Site-selective C–H functionalization in a cyclodextrin metal-organic framework

Aspen X.Y. Chen; Tanay Kesharwani; Yong Wu; Charlotte L. Stern; Luka Đorđević; Huang Wu; Yu Wang; Bo Song; Liang Feng; Long Zhang; Xingang Zhao; Yang Jiao; Xuesong Li; Han Han; Chun Tang; Ruihua Zhang; Hongliang Chen; Kang Cai; Samuel I. Stupp; Haoyuan Chen; Dengke Shen; J. Fraser Stoddart

doi:10.1016/j.chempr.2023.08.028

Site-selective C–H functionalization in a cyclodextrin metal-organic framework

Aspen X.Y. Chen^*, Tanay Kesharwani, Yong Wu, Charlotte L. Stern, Luka Đorđević, Huang Wu, Yu Wang, Bo Song, Liang Feng, Long Zhang, Xingang Zhao, Yang Jiao, Xuesong Li, Han Han, Chun Tang, Ruihua Zhang, Hongliang Chen, Kang Cai, Samuel I. Stupp, Haoyuan Chen^*Dengke Shen^*, J. Fraser Stoddart^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Confinement is a unifying element in selective enzymatic reactions but has rarely been used to control site selectivity of carbon–hydrogen (C–H) bond functionalization in artificial receptors. Herein, we demonstrate the selective functionalization of one of seven C(sp³)–H bonds on a D-glucopyranosyl residue of γ-cyclodextrin (γ-CD) by irradiating 2-benzoylbenzoate in a γ-cyclodextrin-containing metal-organic framework (CD-MOF-1). Both ¹H NMR spectroscopy and X-ray crystallography of the products confirm that functionalization occurs selectively at one of the two C(sp³)–H bonds on the C6 position of a D-glucopyranosyl residue. The alignment of 2-benzoylbenzoate inside (γ-CD)₂ tunnels in CD-MOF-1, as revealed by X-ray crystallography, precludes C–H functionalization on the outer surface of the γ-CD tori. Theoretical calculations indicate less steric hindrance associated with C6-functionalized (γ-CD)₂ tunnels in CD-MOF-1 compared with C3 and C5, leading to the observed site selectivity.

Original language	English (US)
Pages (from-to)	234-249
Number of pages	16
Journal	Chem
Volume	10
Issue number	1
DOIs	https://doi.org/10.1016/j.chempr.2023.08.028
State	Published - Jan 11 2024

Keywords

C–H functionalization
SDG12: Responsible consumption and production
SDG3: Good health and well-being
confinement
cyclodextrin
hydrogen atom transfer
metal-organic framework
site selectivity

ASJC Scopus subject areas

General Chemistry
Biochemistry
Environmental Chemistry
General Chemical Engineering
Biochemistry, medical
Materials Chemistry

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10.1016/j.chempr.2023.08.028

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Chen, A. X. Y., Kesharwani, T., Wu, Y., Stern, C. L., Đorđević, L., Wu, H., Wang, Y., Song, B., Feng, L., Zhang, L., Zhao, X., Jiao, Y., Li, X., Han, H., Tang, C., Zhang, R., Chen, H., Cai, K., Stupp, S. I., ... Stoddart, J. F. (2024). Site-selective C–H functionalization in a cyclodextrin metal-organic framework. Chem, 10(1), 234-249. https://doi.org/10.1016/j.chempr.2023.08.028

@article{1a12d07f6a694dcfac1059a94c2e781c,

title = "Site-selective C–H functionalization in a cyclodextrin metal-organic framework",

abstract = "Confinement is a unifying element in selective enzymatic reactions but has rarely been used to control site selectivity of carbon–hydrogen (C–H) bond functionalization in artificial receptors. Herein, we demonstrate the selective functionalization of one of seven C(sp3)–H bonds on a D-glucopyranosyl residue of γ-cyclodextrin (γ-CD) by irradiating 2-benzoylbenzoate in a γ-cyclodextrin-containing metal-organic framework (CD-MOF-1). Both 1H NMR spectroscopy and X-ray crystallography of the products confirm that functionalization occurs selectively at one of the two C(sp3)–H bonds on the C6 position of a D-glucopyranosyl residue. The alignment of 2-benzoylbenzoate inside (γ-CD)2 tunnels in CD-MOF-1, as revealed by X-ray crystallography, precludes C–H functionalization on the outer surface of the γ-CD tori. Theoretical calculations indicate less steric hindrance associated with C6-functionalized (γ-CD)2 tunnels in CD-MOF-1 compared with C3 and C5, leading to the observed site selectivity.",

keywords = "C–H functionalization, SDG12: Responsible consumption and production, SDG3: Good health and well-being, confinement, cyclodextrin, hydrogen atom transfer, metal-organic framework, site selectivity",

author = "Chen, {Aspen X.Y.} and Tanay Kesharwani and Yong Wu and Stern, {Charlotte L.} and Luka {\D}or{\d}evi{\'c} and Huang Wu and Yu Wang and Bo Song and Liang Feng and Long Zhang and Xingang Zhao and Yang Jiao and Xuesong Li and Han Han and Chun Tang and Ruihua Zhang and Hongliang Chen and Kang Cai and Stupp, {Samuel I.} and Haoyuan Chen and Dengke Shen and Stoddart, {J. Fraser}",

note = "Publisher Copyright: {\textcopyright} 2023 Elsevier Inc.",

year = "2024",

month = jan,

day = "11",

doi = "10.1016/j.chempr.2023.08.028",

language = "English (US)",

volume = "10",

pages = "234--249",

journal = "Chem",

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publisher = "Elsevier Inc.",

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Chen, AXY, Kesharwani, T, Wu, Y, Stern, CL, Đorđević, L, Wu, H, Wang, Y, Song, B, Feng, L, Zhang, L, Zhao, X, Jiao, Y, Li, X, Han, H, Tang, C, Zhang, R, Chen, H, Cai, K, Stupp, SI, Chen, H, Shen, D & Stoddart, JF 2024, 'Site-selective C–H functionalization in a cyclodextrin metal-organic framework', Chem, vol. 10, no. 1, pp. 234-249. https://doi.org/10.1016/j.chempr.2023.08.028

TY - JOUR

T1 - Site-selective C–H functionalization in a cyclodextrin metal-organic framework

AU - Chen, Aspen X.Y.

AU - Kesharwani, Tanay

AU - Wu, Yong

AU - Stern, Charlotte L.

AU - Đorđević, Luka

AU - Wu, Huang

AU - Wang, Yu

AU - Song, Bo

AU - Feng, Liang

AU - Zhang, Long

AU - Zhao, Xingang

AU - Jiao, Yang

AU - Li, Xuesong

AU - Han, Han

AU - Tang, Chun

AU - Zhang, Ruihua

AU - Chen, Hongliang

AU - Cai, Kang

AU - Stupp, Samuel I.

AU - Chen, Haoyuan

AU - Shen, Dengke

AU - Stoddart, J. Fraser

PY - 2024/1/11

Y1 - 2024/1/11

N2 - Confinement is a unifying element in selective enzymatic reactions but has rarely been used to control site selectivity of carbon–hydrogen (C–H) bond functionalization in artificial receptors. Herein, we demonstrate the selective functionalization of one of seven C(sp3)–H bonds on a D-glucopyranosyl residue of γ-cyclodextrin (γ-CD) by irradiating 2-benzoylbenzoate in a γ-cyclodextrin-containing metal-organic framework (CD-MOF-1). Both 1H NMR spectroscopy and X-ray crystallography of the products confirm that functionalization occurs selectively at one of the two C(sp3)–H bonds on the C6 position of a D-glucopyranosyl residue. The alignment of 2-benzoylbenzoate inside (γ-CD)2 tunnels in CD-MOF-1, as revealed by X-ray crystallography, precludes C–H functionalization on the outer surface of the γ-CD tori. Theoretical calculations indicate less steric hindrance associated with C6-functionalized (γ-CD)2 tunnels in CD-MOF-1 compared with C3 and C5, leading to the observed site selectivity.

AB - Confinement is a unifying element in selective enzymatic reactions but has rarely been used to control site selectivity of carbon–hydrogen (C–H) bond functionalization in artificial receptors. Herein, we demonstrate the selective functionalization of one of seven C(sp3)–H bonds on a D-glucopyranosyl residue of γ-cyclodextrin (γ-CD) by irradiating 2-benzoylbenzoate in a γ-cyclodextrin-containing metal-organic framework (CD-MOF-1). Both 1H NMR spectroscopy and X-ray crystallography of the products confirm that functionalization occurs selectively at one of the two C(sp3)–H bonds on the C6 position of a D-glucopyranosyl residue. The alignment of 2-benzoylbenzoate inside (γ-CD)2 tunnels in CD-MOF-1, as revealed by X-ray crystallography, precludes C–H functionalization on the outer surface of the γ-CD tori. Theoretical calculations indicate less steric hindrance associated with C6-functionalized (γ-CD)2 tunnels in CD-MOF-1 compared with C3 and C5, leading to the observed site selectivity.

KW - C–H functionalization

KW - SDG12: Responsible consumption and production

KW - SDG3: Good health and well-being

KW - confinement

KW - cyclodextrin

KW - hydrogen atom transfer

KW - metal-organic framework

KW - site selectivity

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UR - http://www.scopus.com/inward/citedby.url?scp=85186070272&partnerID=8YFLogxK

U2 - 10.1016/j.chempr.2023.08.028

DO - 10.1016/j.chempr.2023.08.028

M3 - Article

AN - SCOPUS:85186070272

SN - 2451-9308

VL - 10

SP - 234

EP - 249

JO - Chem

JF - Chem

IS - 1

ER -

Site-selective C–H functionalization in a cyclodextrin metal-organic framework

Abstract

Keywords

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