17687-72-8Relevant articles and documents
Synthesis of deuterium-labelled polyoctylalkanes
Bolton,Luff,Sutcliffe
, p. 1205 - 1213 (1995)
The synthesis of specifically labelled 9-d-9-octylheptadecane (1) and 9-d-9,10-dioctyloctadecane (2) has been achieved using selective and specific deuterium labelling methods. The precursor to the latter compound, tetraoctyl ethene, has been achieved by a variant of the McMurry reaction which improves upon recently published methods.
Reactions of organoboranes with carbanions bearing three potential leaving groups: unusual processes, products and mechanisms
Saleh, Basil A.,Smith, Keith,Elliott, Mark C.,Jones, D. Heulyn,Kariuki, Benson M.,El Hiti, Gamal A.
, p. 6914 - 6928 (2016/10/14)
Known reagents that transfer three alkyl groups of a trialkylborane intramolecularly to a single carbon atom lack features to influence stereochemistry. We have investigated four reagents of type LiCCl2X, where X might be amenable to variation. All behaved differently. With X=OR (R=cyclohexyl, menthyl), the reagent decomposed, leading to only low yields of triple migration products. With X=S(O)Ph, a single migration occurred, followed by isomerisation to boron enolate-like species that hydrolysed to α-chloroalkyl phenyl sulfoxides or reacted with aldehydes to aldol-like products. With X=SO2Ph, the major product was the corresponding α,α-dichloroalkyl phenyl sulfone, apparently formed through a redox reaction. With X=S(O)(NMe)Ph, products of three intramolecular alkyl migrations were obtained with unhindered trialkylboranes. Attempts have been made to gain understanding of the sulfoxide process by investigating proportions of aldol-like products, using X-ray crystallography and ab initio calculations.
Factors affecting migration of tertiary alkyl groups in reactions of alkylboronic esters with bromomethyllithium
Elliott, Mark C.,Smith, Keith,Heulyn Jones,Hussain, Ajaz,Saleh, Basil A.
, p. 3057 - 3064 (2013/06/27)
The reactions of bromomethyllithium with tert-alkylboronic esters could be of great potential for the formation of quaternary carbon centers but often give poor yields/conversions. Calculations and experimental evidence show that tert-alkyl groups migrate less effectively than other types of alkyl group in such reactions and that O-migration competes. Furthermore, slow/incomplete capture of the bromomethyl reagent by the boronic ester is a problem in more hindered systems, and an additional competing reaction, possibly Li-Br exchange on the bromomethylborate species, also leads to lower yields of migrated products. Based on this, experimental protocols have been devised in which the competing reactions are largely suppressed, leading to higher conversions to migrated product for several substrates.
