Halide-selective sequence

We found that the anion transport by neutral NDI rigid-rod discriminates a halide-selective sequence (CD > F" > Br > T) and the NDI rigid-rod with one... 

Kinetic studies have shown that the enolate and phosphorus nucleophiles all react at about the same rate. This suggests that the only step directly involving the nucleophile (step 2 of the propagation sequence) occurs at essentially the diffusion-controlled rate so that there is little selectivity among the individual nucleophiles. The synthetic potential of the reaction lies in the fact that other substituents which activate the halide to substitution are not required in this reaction, in contrast to aromatic nucleophilic substitution which proceeds by an addition-elimination mechanism (see Seetion 10.5). 

Oxathiane 101 is readily deprotonated using s-BuLi, and the resulting anion reacts with alkyl halides, ketones, and benzonitrile (85JOC657). The majority of work in this area, however, is due to Eliel and coworkers and has involved chiral 1,3-oxathianes as asymmetric acyl anion equivalents. In the earliest work it was demonstrated that the oxathianes 102 and 103, obtained in enantiomeri-cally pure form by a sequence involving resolution, could be deprotonated with butyllithium and added to benzaldehyde. The products were formed with poor selectivity at the new stereocenter, however, and oxidation followed by addition... 

Sequence-specific biosensor, 183, 185 Selectivity, 92, 143, 147, 155 Selectivity coefficient, 143 Self-assembled monolayers, 39, 118 Selenium, 85 Sensor, 171 Silver halide, 159 Simulation, 35... 

Certain esters have often been employed in attempts to confer organ selectivity to molecules possessing carboxyl functions. Thus, for example, treatment of piperidinecarboxylic acid 76 with N-hydroxysuccinimide and DCC affords the ester 77. In a convergent synthesis, the anion from diphenylacetonitrile (78) is alkylated with dibromoethane to afford the bromide 79. Alkylation of the piperidine derivative 77 with that halide 79 gives the anti-diarrheal agent difenoximide (80). The same sequence starting with the phenoxyethyl ester 81 gives fetoxylate (82). 

As an example of the selective reactivity of borazirconocene alkenes, their hydrolysis was examined [1]. The carbon—zirconium bond is more reactive than the carbon—boron bond towards various electrophiles, and so hydrolysis can be expected to occur with preferential cleavage of the former bond. Since hydrolysis of alkenylzirconocenes is known to proceed with retention of configuration [4,127—129], a direct utility of 45 is the preparation of (Z)-1-alkenylboronates 57 (Scheme 7.17) [12]. Though the gem-dimetalloalkenes can be isolated, in the present case it is not necessary. The desired (Z)-l-alkenylboronates can be obtained in a one-pot procedure by hydrozirconation followed by hydrolysis with excess H20. The reaction sequence is operationally simple and is compatible with various functional groups such as halides, acetals, silanes, and silyloxy protecting groups [12]. 

Thermodynamic data reported in Table 2 reflect the affinity of these calix[4]pyrrole derivatives for the fluoride relative to other anions. Among the halides the selectivity trend follows the sequence... 

The palladium-catalyzed formation of diarylamines has been used in several contexts to form molecules with biological relevance. The ability to prepare haloarenes selectively by an ortho-metallation halogenation sequence allows for the selective delivery of an amino group to a substituted aromatic structure. Snieckus has used directed metallation to form aryl halides that were subsequently reacted with anilines to prepare diarylamines (Eq. 34)) [156]. Frost and Mendon a have reported an iterative strategy to prepare (by palladium-catalyzed chemistry) amides and sulfonamides that may act as peptidomimetics. Diarylamine units are constructed using the DPPF-ligated palladium catalysts, and the products are then acylated or sulfo-nated with 4-bromo benzoyl or arylsulfonyl chlorides [157]. 

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