Diastereoselective Synthesis of Open-Chain Secondary Alkyllithium Compounds and Trapping Reactions with Electrophiles

A practical stereoselective iodide–lithium exchange was used in the first general preparation of functionalized stereodefined acyclic secondary nonstabilized lithium reagents from the corresponding secondary alkyl iodides. These lithium reagents react with various electrophiles including carbon elec...

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Published inAngewandte Chemie International Edition Vol. 53; no. 5; pp. 1425 - 1429
Main Authors Dagousset, Guillaume, Moriya, Kohei, Mose, Rasmus, Berionni, Guillaume, Karaghiosoff, Konstantin, Knochel, Paul
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 27.01.2014
WILEY‐VCH Verlag
Wiley
Wiley Subscription Services, Inc
Wiley-VCH Verlag
EditionInternational ed. in English
Subjects
acylation
Carbon
Chemical Sciences
Chemistry
Chemistry, Multidisciplinary
Derivatives
diastereoselectivity
Exchange
Iodides
Kinetics
lithiation
Lithium
nucleophilic substiution
Organic chemistry
Physical Sciences
Quenching
Science & Technology
Synthesis
Trapping
DYNAMIC THERMODYNAMIC RESOLUTION
lithiation
diastereoselectivity
SUBSTITUTION-REACTIONS
acylation
SOLVENT
CONFIGURATIONAL STABILITY
PRIMARY ALKYL IODIDES
EQUILIBRATION
kinetics
LITHIUM
nucleophilic substiution
CHIRAL ORGANOMETALLIC REAGENTS
ORGANOLITHIUM
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Summary:A practical stereoselective iodide–lithium exchange was used in the first general preparation of functionalized stereodefined acyclic secondary nonstabilized lithium reagents from the corresponding secondary alkyl iodides. These lithium reagents react with various electrophiles including carbon electrophiles with high retention of configuration. Kinetic data on the configurational stability of these acyclic alkyllithium reagents are given. This methodology offers a new entry to chiral synthons for the stereoselective synthesis of open‐chain molecules. Stereocontrol in acyclic systems: A practical stereoretentive iodine–lithium exchange served in the first general preparation of functionalized stereodefined acyclic secondary nonstabilized lithium reagents from the corresponding diastereomerically pure syn and anti alkyl iodides. Quenching with a range of electrophiles provides stereospecific access to both syn and anti acyclic alkyl derivatives with excellent diastereoselectivities (up to d.r.=97:3).
Bibliography:ArticleID:ANIE201308679
Deutsche Forschungsgemeinschaft
istex:8B0D721975A4825AD02C31B6656CC73CE3F65EC6
This work was supported by the Deutsche Forschungsgemeinschaft (SFB749, B2), the Alexander-von-Humboldt-Stiftung (fellowships to G.D. and G.B.), and the DAAD (scholarship to K.M.). We also thank BASF SE (Ludwigshafen) and Rockwood Lithium GmbH (Frankfurt) for generous gifts of chemicals and Prof. Dr. H. Mayr for valuable discussions.
ark:/67375/WNG-8JJRD3G1-G
This work was supported by the Deutsche Forschungsgemeinschaft (SFB749, B2), the Alexander‐von‐Humboldt‐Stiftung (fellowships to G.D. and G.B.), and the DAAD (scholarship to K.M.). We also thank BASF SE (Ludwigshafen) and Rockwood Lithium GmbH (Frankfurt) for generous gifts of chemicals and Prof. Dr. H. Mayr for valuable discussions.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201308679