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Journal ArticleDOI

Cooperative dual catalysis: application to the highly enantioselective conjugate cyanation of unsaturated imides.

TLDR
Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide byThe Er complex as the mechanism to achieve a highly reactive system for the enantioselective conjugate addition of cyanides to alpha,beta-unsaturated imides.
Abstract
Cooperative heterobimetallic catalysis was used as a design principle to achieve a highly reactive system for the enantioselective conjugate addition of cyanide to α,β-unsaturated imides. A dual-catalyst pathway involving chiral (salen)Al complex 1b and chiral (pybox)Er complex 4b provides measurable improvements in rates and enantioselectivities relative to single-catalyst systems. Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide by the Er complex.

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Citations
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Journal ArticleDOI

Synergistic catalysis: A powerful synthetic strategy for new reaction development

TL;DR: This perspective aims to highlight the benefits of synergistic catalysis using many of the successful examples of synergism catalysis found in the literature.
Journal ArticleDOI

Enantio- and Diastereodivergent Dual Catalysis: α-Allylation of Branched Aldehydes

TL;DR: A pair of chiral catalysts—an iridium complex and an amine—that operate in concert to facilitate carbon-carbon bond formation, while retaining independent stereoselectivity toward their respective sides of the bond are reported.
Journal ArticleDOI

When Organocatalysis Meets Transition‐Metal Catalysis

TL;DR: In the past several years, applications of transition metal complexes in tuning the reactivity of organocatalyst-promoted transformations have attracted increasing attention in the synthetic community as discussed by the authors.
Journal ArticleDOI

Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium-Salen Complexes

TL;DR: A catalytic cycle that explains why the bimetallic complexes display such high catalytic activity has been developed and it was shown that if enantiomericallypure styrene oxide was used as substrate, then enantiomersically pure styrene carbonate was formed.
References
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Journal ArticleDOI

Two-Metal Ion Catalysis in Enzymatic Acyl- and Phosphoryl-Transfer Reactions

TL;DR: A remarkable diversity is also seen in the structures of the active sites of these di- and trinuclear metalloenzymes, even for enzymes that catalyze very similar reactions, including hydrolytic cleavage of phosphomono-, -di- and -triester bonds, phosphoanhydride bonds as well as of peptide bonds or urea.
Journal ArticleDOI

Highly active oligomeric (salen)co catalysts for asymmetric epoxide ring-opening reactions.

TL;DR: New, easily synthesized oligomeric analogues of 1 are reported that exhibit not only remarkably enhanced reactivity, but also significantly higher enantioselectivity relative to 1.
Journal ArticleDOI

Highly Enantioselective, Catalytic Conjugate Addition of Cyanide to α,β-Unsaturated Imides

TL;DR: Mechanistic data obtained thus far point to a cooperative bimetallic mechanism for nucleophile and electrophile activation.
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