Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis. (7th September 2015)

• Record Type: Journal Article
• Authors: Zheng, Lifei; Sonzini, Silvia; Ambarwati, Masyitha; Rosta, Edina; Scherman, Oren A.; Herrmann, Andreas
• Is Part Of: Angewandte Chemie. Volume 127:Number 44(2015)
• Page Start: 13199
• Page End: 13203
• Publication Date: 2015-09-07
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201505628
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Chiral macromolecules have been widely used as synthetic pockets to mimic natural enzymes and promote asymmetric reactions. An achiral host, cucurbit[8]uril (CB[8]), was used for an asymmetric Lewis acid catalyzed Diels–Alder reaction. We achieved a remarkable increase in enantioselectivity and a large rate acceleration in the presence of the nanoreactor by using an amino acid as the chiral source. Mechanistic and computational studies revealed that both the amino acid–Cu²⁺ complex and the dienophile substrate are included inside the macrocyclic host cavity, suggesting that contiguity and conformational constraints are fundamental to the catalytic process and rate enhancement. These results pave the way towards new studies on asymmetric reactions catalyzed in confined achiral cavities.</p> </abstract>