Simona Tommasi

Highly enantioselective nitroaldol reaction catalyzed by new chiral copper complexes

Remarkable generality in scope of DATs/Cu catalysts for enantioselective nitroaldol reaction is described; excellent levels of stereoinduction are recorded for a range of aldehydes (ee 81-99%, 17 examples) and the possibility to employ the present catalytic system as the key step for the preparation of highly functionalized tetrahydro-isoquinolines is demonstrated.

A practical synthetic route to functionalized THBCs and oxygenated analogues via intramolecular Friedel-Crafts reactions.

A practical catalytic approach to the synthesis of 4-substituted 1,2,3,4-tetrahydro-beta-carbolines (THBCs, 1) and 1,2,3,9-tetrahydropyrano[3,4-b]indoles (2) via InBr3-catalyzed intramolecular Friedel-Crafts (F-C) cyclization is described. The use of cross-metathesis reaction represents a direct route to the cyclization precursors and the use of InBr3 (5 mol%) allowed polycyclic indole compounds to be isolated in high yields under mild reaction conditions (rt, DCM, minutes). Finally, efforts toward the development of a stereocontrolled version of the present cyclization are presented, highlighting [salenAlCl] and bimetallic [(salenAlCl)2-InBr3] system as promising chiral Lewis acids (ee up to 60%).

Practical Aspects in the Gram-Scale Synthesis of Chiral Diamino-Bithiophene ‘DAT2’ Ligand

A gram-scale synthesis of the enantiomerically pure ligand DAT2 is described. The mild reaction conditions, operational simplicity, and satisfying isolated yield (68%) are some of the main features of this two-step reductive amination.