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Oxazolidines as Intermediates in the Asymmetric Synthesis of 3‑Substituted and 1,3-Disubstituted Tetrahydroisoquinolines

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journal contribution
posted on 12.07.2016, 00:00 by Sadagopan Raghavan, Puspamitra Senapati
A diastereoselective mercury­(II)-promoted intramolecular cyclization of unsaturated aldehyde via an oxazolidine to prepare C-3-substituted tetrahydroisoquinoline is disclosed. The C-3 stereogenic center is subsequently exploited to create the C-1 stereocenter by coordination of the nucleophilic reagent to the oxygen atom of oxazolidine. Both cis- and trans-1,3-disubstituted tetrahydroisoquinolines can be readily prepared. In addition, when a cationic rhodium complex was used, intramolecular hydroamination was effected, thus avoiding mercury­(II) salts and demercuration. The reaction is general and works well using aliphatic and aromatic aldehydes.