Amino-alcohols from isocyanides

The adducts from these reactions can be transformed in a variety of compounds. As mentioned earlier, the unstable a-hydrazinoaldehydes are often not isolated but rather subjected to further reactions to yield a more stable compound, such as amino alcohols or oxazolidinones. Other transformations are illustrated in Scheme 11.5. For example, the so-formed a-hydrazinoaldehyde can further react with acetone under catalysis by 1 in a one-pot fashion to give optically active amino alcohols containing two stereogenic centers [19]. A subsequent Passerini reaction of the a-hydrazinoal-dehyde can be performed by reacting the aldehyde with an isocyanide. Schmidt and co-workers [20] have shown that this sequential reaction can provide rapid access to... 

The chemistry of trimethylsilyl cyanide continues to feature in the literature, and the first of several examples described this year is the opening of epoxides to produce P-hydroxy-isocyanides, a reaction which provides entry to a general synthesis of oxazolines and P-amino-alcohols. By using the modified conditions outlined in Scheme 20 it is possible to prepare phenylacetic acids from aryl ketones in moderate to good yield by the MeaSiCN route. ... 

Peptides. In the presence of an aliphatic isocyanide, amino acids and amines condense to form amides. Yields are increased by addition of ZnCl, CH2CI2 is preferable to alcoholic solvents. Yields of dipeptides range from 25 to 90%. ... 

The synthesis of a-benzofuranylacetamides and indolylacetamides has been achieved through a palladium-catalyzed process (Scheme 3.61 and Example 3.10) [67]. The overall reaction consisted of an intramolecular oxy/amino-palladation/isocyanide insertion process starting from functionalized propargyl alcohols. Although a vast array of compounds were successfully generated using this approach, the conversion of nitrated anilines was unsuccessful under the reaction conditions. 

---