Stereochemical lability

All have pyramidal molecules (Cj point group for OSX2), and OSFCl is chiral though stereochemically labile. Dimensions are in Table 15.14 the short O-S distance is notable. The unstable compound OSI2 was mentioned on p. 692. 

On the other hand, the fluorine-induced addition of the diastereomeric silyl-subsliluted sulfides 36 A and 36B to benzaldehyde proceeds without loss of stereochemical information and with retention of configuration32. Since, however, the anionic reagent 35A/35B is known to be configurationally labile, the observed retention of configuration in the fluorine-induced desi-lylative hydroxy alkylation lends experimental evidence to the notion that these reactions proceed via hypervalent silicon species rather than anionic reagents. 

After 12 hours at 4 kbar. this reaction provided only 35% of a 63 27 mixture of 22 and a compound which was tentatively assigned structure 23. It is assumed that 23 derives from epimerization of 21 prior to reaction with (aS,S,S)-5l0b. Whether this stereochemical assignment is correct or not, this result shows that 5 may have problems with configurationally labile aldehydes in demanding cases of mismatched double diastereosclcction. For further examples of double asymmetric induction with 5 or related reagents, see refs 31, 34 and 47. 

As already mentioned, complexes of chromium(iii), cobalt(iii), rhodium(iii) and iridium(iii) are particularly inert, with substitution reactions often taking many hours or days under relatively forcing conditions. The majority of kinetic studies on the reactions of transition-metal complexes have been performed on complexes of these metal ions. This is for two reasons. Firstly, the rates of reactions are comparable to those in organic chemistry, and the techniques which have been developed for the investigation of such reactions are readily available and appropriate. The time scales of minutes to days are compatible with relatively slow spectroscopic techniques. The second reason is associated with the kinetic inertness of the products. If the products are non-labile, valuable stereochemical information about the course of the substitution reaction may be obtained. Much is known about the stereochemistry of ligand substitution reactions of cobalt(iii) complexes, from which certain inferences about the nature of the intermediates or transition states involved may be drawn. This is also the case for substitution reactions of square-planar complexes of platinum(ii), where study has led to the development of rules to predict the stereochemical course of reactions at this centre. 

Bohle and co-workers (133) have demonstrated that varying the electronic and stereochemical properties of porphyrin substituents can strongly influence the rates of NO labilization (Eq. (11)). For example, the displacement of NO from Fe(TPP)(NO) by pyridine is many orders of magnitude slower than from Fe(OBTPP)(NO) (OBTPP = octabromo-tetraphenylporphyrin). An analysis of the kinetics of the latter reaction indicated saturation in [L], and the mechanism was suggested to involve reversible formation of Fe(OBTPP)(L)(NO) followed by NO dissociation (Eq. (50)). Clearly changes in porphyrin properties can lead to enhanced reactivity toward NO loss. 

In addition to providing a novel approach to the preparation of chiral compounds, this type of chemistry may allow one to inquire into the subtle stereochemical details of some crystal-state reactions. For example, what are the approach geometry and the preferred side of attack in the addition of bromine to a chiral olefin (259) What can be learned of the geometry of the labile electronically excited species involved in (2 + 2) photocycloaddition reactions (260) ... 

The reductant may be optically stabilized by using optically active forms of the coordinated ligand. Such ligands may impose stereochemical restraints even with labile oxidation states... 

The aquated Co(III) ion is a powerful oxidant. The value of E = 1.88 V (p = 0) is independent of Co(III) concentration over a wide range suggesting little dimer formation. It is stable for some hours in solution especially in the presence of Co(II) ions. This permits examination of its reactions. The CoOH " species is believed to be much more reactive than COjq Ref. 208. Both outer sphere and substitution-controlled inner sphere mechanisms are displayed. As water in the Co(H20) ion is replaced by NHj the lability of the coordinated water is reduced. The cobalt(III) complexes which have been so well characterized by Werner are thus the most widely chosen substrates for investigating substitution behavior. This includes proton exchange in coordinated ammines, and all types of substitution reactions (Chap. 4) as well as stereochemical change (Table 7.8). The CoNjX" entity has featured widely in substitution investigations. There are extensive data for anation reactions of... 

Allylic a-bromo boronic l,l,2,2-tctramethyl-l,2-ethanediyl esters are too labile to permit preparation in high stereochemical purity. Finacol l-bromo-2-propenylboronate with sodium methoxideyields 1-methoxy-2-propenyl boronic l,l,2,2-tetramethyl-l,2-ethanediyl ester54. Attempted conversion of the corresponding chloro boronic ester to alkoxy derivatives failed54. 

The isomers cis- and trans-[Cr(CN)2(NH3)4]+ as well as m-[Cr(CN)(NH3)4DMS0](G04)2 have also been synthesized by the anation reactions shown in Scheme 29.325 While anation in DMSO is accompanied by stereochemical change, the reaction in H20 is stereoretentive. The dicyano complexes undergo H+-assisted thermal aquation, involving the successive loss of the CN- ligands. The trans complex is about ten-fold more reactive in the first step than the cis, an observation attributed to the trans labilizing effect of CN-. 

Dynamic Resolution of Chirally Labile Racemic Compounds. In ordinary kinetic resolution processes, however, the maximum yield of one enantiomer is 50%, and the ee value is affected by the extent of conversion. On the other hand, racemic compounds with a chirally labile stereogenic center may, under certain conditions, be converted to one major stereoisomer, for which the chemical yield may be 100% and the ee independent of conversion. As shown in Scheme 62, asymmetric hydrogenation of 2-substituted 3-oxo carboxylic esters provides the opportunity to produce one stereoisomer among four possible isomers in a diastereoselective and enantioselective manner. To accomplish this ideal second-order stereoselective synthesis, three conditions must be satisfied (1) racemization of the ketonic substrates must be sufficiently fast with respect to hydrogenation, (2) stereochemical control by chiral metal catalysts must be efficient, and (3) the C(2) stereogenic center must clearly differentiate between the syn and anti transition states. Systematic study has revealed that the efficiency of the dynamic kinetic resolution in the BINAP-Ru(H)-catalyzed hydrogenation is markedly influenced by the structures of the substrates and the reaction conditions, including choice of solvents. 

Paul Pfeiffer discovered a very interesting stereochemical phenomenon, which now bears his name — the Pfeiffer effect this has received a good deal of attention.30 When an optically active substance which is stable in solution is added to a solution of a labile chiral substance, the optical rotation of the solution changes, reaching a new level in some hours. Several theories have been advanced to explain the phenomenon, the most satisfactory based on the supposition that the optically active ion or molecule forms an association with one isomer of the racemic pair of the labile substance and thus shifts the dextro—levo equilibrium. In general it is not possible to use this as a means of resolution, for when the added optically active substance is removed from the labile material, the latter immediately racemizes. 

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