Utilization of Industrial Waste Materials, 10 . – Synthesis of New Chiral Bicyclic 3‐hydroxypiperidines – Highly Diastereoselective Ring Expansion of the Azabicyclo[3.3.0]octane System to Chiral Piperidine Derivatives

New, chiral bicyclic 3‐hydroxypiperidines (4 S )‐ 2a–e are synthesized from the β‐amino alcohols (3 R )‐ 1a–e . In an one‐step reaction (4 S )‐ 2a–e are obtained by a high diastereoselective ring expansion ( dr ⩾ 95:5). As well, the amino alcohol (3 S )‐ 1a leads to the corresponding rearranged epimer bicyclic piperidine derivative (4 R )‐ 2a ( dr ⩾ 95:5). Thus, it is possible to clarify the influence of the three stereogenic centers of the parent compound regarding the diastereoselectivity of the ring expansion. After oxidation of the tert ‐amino sec ‐alcohol (4 S )‐ 2a to the corresponding α‐amino ketone 4 , new 3‐hydroxypiperidines (4 Ξ )‐ 5a, b 12 and (4 RS )‐ 6 are obtained by a diastereoselective Grignard addition. Furthermore, the achiral and the chiral reduction of 4 to the β‐amino alcohols (4 S )‐ 2a and (4 R )‐ 2a is described. These are further examples of the utilization of industrial waste material ( all‐R )‐2‐azabicyclo[3.3.0]octane‐3‐carboxylic acid ( all‐R )‐ 3 .