Photoinduced Dynamic Radical Processes for Isomerizations, Deracemizations, and Dynamic Kinetic Resolutions

Article Chemistry, Multidisciplinary

Leveraging the n→π* Interaction in Alkene Isomerization by Selective Energy Transfer Catalysis

Tomas Nevesely et al.

Summary: Examples of geometric alkene isomerization in nature usually occur in the exergonic direction. This study investigates the reverse isomerization and validates the interactions as the driving force by selective energy transfer catalysis.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Add to Collection

Review Chemistry, Multidisciplinary

Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Amy Y. Chan et al.

Summary: The merger of photoredox catalysis with transition metal catalysis, known as metallaphotoredox catalysis, has become an important part of synthetic methodology. It combines the bond formation capability of transition metal catalysis with the utility of photoinduced electron and energy transfer processes. Photocatalytic substrate activation allows the involvement of simple starting materials in metal-mediated bond-forming processes, while electron or energy transfer with organometallic intermediates provides a complementary activation mode to traditional catalytic platforms.

CHEMICAL REVIEWS (2022)

Add to Collection

Review Chemistry, Multidisciplinary

Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis

Christian A. Malapit et al.

Summary: Synthetic organic electrosynthesis has made significant progress in recent decades, improving both selectivity and efficiency, and exploring new transformations and sustainable reactions. This review discusses the latest advances in combining electrochemistry and homogeneous transition-metal catalysis for organic synthesis, and explores future directions and challenges in the field.

CHEMICAL REVIEWS (2022)

Add to Collection

Review Chemistry, Multidisciplinary

Photoredox-Catalyzed C-H Functionalization Reactions

Natalie Holmberg-Douglas et al.

Summary: The fields of C-H functionalization and photoredox catalysis have gained significant interest and utility in various scientific disciplines. This review focuses on the use of photoredox catalysis in C-H functionalization reactions, highlighting both inorganic/organometallic and organic-based photoredox catalytic systems. The subdivision by reaction class (sp(2) or sp(3) C-H functionalization) provides perspective and tactical strategies for synthetic applications.

CHEMICAL REVIEWS (2022)

Add to Collection

Review Chemistry, Organic

Organocatalytic Dynamic Kinetic Resolution: An Update

Helene Pellissier

Summary: Organocatalytic dynamic kinetic resolution (DKR) has emerged as a promising field in the past two decades, allowing efficient separation of chiral compounds. This review aims to provide an update on organocatalytic DKRs since 2016.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2022)

Add to Collection

Article Chemistry, Multidisciplinary

A Change from Kinetic to Thermodynamic Control Enables trans-Selective Stereochemical Editing of Vicinal Diols

Yu-An Zhang et al.

Summary: This study reports a new method for selectively catalytic isomerization of cis-1,2-diols to trans-diequatorial-1,2-diols, which proceeds under mild conditions, is highly chemoselective, and broadly functional group tolerant. The method provides a concise access to trans-diol products that are not readily obtained using other methods, and operates through a reversible hydrogen atom transfer pathway mediated by the silanethiol catalyst.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Add to Collection

Article Chemistry, Multidisciplinary

Selective Isomerization via Transient Thermodynamic Control: Dynamic Epimerization of trans to cis Diols

Christian J. Oswood et al.

Summary: Traditional approaches to stereoselective synthesis usually require high levels of control in forming new stereocenters. This study presents an alternative method where the stereochemistry of organic substrates is selectively edited without further structural modification, allowing access to rare or valuable stereochemical configurations.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Add to Collection

Article Chemistry, Multidisciplinary

Contra-Thermodynamic Positional Isomerization of Olefins

Kuo Zhao et al.

Summary: A novel light-driven method for the contra-thermodynamic positional isomerization of olefins is described, involving stepwise PCET activation and in situ protodemetalation steps to achieve regioselective and efficient transformation of olefin substrates. The method demonstrated good compatibility with a broad range of isopropylidene substrates and presents promising prospects for further mechanistic investigations.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Add to Collection

Article Chemistry, Multidisciplinary

Catalytic, contra-Thermodynamic Positional Alkene Isomerization

Gino Occhialini et al.

Summary: The study presents a novel dual-catalyst system that enables contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing direct access to terminal alkene isomers from conjugated, internal alkene starting materials. Mechanistic studies suggest a regiospecific bimolecular homolytic substitution mechanism involving an allyl-cobaloxime intermediate.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Add to Collection

Review Chemistry, Applied

Recent Progress and Developments in Chemoenzymatic and Biocatalytic Dynamic Kinetic Resolution

Li-Cheng Yang et al.

Summary: This article summarizes the chemoenzymatic and biocatalytic methodologies for DKR developed in the past decade, highlighting their applications in the preparation of active pharmaceutical ingredients and emerging paradigms.

ORGANIC PROCESS RESEARCH & DEVELOPMENT (2022)

Add to Collection

Review Chemistry, Multidisciplinary

Advances in the E → Z Isomerization of Alkenes Using Small Molecule Photocatalysts

Tomas Nevesely et al.

Summary: Geometrical E → Z alkene isomerization, a critical topic in organic photochemistry, has seen significant advancements in recent years. By utilizing energy transfer catalysis, directed isomerization of alkenes can be achieved. This review summarizes the progress in the field of geometric alkene isomerization enabled by energy transfer catalysis from 2000 to 2020, and discusses the reaction mechanisms, induction models, and applications in total synthesis and regioselective reactions.

CHEMICAL REVIEWS (2022)

Add to Collection

Article Multidisciplinary Sciences

Deracemization through photochemical E/Z isomerization of enamines

Mouxin Huang et al.

Summary: This study presents a distinctive photochemical E/Z isomerization strategy for the deracemization of α-branched aldehydes, which involves the use of simple aminocatalysts and readily available photosensitizers. The method enables the direct transformation of racemic α-branched aldehydes into enantiopure α-tertiary carbonyls with high selectivity.

SCIENCE (2022)

Add to Collection

Article Chemistry, Multidisciplinary

A Change from Kinetic to Thermodynamic Control Enables trans-Selective Stereochemical Editing of Vicinal Diols

Yu-An Zhang et al.

Summary: This report describes a new method for the selective catalytic isomerization of cis-1,2-diols using a silanethiol catalyst. The method is highly chemoselective and tolerant to a wide range of functional groups, providing a concise route to trans-diol products. Mechanistic studies suggest that the isomerization proceeds through a reversible hydrogen atom transfer pathway mediated by the silanethiol catalyst.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

Add to Collection

Article Chemistry, Multidisciplinary

General Light-Mediated, Highly Diastereoselective Piperidine Epimerization: From Most Accessible to Most Stable Stereoisomer

Zican Shen et al.

Summary: A combined photocatalytic and hydrogen atom transfer (HAT) approach was developed for light-mediated epimerization of piperidines, providing the more stable diastereomer with high selectivity. The generality of the transformation was demonstrated for various substituted piperidines, with observed diastereoselectivities correlating with calculated relative stabilities of isomers. Reversibility of the reaction, luminescence quenching, deuterium labeling studies, and quantum yield measurements were used to provide insights into the mechanism.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Add to Collection

Article Chemistry, Multidisciplinary

Photochemical Deracemization at sp3-Hybridized Carbon Centers via a Reversible Hydrogen Atom Transfer

Johannes Grosskopf et al.

Summary: A photochemical deracemization reaction of 5-substituted 3-phenylimidazolidine-2,4-diones (hydantoins) is reported using a chiral diarylketone catalyst. Mechanistic evidence suggests the reaction occurs through selective hydrogen atom transfer, converting substrate enantiomers into product enantiomers.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Add to Collection

Article Chemistry, Multidisciplinary

Catalytic α-Deracemization of Ketones Enabled by Photoredox Deprotonation and Enantioselective Protonation

Chenhao Zhang et al.

Summary: This study demonstrates the catalytic deracemization of ketones with alpha-stereocenters in a single reaction through photoredox deprotonation and enantioselective protonation. By utilizing a photoredox catalyst and a tertiary amine, nonracemic carbonyl compounds with up to 97% enantiomeric excess can be obtained. This light-driven strategy provides a blueprint for deracemizations of common carbonyl compounds.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Add to Collection

Article Chemistry, Multidisciplinary

Photochemical Deracemization of Primary Allene Amides by Triplet Energy Transfer: A Combined Synthetic and Theoretical Study

Manuel Plaza et al.

Summary: The research investigated the photochemical deracemization of 2,4-disubstituted 2,3-butadienamides using experimental and theoretical approaches. A chiral sensitizer was found to catalyze the reaction, leading to the isolation of enantioenriched allene amides with high yield. The study revealed the binding properties and selectivity differences between the two enantiomers through luminescence data, DFT calculations, and NMR titration.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Add to Collection

Article Chemistry, Physical

Enantiodivergent Prenylation via Deconjugative Isomerization

Tobias Morack et al.

Summary: Researchers have developed a platform for enantioselective prenylation using light, aiming to facilitate chiral drug discovery. Detailed mechanistic analysis has led to the development of an efficient method for preparing enantioselective variants. The chiral pool quasi-enantiomers quinine and quinidine play an important role as catalysts in this process.

ACS CATALYSIS (2021)

Add to Collection

Review Chemistry, Multidisciplinary

Racemisation in Chemistry and Biology

Andrew Ballard et al.

CHEMISTRY-A EUROPEAN JOURNAL (2020)

Add to Collection

Article Multidisciplinary Sciences

Synthesis of rare sugar isomers through site-selective epimerization

Yong Wang et al.

NATURE (2020)

Add to Collection

Article Chemistry, Multidisciplinary

Photochemically Induced Ring Opening of Spirocyclopropyl Oxindoles: Evidence for a Triplet 1,3-Diradical Intermediate and Deracemization by a Chiral Sensitizer

Xinyao Li et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Add to Collection

Article Multidisciplinary Sciences

Static to inducibly dynamic stereocontrol: The convergent use of racemic β-substituted ketones

Jacob S. DeHovitz et al.

SCIENCE (2020)

Add to Collection

Article Multidisciplinary Sciences

Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis

John J. Molloy et al.

SCIENCE (2020)

Add to Collection

Article Chemistry, Multidisciplinary

Site-selective redox isomerizations of furanosides using a combined arylboronic acid/photoredox catalyst system

Victoria Dimakos et al.

CHEMICAL SCIENCE (2020)

Add to Collection

Article Chemistry, Multidisciplinary

Site-Selective and Stereoselective C-H Alkylations of Carbohydrates via Combined Diarylborinic Acid and Photoredox Catalysis

Victoria Dimakos et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

Add to Collection

Article Chemistry, Organic

Visible-Light-Activated Divergent Reactivity of Dienones: Dimerization in Neat Conditions and Regioselective E to Z Isomerization in the Solvent

Sandip Naskar et al.

ORGANIC LETTERS (2019)

Add to Collection

Article Chemistry, Multidisciplinary

Photochemical Alkene Isomerization for the Synthesis of Polysubstituted Furans and Pyrroles under Neutral Conditions

Johannes C. L. Walker et al.

CHEMISTRY-A EUROPEAN JOURNAL (2019)

Add to Collection

Article Chemistry, Organic

Photocatalytic E → Z Isomerization of β-Ionyl Derivatives

Keith Livingstone et al.

ORGANIC LETTERS (2019)

Add to Collection

Article Chemistry, Organic

Sequential Energy Transfer Catalysis: A Cascade Synthesis of Angularly-Fused Dihydrocoumarins

Tomas Nevesely et al.

ORGANIC LETTERS (2019)

Add to Collection

Article Multidisciplinary Sciences

Light-driven deracemization enabled by excited-state electron transfer

Nick Y. Shin et al.

SCIENCE (2019)

Add to Collection

Article Chemistry, Multidisciplinary

Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage of Unactivated C(sp(3))-H Bonds

Yaxin Wang et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2018)

Add to Collection

Article Chemistry, Multidisciplinary

Enantioselective synthesis of amines by combining photoredox and enzymatic catalysis in a cyclic reaction network

Xingwei Guo et al.

CHEMICAL SCIENCE (2018)

Add to Collection

Article Multidisciplinary Sciences

Cooperative asymmetric reactions combining photocatalysis and enzymatic catalysis

Zachary C. Litman et al.

NATURE (2018)

Add to Collection

Article Multidisciplinary Sciences

Catalytic deracemization of chiral allenes by sensitized excitation with visible light

Alena Hoelzl-Hobmeier et al.

NATURE (2018)

Add to Collection

Article Chemistry, Multidisciplinary

Mild dynamic kinetic resolution of amines by coupled visible-light photoredox and enzyme catalysis

Qiong Yang et al.

CHEMICAL COMMUNICATIONS (2018)

Add to Collection

Article Chemistry, Organic

Flavin-Mediated Visible-Light [2+2] Photocycloaddition of Nitrogen- and Sulfur-Containing Dienes

Michael Jirasek et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2017)

Add to Collection

Article Chemistry, Multidisciplinary

Transition-Metal Catalysis of Nucleophilic Substitution Reactions: A Radical Alternative to SN1 and SN2 Processes

Gregory C. Fu

ACS CENTRAL SCIENCE (2017)

Add to Collection

Review Chemistry, Multidisciplinary

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

Ming Yan et al.

CHEMICAL REVIEWS (2017)

Add to Collection

Article Chemistry, Multidisciplinary

Site-selective carbon-carbon bond formation in unprotected monosaccharides using photoredox catalysis

Ieng Chim (Steven) Wan et al.

CHEMICAL COMMUNICATIONS (2017)

Add to Collection

Review Chemistry, Multidisciplinary

Advances in Stereoconvergent Catalysis from 2005 to 2015: Transition-Metal-Mediated Stereoablative Reactions, Dynamic Kinetic Resolutions, and Dynamic Kinetic Asymmetric Transformations

Vikram Bhat et al.

CHEMICAL REVIEWS (2017)

Add to Collection

Review Chemistry, Multidisciplinary

Organic Photoredox Catalysis

Nathan A. Romero et al.

CHEMICAL REVIEWS (2016)

Add to Collection

Article Chemistry, Organic

Photoredox Catalysis in Organic Chemistry

Megan H. Shaw et al.

JOURNAL OF ORGANIC CHEMISTRY (2016)

Add to Collection

Review Chemistry, Multidisciplinary

Radicals: Reactive Intermediates with Translational Potential

Ming Yan et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016)

Add to Collection

Article Chemistry, Multidisciplinary

Chemoenzymatic Dynamic Kinetic Resolution: A Powerful Tool for the Preparation of Enantiomerically Pure Alcohols and Amines

Oscar Verho et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015)

Add to Collection

Article Chemistry, Multidisciplinary

A Bio-Inspired, Catalytic E → Z Isomerization of Activated Olefins

Jan B. Metternich et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015)

Add to Collection

Article Chemistry, Organic

Dynamic Kinetic Resolution of Phthalides via Asymmetric Transfer Hydrogenation: A Strategy Constructs 1,3-Distereocentered 3-(2-Hydroxy-2-arylethyl)isobenzofuran-1(3H)-one

Tanyu Cheng et al.

ORGANIC LETTERS (2015)

Add to Collection

Article Chemistry, Multidisciplinary

Synthetic Control of Retinal Photochemistry and Photophysics in Solution

Giovanni Bassolino et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

Add to Collection

Article Chemistry, Multidisciplinary

Facile Synthesis of Z-Alkenes via Uphill Catalysis

Kamaljeet Singh et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2014)

Add to Collection

Article Chemistry, Organic

Development of a Concise, Asymmetric Synthesis of a Smoothened Receptor (SMO) inhibitor: Enzymatic Transamination of a 4-Piperidinone with Dynamic Kinetic Resolution

Zhihui Peng et al.

ORGANIC LETTERS (2014)

Add to Collection

Review Chemistry, Multidisciplinary

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

Christopher K. Prier et al.

CHEMICAL REVIEWS (2013)

Add to Collection

Article Multidisciplinary Sciences

Photoredox Activation for the Direct β-Arylation of Ketones and Aldehydes

Michael T. Pirnot et al.

SCIENCE (2013)

Add to Collection

Article Chemistry, Organic

Chemoenzymatic Dynamic Kinetic Resolution of Primary Amines Catalyzed by CAL-B at 38-40°C

Florent Poulhes et al.

JOURNAL OF ORGANIC CHEMISTRY (2011)

Add to Collection

Article Chemistry, Organic

Switching from (R)- to (S)-selective chemoenzymatic DKR of amines involving sulfanyl radical-mediated racemization

Lahssen El Blidi et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (2010)

Add to Collection

Article Chemistry, Organic

En Route to (S)-Selective Chemoenzymatic Dynamic Kinetic Resolution of Aliphatic Amines. One-Pot KR/Racemization/KR Sequence Leading to (S)-Amides

Lahssen El Blidi et al.

JOURNAL OF ORGANIC CHEMISTRY (2009)

Add to Collection

Article Chemistry, Organic

Highly efficient photochemically induced thiyl radical-mediated racemization of aliphatic Amines at 30 °C

Lucie Routaboul et al.

JOURNAL OF ORGANIC CHEMISTRY (2008)

Add to Collection

Article Chemistry, Organic

Dynamic kinetic resolution of amines involving biocatalysis and in situ free radical mediated racemization

Stephane Gastaldi et al.

ORGANIC LETTERS (2007)

Add to Collection

Article Chemistry, Organic

Thiyl radical mediated racemization of nonactivated aliphatic amines

Stephanie Escoubet et al.

JOURNAL OF ORGANIC CHEMISTRY (2006)

Add to Collection

Article Chemistry, Organic

Thiyl radical mediated racemization of benzylic amines

Stephanie Escoubet et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2006)

Add to Collection

Article Multidisciplinary Sciences

Asymmetric catalysis in complex target synthesis

MS Taylor et al.

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA (2004)

Add to Collection

Article Chemistry, Organic

Selective radical-chain epimerisation at electron-rich chiral tertiary C-H centres using thiols as protic polarity-reversal catalysts

HS Dang et al.

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 (2001)

Add to Collection

Article Chemistry, Organic

Strategy for contra-thermodynamic radical-chain epimerisation of 1,2-diols using polarity-reversal catalysis

HS Dang et al.

TETRAHEDRON LETTERS (2000)

Add to Collection

Article Multidisciplinary Sciences

The case of medium-dependent dual mechanisms for photoisomerization: One-bond-flip and Hula-Twist

RSH Liu et al.

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA (2000)

Add to Collection

Photoinduced Dynamic Radical Processes for Isomerizations, Deracemizations, and Dynamic Kinetic Resolutions

Related references

Export Citation

Share Paper