Hydrogenation auxiliaries

Chips, semiconductor Chiral additives Chiral-AGP Chiral auxiliaries Chiral crown ethers Chiral hydrogenation Chirality... 

This thoroughly revised and updated new edition is a must for every synthetic organic chemist. New material has been added on homogene- ous diastereoselective hydrogenations, enantioselective oxidations, and novel chiral auxiliaries. 

Crystalline, diastereomerieally pure syn-aIdols are also available from chiral A-acylsultams. lhe outcome of the induction can be controlled by appropriate choice of the counterion in the cnolate boron enolates lead, almost exclusively, to one adduct 27 (d.r. >97 3, major adduct/ sum of all other diastereomers) whereas mediation of the addition by lithium or tin leads to the predominant formation of adducts 28. Unfortunately, the latter reaction is plagued by lower induced stereoselectivity (d.r. 66 34 to 88 12, defined as above). In both cases, however, diastereomerieally pure adducts are available by recrystallizing the crude adducts. Esters can be liberated by treatment of the adducts with lithium hydroxide/hydrogen peroxide, whereby the chiral auxiliary reagent can be recovered106. 

An efficient stereoselective Strecker synthesis of phenylglycine has been achieved using the tert-butyl ester tm-leucine as the chiral auxiliary. Its benzaldimine reacts with hydrogen cyanide in hexane at — 23 °C to furnish the ( )-diastereomer with the excellent diastereoselectivity of >98 254. 

The removal of the carbohydrate auxiliary group and the hydrolysis of the amino nitriles is achieved by acidolytic cleavage of the hemiaminal /V-glycosidic bond and the concomitant acid-catalyzed solvolysis of the nitrile using either hydrogen chloride in formic acid or hydrogen bromide in acetic acid56 57. 

Finally, the chiral auxiliary was removed by a Birch reduction or a catalytic hydrogenation. After ring opening several optically active 6-aminohexanoic acids served as linkers in cyclic peptides as /1-turn mimetics (Table 12, Scheme 49) [51c],... 

Scheme 33 Auxiliary-induced hydrogenative amination of 2-amidocyclohexanones...

Among the various strategies [34] used for designing enantioselective heterogeneous catalysts, the modification of metal surfaces by chiral auxiliaries (modifiers) is an attractive concept. However, only two efficient and technically relevant enantioselective processes based on this principle have been reported so far the hydrogenation of functionalized p-ketoesters and 2-alkanons with nickel catalysts modified by tartaric acid [35], and the hydrogenation of a-ketoesters on platinum using cinchona alk oids [36] as chiral modifiers (scheme 1). 

Figure 6. Side view of energetically most favorable complex formed between L-sorbose and hexamethylentetramine (HMTA) auxiliary. Complex is stabilized by N-H-O hydrogen bond interaction.

In systems of this type, the electrochemical reactions can be realized or greatly accelerated when small amounts of the components of another redox system are added to the solution. These components function as the auxiliary oxidizing or reducing intermediates of the primary reactants (i.e., as electron or hydrogen-atom transfer agents). When consumed they are regenerated at the electrode. 

Cathodic hydrogen evolution is one of the most common electrochemical reactions. It is the principal reaction in electrolytic hydrogen production, the auxiliary reaction in the production of many substances forming at the anode, such as chlorine, and a side reaction in many cathodic processes, particularly in electrohydrometallurgy. It is of considerable importance in the corrosion of metals. Its special characteristic is the fact that it can proceed in any aqueous solution particular reactants need not be added. The reverse reaction, which is the anodic ionization of molecular hydrogen, is utilized in batteries and fuel cells. 

Oven program Initial temperature Initial hold time Ramp rate Final temperature Final hold time Detector Temperature Auxiliary gas Hydrogen Air... 

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