Reversing the Regioselectivity of Halofunctionalization Reactions through Cooperative Photoredox and Copper Catalysis
Abstract
Halofunctionalization of alkenes is a classical method for olefin difunctionalization. It gives rise to adducts which are found in many natural products and biologically active molecules, and offers a synthetic handle for further manipulation. Classically, this reaction is performed with an electrophilic halogen source and leads to regioselective formation of the halofunctionalized adducts. Here, we demonstrate a reversal of the native regioselectivity for alkene halofunctionalization through the use of an acridinium photooxidant in conjunction with a copper cocatalyst.
- Authors:
-
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- University of North Carolina, Chapel Hill, NC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); Eli Lilly and Co., Indianapolis, IN (United States). Eli Lilly Grantee Award
- OSTI Identifier:
- 1463096
- Grant/Contract Number:
- SC0001011; R01 GM098340
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 8; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cooperative catalysis; halofunctionalization; organocatalysis; photoredox catalysis; radicals
Citation Formats
Griffin, Jeremy D., Cavanaugh, Cortney L., and Nicewicz, David A. Reversing the Regioselectivity of Halofunctionalization Reactions through Cooperative Photoredox and Copper Catalysis. United States: N. p., 2017.
Web. doi:10.1002/anie.201610722.
Griffin, Jeremy D., Cavanaugh, Cortney L., & Nicewicz, David A. Reversing the Regioselectivity of Halofunctionalization Reactions through Cooperative Photoredox and Copper Catalysis. United States. https://doi.org/10.1002/anie.201610722
Griffin, Jeremy D., Cavanaugh, Cortney L., and Nicewicz, David A. Fri .
"Reversing the Regioselectivity of Halofunctionalization Reactions through Cooperative Photoredox and Copper Catalysis". United States. https://doi.org/10.1002/anie.201610722. https://www.osti.gov/servlets/purl/1463096.
@article{osti_1463096,
title = {Reversing the Regioselectivity of Halofunctionalization Reactions through Cooperative Photoredox and Copper Catalysis},
author = {Griffin, Jeremy D. and Cavanaugh, Cortney L. and Nicewicz, David A.},
abstractNote = {Halofunctionalization of alkenes is a classical method for olefin difunctionalization. It gives rise to adducts which are found in many natural products and biologically active molecules, and offers a synthetic handle for further manipulation. Classically, this reaction is performed with an electrophilic halogen source and leads to regioselective formation of the halofunctionalized adducts. Here, we demonstrate a reversal of the native regioselectivity for alkene halofunctionalization through the use of an acridinium photooxidant in conjunction with a copper cocatalyst.},
doi = {10.1002/anie.201610722},
journal = {Angewandte Chemie (International Edition)},
number = 8,
volume = 56,
place = {United States},
year = {Fri Jan 20 00:00:00 EST 2017},
month = {Fri Jan 20 00:00:00 EST 2017}
}
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Works referenced in this record:
Katalytische asymmetrische Halogenfunktionalisierung von Alkenen - eine kritische Betrachtung
journal, September 2012
- Denmark, Scott E.; Kuester, William E.; Burk, Matthew T.
- Angewandte Chemie, Vol. 124, Issue 44
Catalytic Hydrochlorination of Unactivated Olefins with para ‐Toluenesulfonyl Chloride
journal, July 2008
- Gaspar, Boris; Carreira, Erick M.
- Angewandte Chemie, Vol. 120, Issue 31
Tertiary Aminourea-Catalyzed Enantioselective Iodolactonization
journal, August 2010
- Veitch, Gemma E.; Jacobsen, Eric N.
- Angewandte Chemie, Vol. 122, Issue 40
Recent advances in asymmetric intra- and intermolecular halofunctionalizations of alkenes
journal, January 2014
- Cheng, Yi An; Yu, Wesley Zongrong; Yeung, Ying-Yeung
- Org. Biomol. Chem., Vol. 12, Issue 15
Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay
journal, September 2016
- Zhang, Wen; Wang, Fei; McCann, Scott D.
- Science, Vol. 353, Issue 6303
A New Tool To Guide Halofunctionalization Reactions: The Halenium Affinity ( HalA ) Scale
journal, September 2014
- Ashtekar, Kumar Dilip; Marzijarani, Nastaran Salehi; Jaganathan, Arvind
- Journal of the American Chemical Society, Vol. 136, Issue 38
One-electron reduction potential and ring opening of the succinimidyl radical in water
journal, February 1993
- Lind, Johan; Jonsson, Mats; Eriksen, Trygve E.
- The Journal of Physical Chemistry, Vol. 97, Issue 8
Atom Transfer Radical Polymerization
journal, September 2001
- Matyjaszewski, Krzysztof; Xia, Jianhui
- Chemical Reviews, Vol. 101, Issue 9
Solvolyses of tertiary .alpha.-arylcycloalkyl and -polycycloalkyl chlorides. Effects of ring size and substituents in the aryl ring on the solvolysis rates
journal, June 1970
- Tanida, Hiroshi.; Tsushima, Tadahiko.
- Journal of the American Chemical Society, Vol. 92, Issue 11
C 3 -Symmetric Cinchonine-Squaramide-Catalyzed Asymmetric Chlorolactonization of Styrene-Type Carboxylic Acids with 1,3-Dichloro-5,5-dimethylhydantoin: An Efficient Method to Chiral Isochroman-1-ones
journal, March 2014
- Han, Xin; Dong, Chune; Zhou, Hai-Bing
- Advanced Synthesis & Catalysis, Vol. 356, Issue 6
[Copper(phenanthroline)(bisisonitrile)] + -Complexes for the Visible-Light-Mediated Atom Transfer Radical Addition and Allylation Reactions
journal, August 2015
- Knorn, Matthias; Rawner, Thomas; Czerwieniec, Rafał
- ACS Catalysis, Vol. 5, Issue 9
Catalytic Asymmetric Bromoamination of Chalcones: Highly Efficient Synthesis of Chiral α-Bromo-β-Amino Ketone Derivatives
journal, July 2010
- Cai, Yunfei; Liu, Xiaohua; Hui, Yonghai
- Angewandte Chemie International Edition, Vol. 49, Issue 35
Aminothiocarbamate-Catalyzed Asymmetric Bromolactonization of 1,2-Disubstituted Olefinic Acids
journal, May 2011
- Tan, Chong Kiat; Zhou, Ling; Yeung, Ying-Yeung
- Organic Letters, Vol. 13, Issue 10
Reagent -Controlled Stereoselective Iodolactonizations
journal, January 2002
- Haas, Jürgen; Piguel, Sandrine; Wirth, Thomas
- Organic Letters, Vol. 4, Issue 2
Direct Catalytic Anti-Markovnikov Hydroetherification of Alkenols
journal, November 2012
- Hamilton, David S.; Nicewicz, David A.
- Journal of the American Chemical Society, Vol. 134, Issue 45
A Catalytic Asymmetric Chlorocyclization of Unsaturated Amides
journal, February 2011
- Jaganathan, Arvind; Garzan, Atefeh; Whitehead, Daniel C.
- Angewandte Chemie International Edition, Vol. 50, Issue 11
Enantioselective halocyclization of polyprenoids induced by nucleophilic phosphoramidites
journal, February 2007
- Sakakura, Akira; Ukai, Atsushi; Ishihara, Kazuaki
- Nature, Vol. 445, Issue 7130
Dissecting the Stereocontrol Elements of a Catalytic Asymmetric Chlorolactonization: Syn Addition Obviates Bridging Chloronium
journal, September 2013
- Yousefi, Roozbeh; Ashtekar, Kumar Dilip; Whitehead, Daniel C.
- Journal of the American Chemical Society, Vol. 135, Issue 39
Catalytic Enantioselective Iodocyclization of γ-Hydroxy- cis -alkenes
journal, December 2003
- Kang, Sung Ho; Lee, Sung Bae; Park, Chul Min
- Journal of the American Chemical Society, Vol. 125, Issue 51
Photoaddition of alkyl halides to olefins catalyzed by copper(I) complexes
journal, October 1983
- Mitani, Michiharu; Kato, Isao; Koyama, Kikuhiko
- Journal of the American Chemical Society, Vol. 105, Issue 22
Fast hydrolysis of alkyl radicals with leaving groups in the β position
journal, December 1982
- Koltzenburg, G.; Behrens, G.; Schulte-Frohlinde, D.
- Journal of the American Chemical Society, Vol. 104, Issue 25
Catalytic, Asymmetric Halofunctionalization of Alkenes-A Critical Perspective
journal, September 2012
- Denmark, Scott E.; Kuester, William E.; Burk, Matthew T.
- Angewandte Chemie International Edition, Vol. 51, Issue 44
Catalytic Asymmetric Iodocarbocyclization Reaction of 4-Alkenylmalonates and Its Application to Enantiotopic Group Selective Reaction
journal, October 1997
- Inoue, Tadashi; Kitagawa, Osamu; Saito, Akio
- The Journal of Organic Chemistry, Vol. 62, Issue 21
Tertiary Aminourea-Catalyzed Enantioselective Iodolactonization
journal, August 2010
- Veitch, Gemma E.; Jacobsen, Eric N.
- Angewandte Chemie International Edition, Vol. 49, Issue 40
Nucleophile-Assisted Alkene Activation: Olefins Alone Are Often Incompetent
journal, June 2016
- Ashtekar, Kumar Dilip; Vetticatt, Mathew; Yousefi, Roozbeh
- Journal of the American Chemical Society, Vol. 138, Issue 26
Recent advances in stereoselective bromofunctionalization of alkenes using N-bromoamide reagents
journal, January 2013
- Tan, Chong Kiat; Yeung, Ying-Yeung
- Chemical Communications, Vol. 49, Issue 73
Catalytic Hydrochlorination of Unactivated Olefins with para ‐Toluenesulfonyl Chloride
journal, July 2008
- Gaspar, Boris; Carreira, Erick M.
- Angewandte Chemie International Edition, Vol. 47, Issue 31
Radical chain carriers in N-bromosuccinimide brominations
journal, July 1983
- Walling, Cheves; El-Taliawi, Gamil M.; Zhao, Chengxue
- Journal of the American Chemical Society, Vol. 105, Issue 15
Asymmetric Bromolactonization Using Amino-thiocarbamate Catalyst
journal, November 2010
- Zhou, Ling; Tan, Chong Kiat; Jiang, Xiaojian
- Journal of the American Chemical Society, Vol. 132, Issue 44
Silver(I) Assisted Metal Exchange Reaction. A Generalized Synthesis of Tris-Chelated Copper(II) Complexes of Neutral N,N-Donors
journal, April 1998
- Majumdar, Partha; Ghosh, Amit K.; Falvello, Larry R.
- Inorganic Chemistry, Vol. 37, Issue 7
Binuclear copper(I) complexes which reversibly react with carbon monoxide. 1. Di-.mu.-halogeno-bis(2,2'-bipyridine)dicopper(I) and its derivatives
journal, July 1981
- Kitagawa, Susumu.; Munakata, Megumu.
- Inorganic Chemistry, Vol. 20, Issue 7
Achiral Counterion Control of Enantioselectivity in a Brønsted Acid-Catalyzed Iodolactonization
journal, March 2012
- Dobish, Mark C.; Johnston, Jeffrey N.
- Journal of the American Chemical Society, Vol. 134, Issue 14
Cation radicals: aromatic chlorination via peroxydisulphate–copper( II ) chloride systems
journal, January 1974
- Ledwith, Anthony; Russell, Peter J.
- J. Chem. Soc., Chem. Commun., Issue 8
An Organocatalytic Asymmetric Chlorolactonization
journal, March 2010
- Whitehead, Daniel C.; Yousefi, Roozbeh; Jaganathan, Arvind
- Journal of the American Chemical Society, Vol. 132, Issue 10
Catalytic Asymmetric Bromoamination of Chalcones: Highly Efficient Synthesis of Chiral α-Bromo-β-Amino Ketone Derivatives
journal, July 2010
- Cai, Yunfei; Liu, Xiaohua; Hui, Yonghai
- Angewandte Chemie, Vol. 122, Issue 35
Allylic oxidations by peroxy esters catalyzed by copper salts. The potential for stereoselective syntheses
journal, December 1986
- Beckwith, Athelstan L. J.; Zavitsas, Andreas A.
- Journal of the American Chemical Society, Vol. 108, Issue 26
The presence of two reactive intermediates in the photolysis of N-bromosuccinimide: kinetic proofs
journal, February 1989
- Chow, Yuan L.; Zhao, Da Chuan
- The Journal of Organic Chemistry, Vol. 54, Issue 3
A Catalytic Asymmetric Chlorocyclization of Unsaturated Amides
journal, February 2011
- Jaganathan, Arvind; Garzan, Atefeh; Whitehead, Daniel C.
- Angewandte Chemie, Vol. 123, Issue 11
Works referencing / citing this record:
Regioselective Carboiodination of Styrenes: N ‐Iodosuccinimide Affords Complete Reaction Regioselectivity
journal, January 2020
- Goto, Mayuki; Maejima, Saki; Yamaguchi, Eiji
- Asian Journal of Organic Chemistry, Vol. 9, Issue 2
Photoredox Imino Functionalizations of Olefins
journal, September 2017
- Davies, Jacob; Sheikh, Nadeem S.; Leonori, Daniele
- Angewandte Chemie, Vol. 129, Issue 43
Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization–Cross‐Coupling Cascade
journal, May 2019
- Weires, Nicholas A.; Slutskyy, Yuriy; Overman, Larry E.
- Angewandte Chemie
Photocatalyzed ortho ‐Alkylation of Pyridine N ‐Oxides through Alkene Cleavage
journal, April 2018
- Zhou, Wang; Miura, Tomoya; Murakami, Masahiro
- Angewandte Chemie International Edition, Vol. 57, Issue 18
Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization–Cross‐Coupling Cascade
journal, June 2019
- Weires, Nicholas A.; Slutskyy, Yuriy; Overman, Larry E.
- Angewandte Chemie International Edition, Vol. 58, Issue 25
Aerobic Photooxidative Synthesis of β-Alkoxy Monohydroperoxides Using an Organo Photoredox Catalyst Controlled by a Base
journal, February 2018
- Asano, Yuya; Nagasawa, Yoshitomo; Yamaguchi, Eiji
- Chemistry - An Asian Journal, Vol. 13, Issue 4
Double Activation Catalysis for α′-Alkylidene Cyclic Enones with Chiral Amines and Thiols
journal, July 2017
- Wang, Zhou-Xiang; Zhou, Zhi; Xiao, Wei
- Chemistry - A European Journal, Vol. 23, Issue 44
Enantioselective Bromolactonization of Trisubstituted Olefinic Acids Catalyzed by Chiral Pyridyl Phosphoramides
journal, November 2018
- Nishikawa, Yasuhiro; Hamamoto, Yuhta; Satoh, Rika
- Chemistry - A European Journal, Vol. 24, Issue 71
Metal-Free Arylation-Lactonization Sequence of γ -Alkenoic Acids Using Anilines as Aryl Radical Precursors: Metal-Free Arylation-Lactonization Sequence of γ -Alkenoic Acids Using Anilines as Aryl Radical Precursors
journal, December 2019
- Felipe-Blanco, Diego; Gonzalez-Gomez, Jose C.
- European Journal of Organic Chemistry, Vol. 2019, Issue 47
Visible-light-induced thiotrifluoromethylation of terminal alkenes with sodium triflinate and benzenesulfonothioates
journal, January 2017
- Kong, Weiguang; An, Hejun; Song, Qiuling
- Chemical Communications, Vol. 53, Issue 64
Selective amidation by a photocatalyzed umpolung reaction
journal, January 2019
- Ghosh, Debasish; Nandi, Rajesh; Khamarui, Saikat
- Chemical Communications, Vol. 55, Issue 27
Design and application of aminoacridinium organophotoredox catalysts
journal, January 2020
- Zilate, Bouthayna; Fischer, Christian; Sparr, Christof
- Chemical Communications, Vol. 56, Issue 12
Condensation of 2-methylindole with acetophenones: An unexpected formation of 2-arylanilines
journal, October 2019
- Noland, Wayland E.; Novikov, Alexei V.; Brown, Christopher D.
- Synthetic Communications, Vol. 49, Issue 24
Copper’s rapid ascent in visible-light photoredox catalysis
journal, May 2019
- Hossain, Asik; Bhattacharyya, Aditya; Reiser, Oliver
- Science, Vol. 364, Issue 6439
Photocatalyzed ortho ‐Alkylation of Pyridine N ‐Oxides through Alkene Cleavage
journal, March 2018
- Zhou, Wang; Miura, Tomoya; Murakami, Masahiro
- Angewandte Chemie, Vol. 130, Issue 18
Design and application of aminoacridinium organophotoredox catalysts
text, January 2020
- Zilate, Bouthayna; Fischer, Christian; Sparr, Christof
- Royal Society of Chemistry
Condensation of 2-methylindole with acetophenones: An unexpected formation of 2-arylanilines
text, January 2019
- Noland, Wayland E.; Novikov, Alexei V.; Brown, Christopher D.
- Taylor & Francis
Photoredox Imino Functionalizations of Olefins
journal, September 2017
- Davies, Jacob; Sheikh, Nadeem S.; Leonori, Daniele
- Angewandte Chemie International Edition, Vol. 56, Issue 43
Condensation of 2-methylindole with acetophenones: An unexpected formation of 2-arylanilines
text, January 2019
- Noland, Wayland E.; Novikov, Alexei V.; Brown, Christopher D.
- Taylor & Francis