Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications

Aimee K Clarke; Alison Parkin; Richard J K Taylor; William P Unsworth; James A Rossi-Ashton

doi:10.1021/acscatal.0c00690

Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications

Aimee K Clarke, Alison Parkin, Richard J K Taylor, William P Unsworth, James A Rossi-Ashton

Chemistry

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

Abstract

The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.

Original language	English
Pages (from-to)	5814-5820
Number of pages	7
Journal	ACS Catalysis
Volume	10
Issue number	10
Early online date	17 Apr 2020
DOIs	https://doi.org/10.1021/acscatal.0c00690
Publication status	Published - 15 May 2020

Bibliographical note

© 2020 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

Access to Document

10.1021/acscatal.0c00690

sulfoxide ACS Catal - revisons 3 FINAL
© 2020 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.
Accepted author manuscript, 824 KB

Cite this

@article{ebc7c823eebf4522a812e1a30b85d24b,

title = "Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications",

abstract = "The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.",

author = "Clarke, {Aimee K} and Alison Parkin and Taylor, {Richard J K} and Unsworth, {William P} and Rossi-Ashton, {James A}",

note = "{\textcopyright} 2020 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher{\textquoteright}s self-archiving policy. Further copying may not be permitted; contact the publisher for details.",

year = "2020",

month = may,

day = "15",

doi = "10.1021/acscatal.0c00690",

language = "English",

volume = "10",

pages = "5814--5820",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

T1 - Photocatalytic Deoxygenation of Sulfoxides Using Visible Light

T2 - Mechanistic Investigations and Synthetic Applications

AU - Clarke, Aimee K

AU - Parkin, Alison

AU - Taylor, Richard J K

AU - Unsworth, William P

AU - Rossi-Ashton, James A

N1 - © 2020 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2020/5/15

Y1 - 2020/5/15

N2 - The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.

AB - The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.

U2 - 10.1021/acscatal.0c00690

DO - 10.1021/acscatal.0c00690

M3 - Article

C2 - 32582464

SN - 2155-5435

VL - 10

SP - 5814

EP - 5820

JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -