can create a new stereocenter in three ways. First, the arene tricarbonyl chromium complex contains a plane of chriality, thus the complexes 35 and ent-35 are enantiomers when RL Ri and RS R2. Second, when phenyl substituents are included in the reactants the resulting biaryls can posess axial chirality if there is hindered rotation about the new aryl-aryl bond as in 36. Finally, all DBRs with differentially p-disubstitued alkenes give rise to cyclohexadienones 37 with a new stereocenter adjacent to the carbonyl. When Ri and R2 are not hydrogen, tautomerization cannot occur and the final product possesses a chiral center. 

Complexes bearing protic NHC ligands are accessible by various synthetic routes such as the deprotonation of azoles followed by reaction with a transition metal complex, the template-controlled cyclization of functionalized isocyanides, and the oxidative addition of different azoles to transition metal complexes. The complexes with simple monodentate NR,NH-NHCs often tend to tautomerize to give the N-bound azoles. This type of tautomerization is prevented in complexes with donor-functionalized NR,NH-NHCs. Recent smdies demonstrate that complexes with protic NHCs obtained from C2-H azoles are formed by an oxidative addition/reductive elimination reaction sequence. The N—H group in complexes with protic NR,NH-NHCs can serve as a hydrogen bond donor and thus as a molecular recognition unit and may enable various types of bifunctional catalysis. Recent smdies indicate that even biomolecules such as caffeine can be C8-metallated. It... 

In this chapter, we discussed a number of examples of NH tautomerization, which demonstrate that a particular proton transfer reaction can be fine-tuned by chemical modifications, so that it may become controlled, either dynamically or thermodynamically. We also reviewed a crucial role played by hydrogen bonding in the complexation process, which may vary greatly, depending on the specific guest and host pair, as well as the solvent... 

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