Hexylmagnesium bromide, reaction with

Hexylmagnesium bromide, reaction of with acetaldehyde, 555 with ethylene oxide, 588 1-Hexyne, 556... 

Reaction of l-bromo-2-butyne with hexylmagnesium bromide to give a mixture containing equal amounts of 1-methyl-1-hexylallene and 2-decyne... 

The stereoselective total synthesis of ( )-lepadiformine was accomplished in the laboratory of S.M. Weinreb. The introduction of the hexyl chain in a stereoselective fashion was achieved by a Grignard reaction to an iminium salt during the last steps of the synthetic sequence. The iminium salt was generated in situ from an a-amino nitrile with boron trifluoride etherate, and the addition of hexylmagnesium bromide gave a 3 1 mixture of alkylated products favoring the desired stereoisomer. Removal of the benzyl group completed the total synthesis. 

A selective reducing agent for double bonds (potassium azodicarboxylate-acetic acid) allowed the preparation of the epidioxide (268) from the A -compound/ A synthesis was reported for the 18,20-lactone (269) through the hypoiodite reaction of (205)-20-hydroxy-5a-cholestan-3/3-yl acetate/ A second synthesis of the 18,20-lactone (269) from the known lactone (270) involved the stereoselective reaction of the acetoxy-ketone (271) with iso-hexylmagnesium bromide to give the (205)-20-hydroxy-compound (272)/ These syntheses served as models for the synthesis of seychellogenin (273) and the 7,8,9,11-tetrahydro-derivative/ ... 

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). 

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