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The First Asymmetric Carroll Rearrangement Diastereo‐ and Enantioselective Synthesis of Polyfunctional Ketones with Vicinal Quaternary and Tertiary Stereogenic Centers
Author(s) -
Enders Dieter,
Knopp Monika,
Runsink Jan,
Raabe Gerhard
Publication year - 1996
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199619960708
Subject(s) - stereocenter , vicinal , enantioselective synthesis , chemistry , stereochemistry , enantiomer , sigmatropic reaction , organic chemistry , catalysis
The first asymmetric Carroll rearrangement opens up an efficient access to highly functionalised ketones 4 and 7 with vicinal quaternary and tertiary stereogenic centres of excellent diastereo‐ and enantiomeric purity ( de =89–96%, ee =82 to >98%) by using the SAMP/RAMP hydrazone methodology. Starting from hydrazones ( S )‐ 2 , we describe a dianionic and a Lewis acid‐mediated variant of the [3.3]‐sigmatropic Carroll rearrangement. The relative and absolute configuration of the new stereogenic centres created by C–C bond formation were assigned by X‐ray crystallographic analysis of the hydrazones 3h and 3j .