Vinyl Ether Protecting Group

Silyl ethers are a group of chemical compounds which contain a silicon atom covalently bonded to an alkoxy group.

Vinyl ether protecting group.

A readily recyclable fluorous alkoxy ethyl ether protecting group has been developed that allows for simple purification of small to medium sized organic molecules by liquid liquid extraction with fc 72 organic aqueous solvents. With catalytic amounts of acids ethyl vinyl ether adds to alcohols to give the mixed acetal. The general structure is r 1 r 2 r 3 si o r 4 where r 4 is an alkyl group or an aryl group. The acetal is then called a protecting group for the carbonyl.

Etoch ch 2 roh etoch or ch 3. The optimal route to this vinyl ether was found to be a remarkably selective ring opening of a cyclic acetal with tmsotf and net 3. The step to form the protected intermediate and a deprotection once the. After the step involving the hydride is complete the acetal is removed by reacting it with an aqueous acid giving back the original carbonyl.

Silyl ethers are usually used as protecting groups for alcohols in organic synthesis. Protecting an amine as a carbamate therefore enables other functional groups to undergo selective reactions with electrophiles whereby the carbamate protected amino group is left intact. Isomerization to the more labile enol ether employing ko t bu with subsequent mild acidic hydrolysis is one of the most common deprotection methods. The precursor vinyl ether 3 can be prepared in large quantity in a straightforward two step reaction sequence.

1 when a propionaldehyde derived super silyl enol ether was used syn selectivity was observed scheme 1 table 1. The super silyl group allows for the construction of β hydroxy aldehydes for a broad range of aldehydes providing 1 1 adducts in high yield. This step is called deprotection. During efforts to employ a claisen rearrangement in the synthesis of a complex nucleoside a highly functionalized protected vinyl ether was required as a key intermediate.

However two additional synthetic steps are needed to achieve this protection. 21 the vinyl ether transfer agents like other vinyl ethers generally show marked acid sensitivity and are not suited for use with acidic monomers e g acrylic acid aa methacrylic acid maa. Ethyl vinyl ether participates in many reactions of interest to organic synthesis.