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Synthetic Studies for the 1,3‐Iterative Organoiron Approach to the Synthesis of Siculinine: Efficient Arylation Using a Diarylcuprate Reagent
Author(s) -
Stephenson G. Richard,
Palotai Ian M.,
Thomas Sarah,
Tinkl Michael
Publication year - 2013
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201201056
Subject(s) - chemistry , reagent , yield (engineering) , hydride , dimethyl sulfide , hydrolysis , medicinal chemistry , sulfide , chelation , combinatorial chemistry , organic chemistry , sulfur , metal , materials science , metallurgy
Disubstituted (cyclohexadienyl)iron(1+) complex 2b is prepared by an improved route that starts from 1,2‐dimethoxycyclohexa‐1,4‐diene 3 . In five steps, the synthesis of 2b is achieved by complexation with Fe(CO) 5 , hydride abstraction, hydrolysis, addition of EtO 2 CCH 2 ZrBr, and reaction with HBF 4 . In the presence of dimethyl sulfide, the reaction of 2b with 2‐[CH 2 N(CH 2 CH=CH 2 ) 2 ]‐functionalized diarylcuprate reagent 7 gave the 5α‐arylcyclohexadiene complex 1b in 88 % yield. A DFT study compared diarylzinc and diarylcuprate reagents containing chelating CH 2 NMe 2 substituents.