Synthesis of Amines and Amino Alcohols by Electrophilic Amination and Highly Stereoselective Reduction

A practical and selective method for the synthesis of the β‐arylamines 5 and the cis ‐ or trans ‐amino alcohols 8 or 11 is reported. The reaction sequence starts from α‐tetralones 1 which readily react with dibenzyl azodicarboxylate to afford the protected α‐hydrazino ketones 2 . Then, depending on the reduction conditions , the trans ‐hydrazino alcohols 10 or the cis isomers 7 are formed predominantly. The stereoselectivities which range between 18:1 and 1:67 ( trans/cis ) are explained by stereoelectronic effects (σ,σ   ≠ *interactions) and steric hindrance. Depending on the workup procedure , we can control, whether the cis ‐hydrazino alcohols 7 or the oxazolidinone derivatives 3 are isolated. Subsequent hydrogenolyses of 4, 7 and 10 lead to the target molecules 5, 8 and 11 , respectively.