Intramolecular Schmidt reaction involving primary azidoalcohols under nonacidic conditions: synthesis of indolizidine (-)-167B

A powerful intramolecular Schmidt reaction starting from primary azidoalcohols is reported. This approach involves a nonacidic activation of the alcohol via triflation. The synthetic potential offered by the mild reaction conditions is demonstrated by a highly selective synthesis of (−)-indolizidine 167B.