Allylamines Subject

Allyl groups are subject to oxidative deprotection with Chromiapillared Montmorillonite Clay, -BuOOH, CH2CI2, isooctane, 85% yield. Allylamines are cleaved in 84—90% yield, and allyl phenyl ethers are cleaved in 80% yield. 

Pyrrolidone is the major product when allylamine is subjected to the conditions of the oxo process using dicobalt octacarbonyl as the catalyst.203 The by-products are pyridine derivatives 112 and 113 and these compounds become the major products when iron pentacarbonyl is used as the catalyst ... 

A-allylamine 23 (obtained by standard transformations of 6-iodogluco-side 22) underwent cyclization into the monocycle 24. However, when the amine was in situ protected as a Boc derivative it could be subjected to the RCM process. The products were further converted into the bicyclic aza sugar 26.19 A similar approach to eight-membered ring aza sugars was recently reported (Fig. 9).20... 

The rearrangement of unsymmetrical allylamines 9 was investigated to exclude any competing 1,3-rearrangement during the course of the reaction. Allyl vinyl amines 10 were generated via condensation starting from allylamine 9 and isobutyraldehyde 2. The substrates 10 were subjected to the acid-accel-... 

Reaction of 5-substituted isatoic anhydride with allylamines gave 2-amino-5-substituted-jV-alkyl-A -(2-propenyl)benzamides which were subjected to diazotization followed by subsequent nucleophilic substitution and cyclization to give 2-methyl-l,4-benzodiazepin-5-ones. A non-covalent DNA-binding agent like pyrrolo[2,l-c][l,4]benzodiazepine-5,ll-dione has been synthesized. 

As a special case, the formation of hemiacetals 2 (lactolization) during the hydroformylation of hydroxy-functionalized olefins, such as allyl or homoallyl alcohols, has to be mentioned (1, Y= O, Scheme 5.70). With these substrates, the reaction occurs in an intramolecular manner. In the presence of an external alcohol, the cyclic hemiacetal can further react to give a nonsymmetric cyclic acetal 3. Hemiacetals can be subjected to hydrogenation to afford diols 4. Under reducing conditions and in the presence of amines, amino alcohols 5 are formed both are valuable building blocks in fine chemistry. Alternatively, oxidation gives lactones 6 [5]. By dehydration of hemiacetals, cychc vinyl ethers 7 are formed. The same transformation with allylamines (Y=NR) gives cyclic hemiaminals, A/ ,0-acetals, lactames, or vinyl amines. 

---