Hydroxyl-directed C–C bond activation of benzophenones for the O-acylation of phenols

Connie Bader; Siri Bruhn; Letitia J. Yao; Christopher J. Douglas

doi:10.1016/j.tet.2022.133074

Hydroxyl-directed C–C bond activation of benzophenones for the O-acylation of phenols

Connie Bader, Siri Bruhn, Letitia J. Yao, Christopher J. Douglas

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

Abstract

We report that 2-hydroxyl benzophenones can be converted to phenyl salicylate esters by loss of an aryl group and O-acylation of the phenols. Iridium, cyclooctadiene, and bulky monodentate phosphine ligands catalyze the ketone C–C bond activation and fragmentation. We identified common side products in this process, which include C-acylation of the phenol reactant or trapping on cyclooctadiene. Several of the processes reported here appear to be under equilibrium control. Overall, our report provides insight into the activation and functionalization of unstrained C–C bonds with group 9 catalysts.

Original language	English (US)
Article number	133074
Journal	Tetrahedron
Volume	128
DOIs	https://doi.org/10.1016/j.tet.2022.133074
State	Published - Dec 3 2022

Bibliographical note

Funding Information:
We thank the National Science Foundation , Graduate Research Fellowship program, Grant No. 00039202 to CBA and the University of Minnesota – Twin Cities Lando Program for a summer research fellowship to SB. We thank colleagues Michael Grillo (UMN) for assistance in acquiring high field 13 C NMR data and Hannah Holst (UMN) for assistance with purification of several samples.

Publisher Copyright:
© 2022

Keywords

Benzophenones
C–C bond Activation
Iridium
Mechanism

Publisher link

10.1016/j.tet.2022.133074

Find It

Find It at U of M Libraries

Cite this

@article{598fcd8329f146ac86e7f807d7f7a7b8,

title = "Hydroxyl-directed C–C bond activation of benzophenones for the O-acylation of phenols",

abstract = "We report that 2-hydroxyl benzophenones can be converted to phenyl salicylate esters by loss of an aryl group and O-acylation of the phenols. Iridium, cyclooctadiene, and bulky monodentate phosphine ligands catalyze the ketone C–C bond activation and fragmentation. We identified common side products in this process, which include C-acylation of the phenol reactant or trapping on cyclooctadiene. Several of the processes reported here appear to be under equilibrium control. Overall, our report provides insight into the activation and functionalization of unstrained C–C bonds with group 9 catalysts.",

keywords = "Benzophenones, C–C bond Activation, Iridium, Mechanism",

author = "Connie Bader and Siri Bruhn and Yao, {Letitia J.} and Douglas, {Christopher J.}",

note = "Funding Information: We thank the National Science Foundation , Graduate Research Fellowship program, Grant No. 00039202 to CBA and the University of Minnesota – Twin Cities Lando Program for a summer research fellowship to SB. We thank colleagues Michael Grillo (UMN) for assistance in acquiring high field 13 C NMR data and Hannah Holst (UMN) for assistance with purification of several samples. Publisher Copyright: {\textcopyright} 2022",

year = "2022",

month = dec,

day = "3",

doi = "10.1016/j.tet.2022.133074",

language = "English (US)",

volume = "128",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Limited",

}

TY - JOUR

T1 - Hydroxyl-directed C–C bond activation of benzophenones for the O-acylation of phenols

AU - Bader, Connie

AU - Bruhn, Siri

AU - Yao, Letitia J.

AU - Douglas, Christopher J.

N1 - Funding Information: We thank the National Science Foundation , Graduate Research Fellowship program, Grant No. 00039202 to CBA and the University of Minnesota – Twin Cities Lando Program for a summer research fellowship to SB. We thank colleagues Michael Grillo (UMN) for assistance in acquiring high field 13 C NMR data and Hannah Holst (UMN) for assistance with purification of several samples. Publisher Copyright: © 2022

PY - 2022/12/3

Y1 - 2022/12/3

N2 - We report that 2-hydroxyl benzophenones can be converted to phenyl salicylate esters by loss of an aryl group and O-acylation of the phenols. Iridium, cyclooctadiene, and bulky monodentate phosphine ligands catalyze the ketone C–C bond activation and fragmentation. We identified common side products in this process, which include C-acylation of the phenol reactant or trapping on cyclooctadiene. Several of the processes reported here appear to be under equilibrium control. Overall, our report provides insight into the activation and functionalization of unstrained C–C bonds with group 9 catalysts.

AB - We report that 2-hydroxyl benzophenones can be converted to phenyl salicylate esters by loss of an aryl group and O-acylation of the phenols. Iridium, cyclooctadiene, and bulky monodentate phosphine ligands catalyze the ketone C–C bond activation and fragmentation. We identified common side products in this process, which include C-acylation of the phenol reactant or trapping on cyclooctadiene. Several of the processes reported here appear to be under equilibrium control. Overall, our report provides insight into the activation and functionalization of unstrained C–C bonds with group 9 catalysts.

KW - Benzophenones

KW - C–C bond Activation

KW - Iridium

KW - Mechanism

UR - http://www.scopus.com/inward/record.url?scp=85142141612&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85142141612&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2022.133074

DO - 10.1016/j.tet.2022.133074

M3 - Article

AN - SCOPUS:85142141612

SN - 0040-4020

VL - 128

JO - Tetrahedron

JF - Tetrahedron

M1 - 133074

ER -

Hydroxyl-directed C–C bond activation of benzophenones for the O-acylation of phenols

Abstract

Bibliographical note

Keywords

Publisher link

Find It

Other files and links

Fingerprint

Cite this