Pinacol Rearrangement

Written by 525 days ago

The is essentially a of an , specifically a . The following is an example of a pinacol rearrangement in which the (R,R)- (TBDMS is tert-butyldimethylsilyl) was allowed to react with 2,2 dimethylpropane (2,2-DMP) in the of at . This particular reaction was done in order to attain the derivative.

Interestingly, instead of retaining its , the product of the pinacol arrangement actually resulted in a . Subsequent of this product eventually yield benzophenone (hydroxyphenstatin), which, biologically, is a potent antitumor and antimitotic agent. Accordingly, hydroxyphenstatin has also been proven to inhibit tubulin assembly.

D,L-1,2,4-butanetriol can be made in ; the first way is commercial through reduction of esterified D,L-malic acid with borohydride, , while the second way involves . The latter method was the focus of the journal article. of racemic D,L-1,2,4-butanetriol results in D,L-1,2,4-butanetriol trinitrate, a compound that is the energetic equivalent of , but is less shock sensitive, more thermally stable, and less volatile. One of the final steps in the synthesis of D, L-1,2,4-butanetriol via microbes is the reduction of a racemic mixture of D,L-3,4-dihydroxybutanal (aldehyde), to the final product, as seen in the reaction below. The for the reaction is dehydrogenase from E. coli.


The picture above shows a few of the steps in the creation of . In these steps, tosyl chloride is added to (2,5-dimethoxyl-4-methylphenyl)-2- to create the tosylate. After this step, the reaction can proceed in one of . If the chirality of the is not important, is added to the tosylate to give 2,5-dimethoxy-4-. This reaction has an 80% yield, but has a of products because it is thought to be an SN1 reaction. If the chirality is important, the tosylate is converted into an with azide, then hydrogenated using a paladium to form 2,5-dimethoxy-4-methylamphetamine. Forming the amphetamine using this method gives a final yield of about 77%. The chirality of the original is inverted by the tosylation, so reacting an (S)- with the tosyl-azide-hydrogen sequence would give an (R)-amphetamine, and vice versa.

Williamson Synthesis of Ethers

Written by 531 days ago


The above reaction is an example of a Williamson of an ether. It is one the earlier steps in the reaction mechanism resulting in the octaethylene derivative of 1,1,1,3,5,5,5-heptamethyltrisiloxane. Such an initial Williamson reaction had to be carried out so that later steps in the reaction—that is, ones involving not readily accessible—could successfully yield the derivative product. The resultant glycol derivative is an example of a defined . This particular journal article focused on the correlation between and the effect on properties such as spreading performance.
The Williamson synthesis involves an SN2 reaction in which a , , or sulfate group is replaced by an alkoxide ion, which can itself be prepared by a reaction of the alcohol with an active metal such as or its (i.e. NaH). The resultant alkoxide salt then reacts with the alkyl halide (must be primary) to produce an ether via the .
Other examples of Williamson synthesis of can be found in this same reaction mechanism used to produce the surfactant. 

This is one of the steps in the of . is an found in the bark of the . In the step outlined, an is reduced by 4 and to an .

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