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Mechanism-based enhancement of scope and enantioselectivity for reactions involving a copper-substituted stereogenic carbon centre
- Source :
- Nature Chemistry. 10:99-108
- Publication Year :
- 2017
- Publisher :
- Springer Science and Business Media LLC, 2017.
-
Abstract
- A rapidly emerging set of catalytic reactions involves intermediates that contain a copper-substituted stereogenic carbon centre. Here, we demonstrate that intimate understanding of this distinction provides ways for addressing limitations in reaction scope and explaining why unexpected variations in enantioselectivity often occur. By using catalytic enantioselective Cu–boryl addition to alkenes as the model process, we have been able to elucidate several key mechanistic principles. We show that higher electrophile concentration can lead to elevated enantioselectivity; this is because diastereoselective Cu–H elimination may be avoided and/or achiral Cu–boryl intermediates can be converted to allyl–B(pin) rather than add to an alkene. We illustrate that lower alkene amounts and/or higher chiral ligand concentration can minimize the deleterious influence of achiral Cu–alkyl species, resulting in improved enantiomeric ratios. Moreover, and surprisingly, we find that enantioselectivities are higher with the less reactive allylphenyl carbonates as chemoselective copper–hydride elimination is faster with an achiral Cu-alkyl species.
- Subjects :
- Boron Compounds
Reaction mechanism
General Chemical Engineering
Stereoisomerism
Chemistry Techniques, Synthetic
Alkenes
010402 general chemistry
01 natural sciences
Catalysis
Article
Stereocenter
Organometallic Compounds
Organic chemistry
chemistry.chemical_classification
010405 organic chemistry
Chemistry
Alkene
Chiral ligand
Enantioselective synthesis
General Chemistry
Combinatorial chemistry
0104 chemical sciences
Models, Chemical
Electrophile
Copper
Subjects
Details
- ISSN :
- 17554349 and 17554330
- Volume :
- 10
- Database :
- OpenAIRE
- Journal :
- Nature Chemistry
- Accession number :
- edsair.doi.dedup.....67f65f969971d80ed2f0bb3225227983