Copper-Catalyzed Enantioselective Conjugate Addition to alpha,beta-Unsaturated Aldehydes with Various Organometallic Reagents

beta-Substituted aldehydes constitute a very important class of compounds found in nature. Synthesis of this motif can be envisioned by C-C bond formation on enals. For this purpose, we report herein the development of enantioselective copper-catalyzed conjugate addition of various organometallic re...

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Published inSynthesis (Stuttgart) Vol. 48; no. 19; pp. 3301 - 3308
Main Authors Goncalves-Contal, Sylvie, Gremaud, Ludovic, Palais, Laetitia, Babel, Lucille, Alexakis, Alexandre
Format Journal Article
LanguageEnglish
Published STUTTGART Thieme Medical Publishers 04.10.2016
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
enantioselectivity
ASYMMETRIC-SYNTHESIS
alpha,beta-unsaturated aldehydes
ORGANOZINC COMPOUNDS
CARBONYL-COMPOUNDS
ALPHA
organometallic reagents
conjugate addition
ENANTIOMERICALLY ENRICHED ZINC
natural products
DEHYDROGENATION
LIGANDS
CHLOROTRIMETHYLSILANE
1,4-ADDITION
GRIGNARD-REAGENTS
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Summary:beta-Substituted aldehydes constitute a very important class of compounds found in nature. Synthesis of this motif can be envisioned by C-C bond formation on enals. For this purpose, we report herein the development of enantioselective copper-catalyzed conjugate addition of various organometallic reagents to alpha,beta-unsaturated aldehydes with (R)-H(8)BINAP, (R)-TolBINAP, and (R)-SEGPHOS as chiral ligands. Three sets of conditions were successfully developed and several enals were used. Reactivity and regio- and enantioselectivities were strongly dependent on reaction conditions and substrates. Good to excellent regio- and enantioselectivities were obtained with zinc reagents R2Zn and aluminum reagents R3Al. However, the asymmetric conjugate addition of Grignard reagents afforded only moderate to good regio- and enantioselectivities.
ISSN:0039-7881
1437-210X
DOI:10.1055/s-0035-1562487