Etiol

Because etiolate anions are sources of nucleophilic carbon one potential use m organic syn thesis IS their reaction with alkyl halides to give a alkyl denvahves of aldehydes and ketones... 

Carbanions derived from carbonyl compoimds are often referred to as etiolates. This name is derived from the enol tautomer of carbonyl compounds. The resonance-stabilized enolate anion is the conjugate base of both the keto and enol forms of carbonyl... 

Fig. 7.3. Crystal structures of some lithium etiolates of ketones. (A) Unsolvated hexameric enolate of methyl t-butyl ketone (B) tetrahydrofuran solvate of tetramer of enolate of methyl r-butyl ketone (C) tetrahydrofuran solvate of tetramer of enolate of cyclopentanone (D) dimeric enolate of 3,3-dimethyl-4-(r-butyldimethylsiloxy)-2-pentanone. (Structural diagrams are reproduced from Refs. 66-69.) by permission of the American Chemical Society and Verlag Helvetica Chimica Acta AG.

A -Fluoropyridmium Inflates react with cyclic etiol ethers to give addition products as mixtures of as and trans isomers [172] (equation 39)... 

The extent of mono- versus difluorination of etiolates may also be controlled through the use of N-fluorosultam (Table 3a, G). With a base/W-fIiioro com-pound/substrate ratio of 1.2/1.3-1 6/1, the reaction yields inonofluoro products, but with a ratio of 2.4-3.6/2.6-3 6/1, the difluorinated compounds are obtained [68] (equation 42)... 

The final step in the /3-oxidation cycle is the cleavage of the /3-ketoacyI-CoA. This reaction, catalyzed by thiolase (also known as j8-ketothiolase), involves the attack of a cysteine thiolate from the enzyme on the /3-carbonyI carbon, followed by cleavage to give the etiolate of acetyl-CoA and an enzyme-thioester intermediate (Figure 24.17). Subsequent attack by the thiol group of a second CoA and departure of the cysteine thiolate yields a new (shorter) acyl-CoA. If the reaction in Figure 24.17 is read in reverse, it is easy to see that it is a Claisen condensation—an attack of the etiolate anion of acetyl-CoA on a thioester. Despite the formation of a second thioester, this reaction has a very favorable A).q, and it drives the three previous reactions of /3-oxidation. 

Tliese observed stereoselectivites can be forcned by ryn addition at low temperatut [60a] to afford tlie E adduct Selective for temperatures, requires ritlier forenation allenyl etiolate or isomerization of tlie Z a stereoselective protonation. Recetit mecliat... 

Prior to tlie advent of tripbenylpbospbine-stab dized CuH [6a, b, 11], Tsuda and Saegusa described use of Gve mole percent MeCu/DtBAL in THE/HMPA to effect bydtoaluminaiion of conjugated ketones and esters [26], Hie likely aluminium etiolate intermediate could be quendied witli water ot TMSCl, ot alkylated/acylated widi various electrophiles fsudi as Mel, allyl bromide, etc. Sdieme 5.5). Mote... 

Stereoselective addition of cuprates to ji-alkoxy enoates of type 49 [17] isee Sdiemes 6.8 and 6.9) bas been used in die crrnstruction of polypropionate-type structures. Tlius, a sequence of diastereoselective cuprate addition, etiolate for-ruabon, and diastereoselective oxygenation widi Davis s reagent bas been applied iteratively to provide a Cio segment of Rifaruycin S i60) [ 17c, d]. 

The Michael additkin of Lithium etiolates to tiitroalkenes folbwed by reaction with acetic anhydnde gives acetic niironic anhydndes, which are good precursors for 1,4-diketones, pyrroles, and pyrrolidines fEq. 10.73. ... 

The influence of sunlight on vegetable growth, and the results of etiolation are, of course, well known to botanical students. There is no room for doubt that the production and evolution of the odour-bearing constituents of a plant are in direct relationship with the chlorophyll... 

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