Hydroaminomethylation allyl amines

Scheme 12.16. Hydroaminomethylation of allylic amines leads to cyclic amides in conventional solvents, but pyrrolidines are formed preferentially in SCCO2.

Rische T, Muller K, Eilbracht P (1999) One-pot synthesis of pharmacologically active diamines via rhodium-catalysed carbonylative hydroaminomethylation of heterocyclic allylic amines. Tetrahedron 55 9801-9816... 

Scheme 5.113 Hydroaminomethylation of an allyl amine derivative using urea as source for ammonia.

Scheme 5.115 Ring-closing hydroaminomethylation of allyl amines.

Scheme 5.116 Hydroaminomethylation of quinazolinone-substituted allyl amines with phenylhydrazine and some products with pharmaceutical relevance.

Given our interest in a synthesis of nicotine, we wondered whether the hydroaminomethylation could be applied as described in Scheme 11.13. While the Ir-catalyzed allylic amination with methylamine again gave an excellent... 

Abstract Aldehydes obtained from olefins under hydroformylation conditions can be converted to more complex reaction products in one-pot reaction sequences. These involve heterofunctionalization of aldehydes to form acetals, aminals, imines and enamines, including reduction products of the latter in an overall hydroaminomethylation. Furthermore, numerous conversions of oxo aldehydes with additional C.C-bond formation are conceivable such as aldol reactions, allylations, carbonyl olefinations, ene reactions and electrophilic aromatic substitutions, including Fischer indole syntheses. 

General Procedure for the Stepwise Hydroformylation/Reductive Amination on Allylated Hyperbranched Polyglycerols (PG). Synthesis of Hydroaminomethylated Hyperbranched PG-dendrimers. PG-Allyl, Rh(acac)(CO)2 and XANTPHOS were dissolved in dry toluene and placed in an autoclave. The autoclave was pressurized with CO/H2 (1 1, 30 bar), heated at 70 °C for 5d. After cooling, the amine was added to the crude PG-aldehyde (1H NMR was used to confirm full conversion) and stirred for 1-2 h. After stirring, Rh(acac)(CO)2 was added and the autoclave was pressurized with CO/H2 (1 6, 70 bar) and heated at 85 °C for 2-5 days. After cooling, the solvent was removed in vacuo and the crude mixture was purified by dialysis (benzoylated cellulose tubing) to give the re-... 

Diamines are also obtained from allyl chlorides by initial halogen substitution to give the aUylamine and subsequent hydroaminomethylation [99]. With primary amines or diamines this method can also be nsed in the synthesis of heterocyclic systems. 

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