Alkyl sulfonates alcohol inversion

Alkylation of hydroxylamines with secondary alkyl halides and alkyl sulfonates like 10 (equation 7) is one of the most frequently used synthetic approaches, especially to enantiomerically pure hydroxylamines such as 11 (equation 7). The reaction proceeds with inversion of configuration and does not produce appreciable amounts of diaUcyla-tion products. Both hydroxylamine as well as N- and O-alkylhydroxylamines have been successfully used. Alkyl trillates are probably the most useful substrates for these transformations since they can be prepared from a large pool of commercially available enantiomerically pure chiral secondary alcohols. 

The reactions of alkyl sulfonates with superoxide ion and with nitrite ion directly afford the corresponding inverted alcohols. - Although displacement by superoxide ion has been successfully utilized in prostaglandin chemistry, elimination again takes place to some extent, depending on the structures of the substrates. In the reaction with nitrite ion, ketone and nitroalkane are also formed. The inversion of cyclopentanol derivatives via tosylates has been studied by the use of various methods involving displacement by benzoate, nitrite ion and superoxide ion as well as the diethyl azodicarboxylate (DEAD)-PhsP procedure, where varied amounts of elimination products are invariably formed. ... 

Chiral derivatives of hemiacetal from fluoral have been prepared by adding an alcohol to fluoral in the presence of (l )-BlNOL— Ti(0—iPr)2 or by HPLC resolution of the racemate. The displacement of the sulfonate moiety from the tosyl derivative, by an alkyl lithium aluminate, affords the trifluoromethyl ether with inversion of configuration and an excellent chirality transfer (Figure 2.49). ° ... 

The sulfonyl halides (ArSOjCl) convert the alcohol into a sulfonate (ArSOjOR), which is a better leaving group than the hydroxyl group. This allows a range of nucleophilic substitutions to be carried out, many of which parallel those found with alkyl halides. Alkyl halides such as iodides are formed by the nucleophilic substitution of the sulfonate by an iodide ion. The reaction in this case proceeds with inversion of configuration. Treatment of the sulfonate esters with bases such as sodium methoxide or collidine (2,4,6-trimethylpyridine), or even just heating them, can lead to the elimination of toluene-4-sulfonic acid and the formation of an alkene. 

The phase behavior of surfactant formulations for enhanced oil recovery is also affected by the oil solubilization capacity of the mixed micelles of surfactant and alcohol. For low-surfactant systems, the surfactant concentration in oil phase changes considerably near the phase inversion point. The experimental value of partition coefficient is near unity at the phase inversion point (28). The phase inversion also occurs at the partition coefficient near unity in the high-surfactant concentration systems (31). Similar results were also reported by previous investigators (43) for pure alkyl benzene sulfonate systems. 

Inversion of configuration (cf Epimerization) of alcohols (Mitsunobu reaction), 160-161, 286 of ally lie acetates with Pd, 27, 164 of allylpalladium with d-synthons, 27, 264 of alkyl halides or sulfonates by 1,3-dithiane anions, 22 by organylcuprates, 36 by tetracarbonylferrate<2 -X 46-47 in triorganylborane rearr., 37-38 of glycosides with free 2-OH by DAST, 272 of glycosyl halides, 271 of oxiranes by 1-alkync anions, 64, 204 by enolate type anions, 63-64 by internal alcoholate addition, 265 Inversion-esterification of alcohols, 160-161, 286 Inverted DNA , 345-346 Iodide, hydrogen porphyrin synthesis with, 255 Iodine = diiodine (Ij) ... 

The reaction of primary alkyl bromides or sulfonate esters with potassium superoxide solubilized in benzene gives dialkyl peroxides, ROOR, as the major product. Significant amounts of alcohols and olefins are also formed. If the reaction is carried out in DMSO or DMSO-DMF, primary alcohols are formed very rapidly with inversion of configuration. Catalytic amounts of a crown ether are sufficient, but use of 1-2 eq. leads to a more rapid reaction. Secondary alcohols can be obtained, often in high yield, by this displacement reaction, but elimination predominates with tertiary substrates. This Sn2 reaction has been... 

The nucleophilicity of 02 - toward primary alkyl halides (Scheme 10) results in an Sn2 displacement of halide ion from the carbon center. The normal reactivity order, benzyl > primary > secondary > tertiary, and leaving group order, I > Br > OTs > Cl, are observed, as are the expected stereoselectivity and inversion at the carbon center. In DMF, the final product is the dialkyl peroxide. The peroxy radical (ROO-), which is produced in the primary step and has been detected by spin trapping,is an oxidant that is readily reduced by 02 - to form the peroxy anion (ROO ). Because the latter can oxygenate Me2SO to its sulfone, the main product in this solvent is the alcohol (ROH) rather than the dialkyl peroxide. 

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