Compartmentalization and Photo-Regulating Pathways for Incompatible Tandem Catalysis

Qu, Peiyuan; Kuepfert, Michael; Hashmi, Maryam; Weck, Marcus

doi:10.1021/jacs.1c00257

Title: Compartmentalization and Photo-Regulating Pathways for Incompatible Tandem Catalysis

Journal Article · Tue Mar 16 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c00257· OSTI ID:1768882

Qu, Peiyuan ^[1]; Kuepfert, Michael ^[1]; Hashmi, Maryam ^[1]; Weck, Marcus ^[1]

New York Univ. (NYU), NY (United States)

This contribution describes an advanced compartmentalized micellar nanoreactor that possesses a reversible photoresponsive feature and its application towards photo-regulating reaction pathways for incompatible tandem catalysis under aqueous conditions. The smart nanoreactor is based on multi-functional amphiphilic poly(2-oxazoline)s and covalently crosslinked with spiropyran upon micelle formation in water. It responds to light irradiation in a wavelength-selective manner switching its morphology as confirmed by dynamic light scattering and cryo-transition electron microscopy. The compartmental structure renders distinct nanoconfinements for two incompatible enantioselective transformations: a rhodium-diene complex-catalyzed asymmetric 1,4-addition occurs in the hydrophilic corona while a Rh-TsDPEN-catalyzed asymmetric transfer hydrogenation proceeds in the hydrophobic core. Control experiments and kinetic studies showed that the gated behavior induced by the photo-triggered reversible spiropyran to merocyanine transition in the cross-linking layer is key to discriminate among substrates/reagents during the catalysis. Here, the smart nanoreactor realized photo-regulation to direct the reaction pathway to give a multi-chiral product with high conversions and perfect enantioselectivities in aqueous media. Our SCM catalytic system, on a basic level, mimics the concepts of compartmentalization and responsiveness Nature uses to coordinate thousands of incompatible chemical transformations into streamlined metabolic processes.

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Research Organization:: New York Univ. (NYU), NY (United States)

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

Grant/Contract Number:: FG02-03ER15459

OSTI ID:: 1768882

Journal Information:: Journal of the American Chemical Society, Vol. 143, Issue 12; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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