Reagents reduction number

One approach to enantioselective reduction of prochiral carbonyl compounds is to utilize chiral ligand-modified metal hydride reagents. In these reagents, the number of reactive hydride species is minimized in order to get high chemo-selectivity. Enantiofacial differentiation is due to the introduced chiral ligand. 

The ether linkage is stable during the reduction of an aldehyde or ketone group by most reagents. A number of alkoxy and aryloxy alcohols are prepared in excellent yields by this method. Catalytic hydrogenation, sodium and wet ether, and sodium with alcohol have been used. 

There are a number of commercially available surfactants that can be employed as an aid in filter cake moisture reduction. These reagents can be added to the filter feed sluriy or to the filter cake wash water, if washing is used. Since these reagents have a dispersing effect, flocculation may be required subsequently Typical moisture reduc-... 

The hydride-donor class of reductants has not yet been successfully paired with enantioselective catalysts. However, a number of chiral reagents that are used in stoichiometric quantity can effect enantioselective reduction of acetophenone and other prochiral ketones. One class of reagents consists of derivatives of LiAlH4 in which some of die hydrides have been replaced by chiral ligands. Section C of Scheme 2.13 shows some examples where chiral diols or amino alcohols have been introduced. Another type of reagent represented in Scheme 2.13 is chiral trialkylborohydrides. Chiral boranes are quite readily available (see Section 4.9 in Part B) and easily converted to borohydrides. 

The intermediate hydroperoxide is sufficiently stable to be isolated, and reduction with any one of a number of reagents (zinc-acetic acid is preferred) then gives the 17a-hydroxy-20-keto compound. 

In contrast to alcohols with their- rich chemical reactivity, ethers (compounds containing a C—O—C unit) undergo relatively few chemical reactions. As you saw when we discussed Grignaid reagents in Chapter 14 and lithium aluminum hydride reductions in Chapter 15, this lack of reactivity of ethers makes them valuable as solvents in a number of synthetically important transfonnations. In the present chapter you will leain of the conditions in which an ether linkage acts as a functional group, as well as the methods by which ethers are prepared. 

The reagents listed above can be applied to the reduction of many other ions in addition to Fe3+, and there are also a number of other substances which can be employed as reducing agents thus for example hydroxylammonium salts are frequently added to solutions to ensure that reagents do not undergo atmospheric oxidation, and as an example of an unusual reducing agent, phosphorous (III) acid may be used to reduce mercury(II) to mercury(I) see Section 10.129. 

A number of other sulphoxide reduction reactions bear mentioning. The first, due to Marchelli and coworkers , is a very simple procedure whereby the sulphoxide is refluxed with t-butyl bromide and chloroform. A useful range of sulphoxides was studied and distillation of the reaction mixture (or percolation through a column of silica gel) gave pure sulphides in yields of > 90%. The procedure is appealing because of its experimental simplicity, and its use of a relatively inexpensive reagent. It may not be very successful with sterically hindered sulphoxides and the authors do not comment on this possibility. The mechanism of this reduction reaction is akin to that of BBrj (cf. Section II.A.3), except that the bromine trap is provided by a second mole of t-butyl bromide, as shown in equation (13) ... 

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