Alanes synthesis with addition

The aziridine-2-carboxaldehyde 56 can also serve as synthon for the synthesis of sphingosines, which are important biomembrane constituents [64]. One possible route involves the addition of an alanate to the aldehyde. In a later stage of this synthetic plan the aziridine can be opened, either via the intermediacy of an oxazoline or directly with dilute acid. Unfortunately, the reaction of aldehyde 56 with a vinylalanate has a poor diastereoselectivity of 3 2. Therefore, an alternative approach was considered, namely one involving the addition of a vinylzinc reagent to the aldehyde thereby employing our N-tritylaziridinediphenyl-methanol 51 as the chiral catalyst. Gratifyingly, only one diastereomer was obtained. Reductive removal of the trityl function, acetylation of the hydroxy... 

Irrespective of the stereochemistry of the ot,p-enones, lithium alkenyltrialkylalanates, e.g. (28) and (29), obtainable by treatment of alkenylalanes with methyllithium (or n-butyllithium), are also excellent 1,4-conjugate alkenyl transfer reagents. The cornerstone of a general prostaglandin synthesis, as exemplified in Scheme 6, employs the alanate conjugate addition process exclusively.13... 

Preparation. - By Addition to Alkenes. Triethylborane and phenyl-borinic acid have been found to catalyse hydroalumination of alkenes, and reaction of the intermediate alane with atmospheric oxygen efficiently furnished alcohols resulting from anti-Markovnikov hydration.1 Procedures for the preparation of methylborane and dimethylborane and their use in the synthesis of... 

Another way to generated vinyl alanes is the transition metal catalyzed addition of trialkylaluminum reagents to alkynes. In Hoye s synthesis of elenic acid, 10 1-dodecyne was treated with Me3Al in the present of Cp2ZrCl2 and then MeLi. The resulting ate complex 730 was then reacted with triflate 731 to give a 96% yield of the alkene, 732. 

The reaction of tosylhydrazones of a -unsaturated enones with sodium boro-hydride in alcoholic solution leads not to reduction, but instead to elimination according to Scheme 35, to provide a synthesis of allyl ethers in good yields. Potassium carbonate or sodium alkoxides can replace borohydride as the base in this sequence. trans-A y ethyl ethers (74) may be synthesized stereoselectively by the addition of aluminium hydrides to 1-alkynes and subsequent reaction of the vinyl alane formed (Scheme 36). This route complements the same authors ... 

In the synthesis of (—)-lupinine (926) by Santos et al., (lR,2S,5R)-8-phenyhnenthol was used as the chiral auxiliary in controlling the stereochemical outcome of the reaction of the piperidine-containing carbamate 1042 with the 2-silyloxyfuran 1043 (Scheme 130). With trimethylsilyl triflate as Lewis acid catalyst and butyhnethylimidazolinium tetrafluorobo-rate as additive, an 80% yield was obtained as a 9.7 1 mixture in favor of threo-product (—)-1044. After hydrogenation of the double bond, treatment of the intermediate (—)-1045 with sodium methoxide effected rearrangement to the (R,R)-(- -)-l-hydroxyquinolizidin-4-one (- -)-1046 in 93% overall yield. Mitsunobu inversion of the alcohol to the (lS)-epimer (—)-1047 followed by alane reduction of the lactam afforded the quinolizi-din-l-ol (—)-1048. A second inversion at C-1 with cyanide produced the... 

---