85268-66-2Relevant academic research and scientific papers
Alkene protection against acid using a bromide substituent: Application in a total synthesis of (-)-6,7-dideoxysqualestatin H5
Almohseni, Hasanain A. A.,Al Mamari, Hamad H.,Valade, Anne,Sintim, Herman O.,Hodgson, David M.
, p. 5354 - 5356 (2018)
The presence of a bromide substituent, instead of a hydrogen or methyl group, on a carbon-carbon double bond, protects the alkene from addition reactions when exposed to trifluoroacetic acid. This concept is used to circumvent concomitant loss of unsaturation in a late-stage acid-catalysed 6,8- to 2,8-dioxabicyclo[3.2.1]octane rearrangement towards (-)-6,7-dideoxysqualestatin H5. The inertness of the alkenyl bromide functionality is demonstrated through several synthetic transformations in the assembly of the rearrangement substrate. Completion of the natural product synthesis is facilitated by post-rearrangement removal of the bromide substituent through stereoselective C-C cross-coupling in the presence of ester and hydroxyl functionalities.
THE STEREOCHEMISTRY OF THE INTRAMOLECULAR ELECTROPHILIC ATTACK OF AN ALDEHYDE ON A CARBON-TIN BOND
Fleming, Ian,Rowley, Michael
, p. 3181 - 3198 (2007/10/02)
The cyclopentane-forming reaction (20-43) of (4RS,5SR)-2,2,4-trimethyl-5-trimetstannylhexanal takes place with retention of configuration at the carbon atom undergoing electrophilic substitution, in contrast to similar cyclopropane-forming reactions (e.g. 47-48), which take place with inversion of configuration.The hydride transfer (24-45) of the 4RS,5RS diastereoisomeric hexanal takes place from a conformation with hydride anti to the stannyl group.In the case of reacions which might have formed four-membered rings, fragmentation takes place (16-28 and 17-30).The presence of a phenyl ring on the carbon carrying the stannyl group interferes with the reactions designed to test the stereochemistry of the SE2 reaction, diverting the reaction to the formation of tetralins (10-26 and 34-38) or benzcycloheptenes (34-37).
