Photoredox-Mediated Deoxygenative Radical Additions of Aromatic Acids to Vinyl Boronic Esters and gem-Diborylalkenes**

Anugula Nagaraju; Tamer Saiaede; Nadim Eghbarieh; Ahmad Masarwa

doi:10.1002/chem.202202646

Photoredox-Mediated Deoxygenative Radical Additions of Aromatic Acids to Vinyl Boronic Esters and gem-Diborylalkenes**

Anugula Nagaraju, Tamer Saiaede, Nadim Eghbarieh, Ahmad Masarwa^*

^*Corresponding author for this work

Institute of Chemistry

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

2 Scopus citations

Abstract

A new method to access β-keto-gem-diborylalkanes, by direct deoxygenative radical addition of aromatic carboxylic acids to gem-dibortlalkenes, is described. The reaction proceeds under mild photoredox catalysis and involves the photochemical C−O bond activation of aromatic carboxylic acids in the presence of PPh₃. It generates an acyl radical, which further undergoes an additional reaction with gem-diborylalkenes to form an α-gem-diboryl alkyl radical intermediate, which then reduces to the corresponding anion, which after protonation, affords the β-keto-gem-diborylalkane product. Moreover, the same scenario has been extended to the vinyl boronic esters, for example, gem-(Ar, Bpin)-alkenes, and gem-(Alkyl, Bpin)-alkenes. Importantly, this protocol provides a general platform for the late-stage functionalization of bio-active and drug molecules containing a carboxylic acid group.

Original language	American English
Article number	e202202646
Journal	Chemistry - A European Journal
Volume	29
Issue number	3
DOIs	https://doi.org/10.1002/chem.202202646
State	Published - 12 Jan 2023

Bibliographical note

Funding Information:
This research was supported by a grant from the Israel Science Foundation (Grant No. 287/21). We thank Dr. Benny Bogoslavsky (The Hebrew University of Jerusalem, Israel) for X‐ray crystallographic analysis. A.N. gratefully acknowledges the Lady Davies fellowship trust for postdoctoral fellowship support. T.S. is grateful for a M.Sc. fellowship from The Hebrew University of Jerusalem, Israel. N.E. is thankful for a Ph.D. fellowship from the Neubauer Foundation.

Publisher Copyright:
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Keywords

carboxylic-acids
deoxygenation
gem-diborylalkenes
organoborones
photochemistry

Access to Document

10.1002/chem.202202646

Cite this

@article{0de1fc0e211b414abb2f1e40ce49a254,

title = "Photoredox-Mediated Deoxygenative Radical Additions of Aromatic Acids to Vinyl Boronic Esters and gem-Diborylalkenes**",

abstract = "A new method to access β-keto-gem-diborylalkanes, by direct deoxygenative radical addition of aromatic carboxylic acids to gem-dibortlalkenes, is described. The reaction proceeds under mild photoredox catalysis and involves the photochemical C−O bond activation of aromatic carboxylic acids in the presence of PPh3. It generates an acyl radical, which further undergoes an additional reaction with gem-diborylalkenes to form an α-gem-diboryl alkyl radical intermediate, which then reduces to the corresponding anion, which after protonation, affords the β-keto-gem-diborylalkane product. Moreover, the same scenario has been extended to the vinyl boronic esters, for example, gem-(Ar, Bpin)-alkenes, and gem-(Alkyl, Bpin)-alkenes. Importantly, this protocol provides a general platform for the late-stage functionalization of bio-active and drug molecules containing a carboxylic acid group.",

keywords = "carboxylic-acids, deoxygenation, gem-diborylalkenes, organoborones, photochemistry",

author = "Anugula Nagaraju and Tamer Saiaede and Nadim Eghbarieh and Ahmad Masarwa",

note = "Funding Information: This research was supported by a grant from the Israel Science Foundation (Grant No. 287/21). We thank Dr. Benny Bogoslavsky (The Hebrew University of Jerusalem, Israel) for X‐ray crystallographic analysis. A.N. gratefully acknowledges the Lady Davies fellowship trust for postdoctoral fellowship support. T.S. is grateful for a M.Sc. fellowship from The Hebrew University of Jerusalem, Israel. N.E. is thankful for a Ph.D. fellowship from the Neubauer Foundation. Publisher Copyright: {\textcopyright} 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2023",

month = jan,

day = "12",

doi = "10.1002/chem.202202646",

language = "American English",

volume = "29",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "3",

}

TY - JOUR

T1 - Photoredox-Mediated Deoxygenative Radical Additions of Aromatic Acids to Vinyl Boronic Esters and gem-Diborylalkenes**

AU - Nagaraju, Anugula

AU - Saiaede, Tamer

AU - Eghbarieh, Nadim

AU - Masarwa, Ahmad

N1 - Funding Information: This research was supported by a grant from the Israel Science Foundation (Grant No. 287/21). We thank Dr. Benny Bogoslavsky (The Hebrew University of Jerusalem, Israel) for X‐ray crystallographic analysis. A.N. gratefully acknowledges the Lady Davies fellowship trust for postdoctoral fellowship support. T.S. is grateful for a M.Sc. fellowship from The Hebrew University of Jerusalem, Israel. N.E. is thankful for a Ph.D. fellowship from the Neubauer Foundation. Publisher Copyright: © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

PY - 2023/1/12

Y1 - 2023/1/12

N2 - A new method to access β-keto-gem-diborylalkanes, by direct deoxygenative radical addition of aromatic carboxylic acids to gem-dibortlalkenes, is described. The reaction proceeds under mild photoredox catalysis and involves the photochemical C−O bond activation of aromatic carboxylic acids in the presence of PPh3. It generates an acyl radical, which further undergoes an additional reaction with gem-diborylalkenes to form an α-gem-diboryl alkyl radical intermediate, which then reduces to the corresponding anion, which after protonation, affords the β-keto-gem-diborylalkane product. Moreover, the same scenario has been extended to the vinyl boronic esters, for example, gem-(Ar, Bpin)-alkenes, and gem-(Alkyl, Bpin)-alkenes. Importantly, this protocol provides a general platform for the late-stage functionalization of bio-active and drug molecules containing a carboxylic acid group.

AB - A new method to access β-keto-gem-diborylalkanes, by direct deoxygenative radical addition of aromatic carboxylic acids to gem-dibortlalkenes, is described. The reaction proceeds under mild photoredox catalysis and involves the photochemical C−O bond activation of aromatic carboxylic acids in the presence of PPh3. It generates an acyl radical, which further undergoes an additional reaction with gem-diborylalkenes to form an α-gem-diboryl alkyl radical intermediate, which then reduces to the corresponding anion, which after protonation, affords the β-keto-gem-diborylalkane product. Moreover, the same scenario has been extended to the vinyl boronic esters, for example, gem-(Ar, Bpin)-alkenes, and gem-(Alkyl, Bpin)-alkenes. Importantly, this protocol provides a general platform for the late-stage functionalization of bio-active and drug molecules containing a carboxylic acid group.

KW - carboxylic-acids

KW - deoxygenation

KW - gem-diborylalkenes

KW - organoborones

KW - photochemistry

UR - http://www.scopus.com/inward/record.url?scp=85143210803&partnerID=8YFLogxK

U2 - 10.1002/chem.202202646

DO - 10.1002/chem.202202646

M3 - Article

C2 - 36222076

AN - SCOPUS:85143210803

SN - 0947-6539

VL - 29

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 3

M1 - e202202646

ER -

Photoredox-Mediated Deoxygenative Radical Additions of Aromatic Acids to Vinyl Boronic Esters and gem-Diborylalkenes**

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Fingerprint

Cite this