Codex @codex  0

The singly charged anion of fluorine. Its affinity for silicon makes it useful for cleaving silyl protecting groups.

Only one bromine is replaced by hydrogen. Writing the unchanged protected chain as $R=\mathrm{THPOC}{\mathrm{H}}_2\mathrm{CH}(\mathrm{Me})$, the product is $R\mathrm{CH}=\mathrm{C}(\mathrm{Me})\mathrm{CH}=\mathrm{CHBr}$, retaining the original internal alkene geometry and forming predominantly the $Z$ terminal bromoalkene: bromine and the carbon chain lie on the same side of that new stereodefined double bond. The formula is consequently ${\mathrm{C}}_{13}{\mathrm{H}}_{21}\mathrm{Br}{\mathrm{O}}_2$.

Phosphine dissociation exposes Pd(0), which undergoes preferential oxidative addition into the less hindered C–Br bond, the bromine trans to the carbon chain in the gem-dibromoalkene. hydride transfer from tributyltin hydride replaces the palladium bromide ligand, producing tributyltin bromide and an alkenyl–Pd–H intermediate. reductive elimination joins the alkenyl carbon and hydride, regenerating Pd(0). Retention of the alkenyl geometry through this sequence puts the surviving bromine cis to the chain. The conjugated carbon skeleton and protecting group remain intact; this is not addition of tin hydride across either alkene. The stereoselective monohydrogenolysis is established for this reagent combination.^[ref]

A suitable sequence is selective alpha-bromination, then enol O-methylation. Use one equivalent of Br${}_2$ under controlled acidic enolization conditions to introduce bromine at the enolizable alpha carbon that becomes the brominated vinyl carbon. The other alpha site is a constrained bridgehead and cannot form the required ordinary enol double bond. Then O-alkylate the ketone with trimethyloxonium tetrafluoroborate and remove the brominated alpha proton with a nonnucleophilic base such as triethylamine. Collapse of the O-methylated carbonyl oxonium gives the alpha-bromo methyl enol ether E.

The methyl group belongs on oxygen, not on the alpha carbon. Simply writing methyl iodide with an unspecified enolate would not guarantee this outcome because competitive C-alkylation is possible. Use conditions designed for carbonyl O-alkylation followed by deprotonation, and limit bromine to avoid overbromination or damage to the protecting group.

Cleavage of a silicon–oxygen protecting group to reveal an alcohol. Fluoride can drive the transformation through strong silicon–fluorine bond formation.

A cyclic acetal protecting group made from an alcohol and dihydropyran. It protects the original alcohol oxygen and can be removed under suitable acidic hydrolysis conditions.