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Manganese-Catalyzed Electrochemical Deconstructive Chlorination Of Cycloalkanols Via Alkoxy Radicals

B. W. Allen, Mishra Deepak Hareram, Alex C Seastram, Tom McBride, T. Wirth, D. L. Browne, Louis C Morrill
Published 2019 · Chemistry, Medicine

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A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.
This paper references
10.1002/anie.201806296
Radical Trifluoromethoxylation of Arenes Triggered by a Visible-Light-Mediated N-O Bond Redox Fragmentation.
Benson J Jelier (2018)
10.1016/J.TET.2016.10.068
Asymmetric induction in cyclohexadienones carrying α-d-glucopyranosyl moiety
S. Yajima (2016)
10.1002/chem.201802167
Synthesis of Chlorotrifluoromethylated Pyrrolidines by Electrocatalytic Radical Ene-Yne Cyclization.
Ke-Yin Ye (2018)
10.1002/anie.201200878
Anodic oxidation on a boron-doped diamond electrode mediated by methoxy radicals.
T. Sumi (2012)
10.1002/anie.201806522
Alkoxyl Radicals Generated under Photoredox Catalysis: A Strategy for anti-Markovnikov Alkoxylation Reactions.
Anne-Laure Barthelemy (2018)
10.1002/CHIN.201648202
Metal‐Free, Visible Light‐Photocatalyzed Synthesis of Benzo[b]phosphole Oxides: Synthetic and Mechanistic Investigations.
Valentin Quint (2016)
10.1039/c8sc04134b
Photoredox-mediated remote C(sp3)–H heteroarylation of free alcohols† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c8sc04134b
Guo-Xing Li (2019)
Graphical Guide for Set-Up of Electrochemical Mn-Catalyzed Deconstructive Chlorination of Cycloalkanols LEFT. On the ElectraSyn, select "New Experiments". MIDDLE. Select "Constant Current
10.1126/science.aan6206
Metal-catalyzed electrochemical diazidation of alkenes
N. Fu (2017)
10.1002/anie.201709025
Tertiary-Alcohol-Directed Functionalization of Remote C(sp3 )-H Bonds by Sequential Hydrogen Atom and Heteroaryl Migrations.
X. Wu (2018)
10.1002/CHIN.200215285
The Persistent Radical Effect: A Principle for Selective Radical Reactions and Living Radical Polymerizations
H. Fischer (2002)
10.1002/anie.201800598
Catalytic C-H Trifluoromethoxylation of Arenes and Heteroarenes.
Weijia Zheng (2018)
10.1002/tcr.201700090
Recent Advances in Ring-Opening Functionalization of Cycloalkanols by C-C σ-Bond Cleavage.
X. Wu (2018)
10.1002/CJOC.201800455
Recent Advances in Radical‐Mediated C—C Bond Fragmentation of Non‐Strained Molecules
Xinxin Wu (2018)
10.1039/c8cc02642d
Visible-light-induced alkoxyl radical generation for inert chemical bond cleavage/functionalization.
Kunfang Jia (2018)
10.1021/jacs.9b01886
Electrochemically Driven, Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications.
Yu Kawamata (2019)
10.1002/anie.201710790
Photoinduced Remote Functionalisations by Iminyl Radical Promoted C−C and C−H Bond Cleavage Cascades
Elizabeth M. Dauncey (2018)
Alkenes with Nucleophilic Chlorine Sources
K.-Y. Ye (2017)
10.1002/anie.201809879
Visible-Light-Induced Pyridylation of Remote C(sp3 )-H Bonds by Radical Translocation of N-Alkoxypyridinium Salts.
Inwon Kim (2018)
10.1002/anie.201711060
Electrifying Organic Synthesis
A. Wiebe (2018)
10.1515/9783111576855-015
J
Seguin Hen (1824)
10.1002/CHIN.200203289
Stereoselective Construction of the Tetrahydrofuran Nucleus by Alkoxyl Radical Cyclizations
J. Hartung (2002)
10.1021/ACSCATAL.8B03209
Mn-Catalyzed Electrochemical Chloroalkylation of Alkenes.
N. Fu (2019)
10.1021/jacs.8b04891
Divergent Synthesis of Pyrone Diterpenes via Radical Cross Coupling
Rohan R Merchant (2018)
10.1002/CHIN.201628266
Radical-Mediated Ring-Opening Functionalization of Cyclobutanols: A Shortcut to γ-Substituted Ketones
Rongguo Ren (2016)
10.1002/anie.201808495
Redox-Active Reagents for Photocatalytic Generation of the OCF3 Radical and (Hetero)Aryl C-H Trifluoromethoxylation.
Weijia Zheng (2018)
10.1021/JO990652+
Effect of Alkyl Substituents and Ring Size on Alkoxy Radical Cleavage Reactions.
S. Wilsey (1999)
10.1021/jacs.6b06517
Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds.
Hatice G. Yayla (2016)
10.1021/ACS.OPRD.5B00260
A Microflow Electrolysis Cell for Laboratory Synthesis on the Multigram Scale
Robert A. Green (2015)
Prepared following General Procedure G using S25 (46 mg). The crude residue was purified by flash column chromatography (5% Et2O/Pentane, silica gel) to afford 24 (24 mg, 42%) as a colourless oil
10.1002/CHIN.199121063
Carbon-Carbon Bond Formation Using Manganese(III) Acetate as an Electrochemical Mediator.
R. Shundo (1991)
10.1055/S-0039-1689934
Three-Component Chlorophosphinoylation of Alkenes via Anodically Coupled Electrolysis
Lingxiang Lu (2019)
10.1002/chin.198135108
PRODUCT AND MECHANISTIC STUDIES OF THE ANODIC OXIDATION OF METHOXYLATED NAPHTHALENES. THE EECRCP MECHANISM
M. G. Dolson (1981)
10.1021/acs.orglett.8b04010
Mn-Mediated Electrochemical Trifluoromethylation/C(sp2)-H Functionalization Cascade for the Synthesis of Azaheterocycles.
Zhenxing Zhang (2019)
No" for using a reference electrode. MIDDLE. Select "Time" to control the reaction duration
Left
10.1016/J.TETLET.2018.04.060
Photocatalytic alkoxy radical-mediated transformations
J. Guo (2018)
10.1002/chin.199147095
Mn3+-Mediated Coupling-Cyclization of 1,5-Cyclooctadienes with Active Methylene Compounds by Electrooxidation.
R. Shundo (1991)
10.1021/acs.chemrev.7b00360
Flow Electrolysis Cells for the Synthetic Organic Chemistry Laboratory.
D. Pletcher (2018)
10.1021/acs.accounts.5b00348
Tuning reactivity and selectivity in hydrogen atom transfer from aliphatic C-H bonds to alkoxyl radicals: role of structural and medium effects.
M. Salamone (2015)
10.1002/9783527652891.CH09
Electrochemical Reactions in Microreactors
Jun-Ichi Yoshida (2013)
10.1039/C6QO00443A
Manganese-catalyzed ring-opening chlorination of cyclobutanols: regiospecific synthesis of γ-chloroketones
Leitao Huan (2016)
10.1021/acs.chemrev.7b00656
Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions.
K. Moeller (2018)
10.1002/CHIN.201611252
Electrochemical Screening for Electroorganic Synthesis
Christoph Guetz (2016)
10.1021/jacs.7b13387
Anodically Coupled Electrolysis for the Heterodifunctionalization of Alkenes.
Ke-Yin Ye (2018)
10.1038/s41596-018-0010-0
A general, electrocatalytic approach to the synthesis of vicinal diamines
N. Fu (2018)
10.1002/anie.201707171
Donor-Acceptor Complex Enables Alkoxyl Radical Generation for Metal-Free C(sp3 )-C(sp3 ) Cleavage and Allylation/Alkenylation.
J. Zhang (2017)
10.1002/anie.201510014
Generation of Alkoxyl Radicals by Photoredox Catalysis Enables Selective C(sp(3))-H Functionalization under Mild Reaction Conditions.
J. Zhang (2016)
Electrosyn - thesis in Continuous Flow
A. A. Folgueiras-Amador (2018)
10.1002/anie.201402023
Late-stage functionalization of biologically active heterocycles through photoredox catalysis.
D. DiRocco (2014)
10.1007/s41981-018-0024-3
Design and application of a modular and scalable electrochemical flow microreactor
Gabriele Laudadio (2018)
10.1021/acs.orglett.9b03652
Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals
Benjamin D W Allen (2019)
Data for minor regioisomer: 1 H NMR (500 MHz, CDCl3) (selected) δ = 3.73 (dd
10.1126/science.aav5606
Scalable and safe synthetic organic electroreduction inspired by Li-ion battery chemistry
Byron K Peters (2019)
10.1039/c9sc01545k
A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms
C. Sandford (2019)
Eur
H. Zeng (2017)
Graphical Set-Up Guide
10.1055/S-2002-33335
Selectivity in the chemistry of oxygen-centered radicals: The formation of carbon-oxygen bonds
J. Hartung (2002)
10.1021/JO991398O
Anodic oxidation of N-protected 4-methoxy anilines: improved synthesis of quinone imine acetals
Carreño (2000)
10.1016/J.CHEMPR.2017.10.001
Electrochemical Oxidative Cross-coupling with Hydrogen Evolution: A Green and Sustainable Way for Bond Formation
S. Tang (2018)
Catalytic radical difluor - omethoxylation of arenes and heteroarenes
J. W. Lee (2019)
Chlorocycloheptan-1-one (41)
10.1002/1521-3765(20010316)7:6<1159::AID-CHEM1159>3.0.CO;2-I
The persistent radical effect in organic synthesis.
A. Studer (2001)
10.1021/acs.orglett.7b00299
Direct Phosphonation of Quinolinones and Coumarins Driven by the Photochemical Activity of Substrates and Products.
Inwon Kim (2017)
10.1021/acs.chemrev.7b00397
Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance.
Ming Yan (2017)
10.1002/anie.201607305
Catalytic Asymmetric Csp3 -H Functionalization under Photoredox Conditions by Radical Translocation and Stereocontrolled Alkene Addition.
Chuanyong Wang (2016)
10.1002/CHIN.201651239
Radicals: Reactive Intermediates with Translational Potential
Ming Yan (2016)
10.1002/CHIN.201624041
Regiospecific Synthesis of Distally Chlorinated Ketones via C-C Bond Cleavage of Cycloalkanols.
Xuefeng Fan (2016)
10.1039/c8cc09208g
Visible-light mediated C-C bond cleavage of 1,2-diols to carbonyls by cerium-photocatalysis.
Johanna Schwarz (2019)
10.1002/CHIN.201630039
Visible-Light-Induced Alkoxyl Radical Generation Enables Selective C(sp3)-C(sp3) Bond Cleavage and Functionalizations.
K. Jia (2016)
10.1021/jacs.7b09388
Electrocatalytic Radical Dichlorination of Alkenes with Nucleophilic Chlorine Sources.
N. Fu (2017)
10.1515/9783111413426-013
L
Il Liceo (1824)
CDCl3) δ = 3.59 -3.52 (t, J = 6.5 Hz, 2H), 2.63 (t, J = 7.0 Hz, 2H), 2.37 -2.30 (m, 1H
10.1002/anie.201905218
Radical-promoted C-C bond cleavage: a deconstructive approach for selective functionalization.
Sara P Morcillo (2019)
10.1002/anie.201707584
Synthetic Organic Electrochemistry: Calling All Engineers.
Ming Yan (2018)
10.1016/S0040-4039(00)00656-0
Electrochemical oxidative cyclisation of ?-hydroxy-tetrahydropyrans to spiroketals Dedicated with
I. Marko (2000)
Deconstructive diversification of cyclic amines
L. T. Göttemann (2018)
10.1021/acs.orglett.9b01866
Electrochemical, Manganese-Assisted Carbon-Carbon Bond Formation between β-Keto Esters and Silyl Enol Ethers.
Julia Strehl (2019)
10.1039/c7cs00619e
Electrochemical strategies for C-H functionalization and C-N bond formation.
M. Kärkäs (2018)
10.1002/anie.201609035
Photocatalytic C-C Bond Cleavage and Amination of Cycloalkanols by Cerium(III) Chloride Complex.
J. Guo (2016)
10.1021/acs.chemrev.7b00353
Applications of Flow Microreactors in Electrosynthetic Processes.
M. Atobe (2018)
10.1246/CL.170834
β-Scission of Alkoxy Radicals in Synthetic Transformations
M. Murakami (2017)
10.1002/anie.201813356
Dual Photoredox/Copper Catalysis for the Remote C(sp3 )-H Functionalization of Alcohols and Alkyl Halides by N-Alkoxypyridinium Salts.
Xu Bao (2019)
Input "0.30 mmol" for the amount of substrate. MIDDLE. Select "No" for alternation of polarity. RIGHT. It is advised to select "Yes" to save the experiment



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