Heterogeneous Supramolecular Catalysis through Immobilization of Anionic M4L6 Assemblies on Cationic Polymers

Miyamura, Hiroyuki; Bergman, Robert G; Raymond, Kenneth N; Toste, F Dean

doi:10.1021/jacs.0c09556

Heterogeneous Supramolecular Catalysis through Immobilization of Anionic M₄L₆ Assemblies on Cationic Polymers

Journal Article · Sun Nov 01 23:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c09556· OSTI ID:1839002

Miyamura, Hiroyuki ^[1]; Bergman, Robert G ^[2]; Raymond, Kenneth N ^[2]; Toste, F Dean ^[2]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Tokyo (Japan)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Although most of the currently developed supramolecular catalysts that emulate enzymatic reactivity with unique selectivity and activity through specific host-guest interactions work under homogeneous conditions, enzymes in nature can operate under heterogeneous conditions as membrane-bound enzymes. In order to develop such a heterogeneous system, an immobilized chiral supramolecular cluster Ga₄1₆ (2) was introduced into cross-linked polymers with cationic functionalities. These heterogeneous supramolecular catalysts were used in aza-Prins and aza-Cope reactions and successfully applied to continuous-flow reactions. Additionally, they showed high durability and maintained high turnovers for long periods of time. In sharp contrast to the majority of examples of heterogenized homogeneous catalysts, the newly developed catalysts showed enhanced activity and robustness compared to those exhibited by the corresponding soluble cluster catalyst. An enantioenriched cluster was also immobilized to enable asymmetric catalysis, and activity and enantioselectivity of the supported chiral catalyst were maintained during recovery and reuse experiments and under a continuous-flow process. Significantly, the structure of the ammonium cations in the polymers affected stability, reactivity, and enantioselectivity, which is consistent with the hypothesis that the cationic moieties in the polymer support interact with cluster as an exohedral protecting shell, thereby influencing their catalytic performance.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; JSPS KAKENHI

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1839002

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 45 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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