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Review
. 2022 Jan 18;27(3):619.
doi: 10.3390/molecules27030619.

Recent Advances in Visible-Light Photoredox Catalysis for the Thiol-Ene/Yne Reactions

Qian Xiao  1   2 , Qing-Xiao Tong  2 , Jian-Ji Zhong  2   3
Affiliations
Review

Recent Advances in Visible-Light Photoredox Catalysis for the Thiol-Ene/Yne Reactions

Qian Xiao et al. Molecules. .

Abstract

Visible-light photoredox catalysis has been established as a popular and powerful tool for organic transformations owing to its inherent characterization of environmental friendliness and sustainability in the past decades. The thiol-ene/yne reactions, the direct hydrothiolation of alkenes/alkynes with thiols, represents one of the most efficient and atom-economic approaches for the carbon-sulfur bonds construction. In traditional methodologies, harsh conditions such as stoichiometric reagents or a specialized UV photo-apparatus were necessary suffering from various disadvantages. In particular, visible-light photoredox catalysis has also been demonstrated to be a greener and milder protocol for the thiol-ene/yne reactions in recent years. Additionally, unprecedented advancements have been achieved in this area during the past decade. In this review, we will summarize the recent advances in visible-light photoredox catalyzed thiol-ene/yne reactions from 2015 to 2021. Synthetic strategies, substrate scope, and proposed reaction pathways are mainly discussed.

Keywords: green chemistry; photoredox catalysis; synthetic methodologies; thiol-ene/yne reaction.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Selected pharmaceuticals bearing thioether moiety.
Scheme 1
Scheme 1
The general reaction pathway for the thiol-ene/yne reactions.
Scheme 2
Scheme 2
Visible-light-promoted thiol-ene reaction using titanium dioxide.
Scheme 3
Scheme 3
Visible-light-photocatalyzed radical thiol-ene reaction using bismuth oxide.
Scheme 4
Scheme 4
Visible-light-photocatalyzed thiol-ene reaction by phenylglyoxylic acid.
Scheme 5
Scheme 5
Visible-light-photocatalyzed thiol-ene reaction by benzophenone.
Scheme 6
Scheme 6
Visible-light-photocatalyzed thiol-ene reaction using 9-mesityl-10-methylacridinium tetrafluoroborate.
Scheme 7
Scheme 7
Visible-light-photocatalyzed thiol-ene reaction for modification of natural lignin.
Scheme 8
Scheme 8
Visible-light-photocatalyzed thiol-ene reaction via a proton-coupled electron transfer process.
Scheme 9
Scheme 9
Cysteine-specific bioconjugation by photocatalytic thiol-ene reaction under biocompatible conditions.
Scheme 10
Scheme 10
Photocatalyzed thiol-ene reaction for difluorostyrenes functionalization with tetrafluoropyridine-4-thiol.
Scheme 11
Scheme 11
Visible-light-photocatalyzed thiol-yne reaction by Eosin Y.
Scheme 12
Scheme 12
Visible-light-photocatalyzed thiol-yne reaction by 9-mesityl-10-methylacridinium tetrafluoroborate.
Scheme 13
Scheme 13
Visible-light-photocatalyzed thiol-ene/yne reaction by ZnIn2S4.
Scheme 14
Scheme 14
General strategy for synthesis of β-hydroxysulfides/β-ketone sulfides.
Scheme 15
Scheme 15
Visible-light-photocatalyzed gem-difunctionalization of alkynes for the synthesis of α,α-aminothio-substituted carbonyl compounds.
Scheme 16
Scheme 16
Visible-light photocatalysis for the synthesis of β-hydroxydithioacetals.
Scheme 17
Scheme 17
Light-promoted hydroxysulfenylation of alkenes with thiophenols in the presence of tertiary amines.
Scheme 18
Scheme 18
Strategy for synthesis of sulfoxides via thiol–ene/oxidation tandem reaction.
Scheme 19
Scheme 19
(a–c) Photocatalyzed selective synthesis of sulfoxides via thiol–ene/yne reaction. (d) General reaction mechanism.
Scheme 20
Scheme 20
The general mechanism of photoredox synthesis of sulfoxides.
Scheme 21
Scheme 21
Photocatalyzed Markovnikov-selective hydrothiolation of enamides and enecarbamates.
Scheme 22
Scheme 22
Photoredox/cobalt catalyzed Markovnikov-selective thiol-ene reaction.
Scheme 23
Scheme 23
Photocatalytic Markovnikov-selective addition of p-toluenethiol to phenylacetylene.
Scheme 24
Scheme 24
A photocatalyzed Markovnikov thiol-yne reaction via associative electron upconversion.
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