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Preparation of Stereodefined Secondary Alkyllithium Compounds
Author(s) -
Seel Stephanie,
Dagousset Guillaume,
Thaler Tobias,
Frischmuth Annette,
Karaghiosoff Konstantin,
Zipse Hendrik,
Knochel Paul
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201204076
Subject(s) - stereospecificity , electrophile , lithium (medication) , chemistry , reagent , quenching (fluorescence) , computational chemistry , ab initio , cis–trans isomerism , combinatorial chemistry , organic chemistry , catalysis , medicine , physics , quantum mechanics , fluorescence , endocrinology
We have developed a practical stereoretentive iodine/lithium‐exchange process that allows the stereodefined preparation of cis ‐ and trans ‐cycloalkyllithium compounds from their corresponding stereodefined iodides. Quenching with electrophiles offers stereospecific access to both cis ‐ (up to 96 % cis ) and trans ‐cycloalkyl derivatives (up to 99 % trans ). A detailed study of the thermodynamic stabilities, stereochemical behavior, and reactivities of axially and equatorially substituted cyclohexyllithium reagents is reported. Ab initio calculations demonstrate that the formation of oligomeric cyclohexyllithium structures is pivotal for explaining the observed stereochemical preference.