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Organocopper‐Triggered Cyclisation of Conjugated Diene‐ynes: Diastereo‐ and Enantioselective Synthesis of Indenes
Author(s) -
Arif Tanzeel,
Borie Cyril,
Tintaru Aura,
Naubron JeanValère,
Vanthuyne Nicolas,
Bertrand Michèle P.,
Nechab Malek
Publication year - 2015
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201500556
Subject(s) - stereocenter , chemistry , enantioselective synthesis , diene , indene , chirality (physics) , alkene , conjugated system , conjugate , stereochemistry , reagent , combinatorial chemistry , organic chemistry , catalysis , mathematical analysis , natural rubber , chiral symmetry breaking , physics , polymer , mathematics , quantum mechanics , quark , nambu–jona lasinio model
Organocopper reagents react with readily available chiral conjugated diene‐ynes to give indene derivatives bearing two stereogenic centres. The investigation of this original reaction in optically pure series demonstrates that a double transfer of chirality is operating. A stereocontrolled cascade involving S N 2′ followed by carbocupration and conjugate addition reactions accounts for the total recovery of the initial chirality. The scope and limitations of the reaction were investigated. The high diastereofacial discrimination in the cyclisation step allowed the construction of the quaternary stereocentre with excellent dr and ee , with the opposite configuration depending on the E ‐ or Z ‐configuration of the alkene in the starting material. Post‐functionalisation of indenes allowed the synthesis of indanyl derivatives containing four contiguous stereocentres.