Photoresponsive Azobenzene-Functionalized Shell Cross-Linked Micelles for Selective Asymmetric Transfer Hydrogenation

Liu, Fangbei; Qu, Peiyuan; Weck, Marcus

doi:10.1021/acs.orglett.2c00925

Title: Photoresponsive Azobenzene-Functionalized Shell Cross-Linked Micelles for Selective Asymmetric Transfer Hydrogenation

Journal Article · Wed Apr 27 00:00:00 EDT 2022 · Organic Letters

DOI:https://doi.org/10.1021/acs.orglett.2c00925· OSTI ID:1865407

Liu, Fangbei ^[1]; Qu, Peiyuan ^[1];

^[1]

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

We describe the substrate-selective asymmetric transfer hydrogenation of aromatic ketones using rhodium complexes immobilized on a photoresponsive nanoreactor. The nanoreactor is based on multifunctional amphiphilic poly(2-oxazoline)s that are covalently cross-linked with functionalized azobenzene after micelle formation in water. The nanoreactor switches its morphology upon light irradiation in a wavelength-selective manner as confirmed by dynamic light scattering. Kinetic studies show that the gated behavior induced by the phototriggered reversible isomerization of trans- azobenzene to cis- azobenzene in the cross-linking layer is key to discriminate among substrates and reagents during catalysis. Under UV light irradiation, the diffusion of larger substrates into the core is slower in comparison to smaller substrates. The nanoreactor displays substrate selectivity, converting smaller ketone-substrates faster to the corresponding secondary alcohols.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15459

OSTI ID:: 1865407

Journal Information:: Organic Letters, Vol. 24, Issue 23; ISSN 1523-7060

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (32)

Reversible Photoswitching in Poly(2‐oxazoline) Nanoreactors Kuepfert, Michael; Qu, Peiyuan; Cohen, Aaron E. Chemistry – A European Journal, Vol. 26, Issue 51 https://doi.org/10.1002/chem.202000179	journal	August 2020
Self-Assembly of Linear−Dendritic Diblock Copolymers: From Nanofibers to Polymersomes del Barrio, Jesús; Oriol, Luis; Sánchez, Carlos Journal of the American Chemical Society, Vol. 132, Issue 11 https://doi.org/10.1021/ja9083946	journal	March 2010
Resolving Optical and Catalytic Activities in Thermoresponsive Nanoparticles by Permanent Ligation with Temperature‐Sensitive Polymers Chen, Yihuang; Wang, Zewei; Harn, Yeu Wei Angewandte Chemie International Edition, Vol. 58, Issue 34 https://doi.org/10.1002/anie.201906329	journal	July 2019
pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis Ansar, Siyam; Chakraborty, Saptarshi; Kitchens, Christopher Nanomaterials, Vol. 8, Issue 5 https://doi.org/10.3390/nano8050339	journal	May 2018
Thermoresponsive Hydrogels in Catalysis Hapiot, Frédéric; Menuel, Stéphane; Monflier, Eric ACS Catalysis, Vol. 3, Issue 5 https://doi.org/10.1021/cs400118c	journal	April 2013
Poly(2-oxazoline)s: A comprehensive overview of polymer structures and their physical properties: Poly(2-oxazoline)s Glassner, Mathias; Vergaelen, Maarten; Hoogenboom, Richard Polymer International, Vol. 67, Issue 1 https://doi.org/10.1002/pi.5457	journal	September 2017
Compartmentalisation of molecular catalysts for nonorthogonal tandem catalysis Qu, Peiyuan; Cleveland, Jacob W.; Ahmed, Eman Chemical Society Reviews, Vol. 51, Issue 1 https://doi.org/10.1039/D1CS00530H	journal	January 2022
Lab-in-a-Shell: Encapsulating Metal Clusters for Size Sieving Catalysis Qiao, Zhen-An; Zhang, Pengfei; Chai, Song-Hai Journal of the American Chemical Society, Vol. 136, Issue 32 https://doi.org/10.1021/ja505903r	journal	August 2014
Supramolecular design principles for efficient photoresponsive polymer–azobenzene complexes Vapaavuori, Jaana; Bazuin, C. Geraldine; Priimagi, Arri Journal of Materials Chemistry C, Vol. 6, Issue 9 https://doi.org/10.1039/C7TC05005D	journal	January 2018
Size-Selective Molecular Flasks Otte, Matthias ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01776	journal	August 2016
Cross‐Linked Polymeric Micelles as Catalytic Nanoreactors Qu, Peiyuan; Kuepfert, Michael; Ahmed, Eman European Journal of Inorganic Chemistry, Vol. 2021, Issue 15 https://doi.org/10.1002/ejic.202100013	journal	March 2021
Hollow Metal–Organic Framework Nanospheres via Emulsion-Based Interfacial Synthesis and Their Application in Size-Selective Catalysis Yang, Yufen; Wang, Fengwei; Yang, Qihao ACS Applied Materials & Interfaces, Vol. 6, Issue 20 https://doi.org/10.1021/am505145d	journal	October 2014
Metal–organic framework materials as catalysts Lee, JeongYong; Farha, Omar K.; Roberts, John Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459 https://doi.org/10.1039/b807080f	journal	January 2009
Azobenzene photomechanics: prospects and potential applications Mahimwalla, Zahid; Yager, Kevin G.; Mamiya, Jun-ichi Polymer Bulletin, Vol. 69, Issue 8 https://doi.org/10.1007/s00289-012-0792-0	journal	June 2012
Responsive Polymers as Smart Nanomaterials Enable Diverse Applications Zhao, Jing; Lee, Victoria E.; Liu, Rui Annual Review of Chemical and Biomolecular Engineering, Vol. 10, Issue 1 https://doi.org/10.1146/annurev-chembioeng-060718-030155	journal	June 2019
Photoswitchable catalysis based on the isomerisation of double bonds Dorel, Ruth; Feringa, Ben L. Chemical Communications, Vol. 55, Issue 46 https://doi.org/10.1039/C9CC01891C	journal	January 2019
Compartmentalization and Photoregulating Pathways for Incompatible Tandem Catalysis Qu, Peiyuan; Kuepfert, Michael; Hashmi, Maryam Journal of the American Chemical Society, Vol. 143, Issue 12 https://doi.org/10.1021/jacs.1c00257	journal	March 2021
Hollow silica nanosphere having functionalized interior surface with thin manganese oxide layer: nanoreactor framework for size-selective Lewis acid catalysis Anisur, Rahman Md; Shin, Jongmin; Choi, Hyung Ho Journal of Materials Chemistry, Vol. 20, Issue 47 https://doi.org/10.1039/c0jm02647f	journal	January 2010
Switchable Stimuli-Responsive Heterogeneous Catalysis Vassalini, Irene; Alessandri, Ivano Catalysts, Vol. 8, Issue 12 https://doi.org/10.3390/catal8120569	journal	November 2018
Shell Cross-Linked Micelle-Based Nanoreactors for the Substrate-Selective Hydrolytic Kinetic Resolution of Epoxides Liu, Yu; Wang, Yu; Wang, Yufeng Journal of the American Chemical Society, Vol. 133, Issue 36 https://doi.org/10.1021/ja206644d	journal	September 2011
Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations Qu, Peiyuan; Kuepfert, Michael; Jockusch, Steffen ACS Catalysis, Vol. 9, Issue 4 https://doi.org/10.1021/acscatal.8b04667	journal	February 2019
Review of the recent progress in photoresponsive molecularly imprinted polymers containing azobenzene chromophores Wei, Yu-bo; Tang, Qian; Gong, Cheng-bin Analytica Chimica Acta, Vol. 900 https://doi.org/10.1016/j.aca.2015.10.022	journal	November 2015
Photo-control of biological systems with azobenzene polymers Goulet-Hanssens, Alexis; Barrett, Christopher J. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 51, Issue 14 https://doi.org/10.1002/pola.26735	journal	May 2013
Metalation of a Thiocatechol-Functionalized Zr(IV)-Based Metal–Organic Framework for Selective C–H Functionalization Fei, Honghan; Cohen, Seth M. Journal of the American Chemical Society, Vol. 137, Issue 6 https://doi.org/10.1021/ja5126885	journal	February 2015
Molecularly Imprinted Polymers BelBruno, Joseph J. Chemical Reviews, Vol. 119, Issue 1 https://doi.org/10.1021/acs.chemrev.8b00171	journal	September 2018
RhIII- and IrIII-Catalyzed Asymmetric Transfer Hydrogenation of Ketones in Water Wu, Xiaofeng; Li, Xiaohong; Zanotti-Gerosa, Antonio Chemistry - A European Journal, Vol. 14, Issue 7 https://doi.org/10.1002/chem.200701258	journal	February 2008
Size‐Selective Hydroformylation by a Rhodium Catalyst Confined in a Supramolecular Cage Nurttila, Sandra S.; Brenner, Wolfgang; Mosquera, Jesús Chemistry – A European Journal https://doi.org/10.1002/chem.201804333	journal	December 2018
Photoresponsive Polymersomes Formed by Amphiphilic Linear–Dendritic Block Copolymers: Generation-Dependent Aggregation Behavior Lin, Yung-Lung; Chang, Hung-Yu; Sheng, Yu-Jane Macromolecules, Vol. 45, Issue 17 https://doi.org/10.1021/ma301251s	journal	August 2012
Industrial applications of metal–organic frameworks Czaja, Alexander U.; Trukhan, Natalia; Müller, Ulrich Chemical Society Reviews, Vol. 38, Issue 5, p. 1284-1293 https://doi.org/10.1039/b804680h	journal	January 2009
The chemistry of poly(2-oxazoline)s Verbraeken, Bart; Monnery, Bryn D.; Lava, Kathleen European Polymer Journal, Vol. 88 https://doi.org/10.1016/j.eurpolymj.2016.11.016	journal	March 2017
The Golden Age of Transfer Hydrogenation Wang, Dong; Astruc, Didier Chemical Reviews, Vol. 115, Issue 13 https://doi.org/10.1021/acs.chemrev.5b00203	journal	June 2015
Chiral Gating for Size- and Shape-Selective Asymmetric Catalysis Li, Xiaowei; Zhao, Yan Journal of the American Chemical Society, Vol. 141, Issue 35 https://doi.org/10.1021/jacs.9b06619	journal	August 2019

Similar Records

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 · OSTI ID:1865407

Qu, Peiyuan; Kuepfert, Michael; Hashmi, Maryam; +1 more

Shell Cross-Linked Micelles as Nanoreactors for Enantioselective Three-Step Tandem Catalysis

Journal Article · Mon Oct 01 00:00:00 EDT 2018 · Chemistry - A European Journal · OSTI ID:1865407

Kuepfert, Michael; Cohen, Aaron E.; Cullen, Olivia; +1 more

Acid–Base Bifunctional Shell Cross-Linked Micelle Nanoreactor for One-Pot Tandem Reaction

Journal Article · Tue Jan 05 00:00:00 EST 2016 · ACS Catalysis · OSTI ID:1865407

Lee, Li-Chen; Lu, Jie; Weck, Marcus; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Photoresponsive Azobenzene-Functionalized Shell Cross-Linked Micelles for Selective Asymmetric Transfer Hydrogenation

Citation Formats

References (32)

Similar Records

Related Subjects