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This review relates all the results that we obtained in the field of the total synthesis of indolizidine and quinolizidine alkaloids using a strategy of the addition of an allylsilane on an N-acyliminium ion. In this paper, we describe the synthesis of racemic indolizidine 167B and chiral indolizidines: (-)-indolizidines 167B, 195B, 223AB, (+)-monomorine, (-)-(3R,5S,8aS)-3-butyl-5-propylindolizidine and (-)-dendroprimine. Next, we relate the synthesis that we have developed in the quinolizidines field: (+/-)-myrtine and epimyrtine, (+/-)-lasubines I and II and chiral quinolizidines: (+)-myrtine, (-)-epimyrtine, (-)-lasubines I and II and (+)-subcosine II.

An enantioselective and diastereoselective synthesis of six 5,7-dimethylindolizidine isomers is described via an intramolecular cyclization that involves an allylsilyl nucleophilic group and an acyliminium ion. The first total synthesis of naturally occurring (-)-dendroprimine has been achieved in five steps.

Enantiomeric analysis and empirical determination of the absolute configuration of amines and amino acids can be easily performed using acetyl-d(3) chloride as a nonchiral derivatizing agent (deuterium probe) and deuterium NMR in a chiral solvent (Courtieu's method). In the case of amino acids, derivatization to amido esters, performed with methanol-d(4) and acetyl-d(3) chloride, gives a double opportunity for enantiomeric analysis.