Hoch diastereoselektive eisenvermittelte C(sp²)‐C(sp³)‐Kreuzkupplungen zwischen Aryl‐Grignard‐Reagentien und cyclischen Iodhydrinderivaten

Diastereoconvergent Synthesis of (–)‐Paroxetine

“…The epoxide‐ring‐opening reaction occurred in high yield with complete retention of configuration (to give 6 ). This unexpected retention of configuration at C‐4 can be explained by an initial S N 2 epoxide‐ring‐opening reaction mediated by CuI to give, in the first instance, the corresponding trans ‐halohydrin E , which, through a subsequent S N 2 substitution with the aryl cuprate provides oxopiperidinylmethanol derivative 6 in good yield [Scheme , Equation (5)]. Additionally, the regio‐ and stereodivergent ring‐opening reaction of 1a can also be explained by considering the chelation complexes F and G as the key intermediates for inversion and retention of configuration, respectively, in the epoxide‐ring‐opening reaction.…”

Alkyl−(Hetero)Aryl Bond Formation via Decarboxylative Cross‐Coupling: A Systematic Analysis

“…The yield for this substrate under Ni‐Suzuki conditions, although modest, would be sufficient for practicing medicinal chemists in need of a key analogue. Quinoline‐based systems such as 26 have only rarely been employed in alkyl–aryl cross‐coupling with the vast majority of such products being prepared instead by ring synthesis . In our hands, the Ni‐Suzuki protocol was the only viable option for the RAE coupling.…”

Alkyl−(Hetero)Aryl Bond Formation via Decarboxylative Cross‐Coupling: A Systematic Analysis

“…This metallated heterocycle has only been reported by Knochel to participate in Fe-o rC o-based cross-coupling with two alkyl iodides and one alkyl bromide. [15] In the case of brominated pyridine 25,toour knowledge there are no reports using such as pecies in any alkyl cross-coupling and even C(sp 2 ) couplings are sparse.T he yield for this substrate under Ni-Suzuki conditions,a lthough modest, would be sufficient for practicing medicinal chemists in need of ak ey analogue. Quinoline-based systems such as 26 have only rarely been employed in alkyl-aryl cross-coupling with the vast majority of such products being prepared instead by ring synthesis.…”