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Terpene Cyclizations inside a Supramolecular Catalyst: Leaving Group-Controlled Product Selectivity and Mechanistic Studies

Zhang, Qi and Catti, Lorenzo and Pleiss, Jürgen and Tiefenbacher, Konrad. (2017) Terpene Cyclizations inside a Supramolecular Catalyst: Leaving Group-Controlled Product Selectivity and Mechanistic Studies. Journal of the American Chemical Society, 139 (33). pp. 11482-11492.

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Official URL: http://edoc.unibas.ch/58983/

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Abstract

The tail-to-head terpene cyclization is arguably one of the most complex reactions found in nature. The hydrogen-bond-based resorcinarene capsule represents the first man-made enzyme-like catalyst that is capable of catalyzing this reaction. Based on noncovalent interactions between the capsule and the substrate, the product selectivity can be tuned by using different leaving groups. A detailed mechanistic investigation was performed to elucidate the reaction mechanism. For the cyclization of geranyl acetate, it was found that the cleavage of the leaving group is the rate-determining step. Furthermore, the studies revealed that trace amounts of acid are required as cocatalyst. A series of control experiments demonstrate that a synergistic interplay between the supramolecular capsule and the acid traces is required for catalytic activity.
Faculties and Departments:05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Chemie > Synthesis of Functional Modules (Tiefenbacher)
UniBasel Contributors:Zhang, Qi and Catti, Lorenzo and Tiefenbacher, Konrad Karl
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:22 Jan 2018 13:14
Deposited On:22 Jan 2018 13:14

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