N-Hexylmagnesium bromide

Peninsular ChemResearch offers methylmagnesium bromide in ether and in di-n-butyl ether methylmagnesium iodide in di-n-butyl ether n-hexylmagnesium bromide in ether tetramethylenedimagnesium bromide in ether phenylmagnesium bromide in ether. 

Alkenyl halides couple readily with Grignard reagents in the presence of iron. -E n-Hexylmagnesium bromide allowed to react at 0° with vinyl bromide in tetrahydrofuran in the presence of FeClg 1-octene. Y 83%. F. e. s. M. Tamura and J. Kochi, Am. Soc. 93, 1487 (1971) also coupling with satd. halides in the presence of Ag - and Cu -catalysts s. Synthesis 1971, 303. 

To a solution of n-hexylmagnesium bromide in 700 ml of ether [prepared from 2 moles (330 gm) of n-hexylbromide, 2 moles (48 gm) of magnesium turnings, and 700 ml of anhydrous ether] is added 95 gm (2.2 moles) of Uquid ethylene oxide over a period of 1 hr while the ether refluxes vigorously as a result of the heat of reaction. After the addition has been completed, the ether is distilled off until 275 ml have been collected. Then 330 ml of dry benzene is added and the distillation is continued until the temperature reaches 6S°C. The mixture is then refluxed for 1 hr and then hydrolyzed with ice water containing 10% sulfuric acid. The benzene layer is separated, washed twice with 10% sodium hydroxide solution, and then distilled to remove the benzene solvent. The residue is distilled under reduced pressure to yield 185 gm (71 %) of 1-octanol, bp 105°C (15 mm). 

Clavepictines A and B (210 and 211, respectively) were obtained from the allenic ester 227. The reduction of its ester group to aldehyde, followed of addition to the latter of hexylmagnesium bromide, OH protection, and N-deprotection gave compound 228. A silver(i)-mediated cyclization of this compound afforded quinolizidine 229 and its C-6 epimer in a 7 1 ratio (Scheme 44). The former compound was readily converted into the target alkaloids <1997JOC4550>. 

---