Online citations, reference lists, and bibliographies.
← Back to Search

Aryl Nitriles From Alkynes Using Tert-Butyl Nitrite: Metal-Free Approach To C≡C Bond Cleavage.

U. Dutta, D. Lupton, D. Maiti
Published 2016 · Chemistry, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy
Share
Alkyne C≡C bond breaking, outside of alkyne metathesis, remains an underdeveloped area in reaction discovery. Recently, nitrogenation has been reported to allow nitrile formation from alkynes. A new protocol for the metal-free C≡C bond cleavage of terminal alkynes to produce nitriles is reported. This method provides an opportunity to synthesize a vast range of nitriles containing aryl, heteroaryl, and natural product derivatives (38 examples). In addition, the potential of (t)BuONO to act as a powerful nitrogenating agent for terminal aryl alkynes is demonstrated.
This paper references
10.1039/C4QO00158C
Chopping unfunctionalized carbon–carbon bonds: a new paradigm for the synthesis of organonitriles
Philippe Bisseret (2014)
10.1021/CR9902594
Element−Element Addition to Alkynes Catalyzed by the Group 10 Metals
I. Beletskaya (1999)
10.1021/ja5115584
Sonogashira cross-coupling and homocoupling on a silver surface: chlorobenzene and phenylacetylene on Ag(100).
C. Sánchez-Sánchez (2015)
10.1021/OL701912S
Ruthenium-catalyzed cycloaddition of aryl azides and alkynes.
L. K. Rasmussen (2007)
10.1021/OL0003937
Ruthenium complex-catalyzed anti-Markovnikov hydration of terminal alkynes.
T. Suzuki (2001)
10.1002/anie.201300193
Silver-catalyzed nitrogenation of alkynes: a direct approach to nitriles through C≡C bond cleavage.
Tao Shen (2013)
10.1021/JA00904A050
Reactions of Unsaturated Free Radicals with Nitric Oxide. Radical-Induced Scission of Carbon-Carbon Triple Bonds
A. Sherwood (2002)
10.1039/B508899M
Ring closing enyne metathesis: a powerful tool for the synthesis of heterocycles.
H. Villar (2007)
10.1039/B412198H
The metathesis reactions: from a historical perspective to recent developments
D. Astruc (2005)
10.1016/J.TET.2008.01.081
Recent advances in syntheses of heterocycles and carbocycles via homogeneous gold catalysis. Part 1: Heteroatom addition and hydroarylation reactions of alkynes, allenes, and alkenes
Hong C. Shen (2008)
10.1039/C5RA04632G
Metal-free regioselective C-3 nitration of quinoline N -oxides with tert -butyl nitrite
Jingjing Zhao (2015)
10.1021/cr9001462
Cu(I)-catalyzed Huisgen azide-alkyne 1,3-dipolar cycloaddition reaction in nucleoside, nucleotide, and oligonucleotide chemistry.
F. Amblard (2009)
10.1021/cr0783479
Cu-catalyzed azide-alkyne cycloaddition.
M. Meldal (2008)
10.1021/JA046360U
A general bifunctional catalyst for the anti-Markovnikov hydration of terminal alkynes to aldehydes gives enzyme-like rate and selectivity enhancements.
D. Grotjahn (2004)
10.1021/ol503025n
Aerobic oxynitration of alkynes with (t)BuONO and TEMPO.
U. Dutta (2014)
10.1021/ol501023n
Copper-mediated tandem oxidative C(sp2)-H/C(sp)-H alkynylation and annulation of arenes with terminal alkynes.
J. Dong (2014)
10.1002/anie.201204513
Alkyne metathesis on the rise.
A. Fürstner (2013)
10.1021/jo3000095
Copper-catalyzed azide-alkyne cycloaddition reaction in water using cyclodextrin as a phase transfer catalyst.
Jung-Ah Shin (2012)
10.1002/asia.201402591
Unstrained carbon-carbon bond cleavage.
H. Liu (2014)
10.1039/c5cc00872g
Metal-free nitro-carbocyclization of 1,6-enynes with (t)BuONO and TEMPO.
X. Hao (2015)
10.1002/EJOC.201403510
Effective Nitration of Anilides and Acrylamides by tert-Butyl Nitrite
Yi-fei Ji (2015)
10.1039/b904091a
Copper-catalyzed azide-alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(I) acetylides.
J. Hein (2010)
10.1021/cr400274j
Transition-metal-free coupling reactions.
Chang-Liang Sun (2014)
10.1021/ol1022036
One-pot three-step synthesis of 1,2,3-triazoles by copper-catalyzed cycloaddition of azides with alkynes formed by a Sonogashira cross-coupling and desilylation.
Frédéric Friscourt (2010)
10.1021/JA038177R
The first applications of carbene ligands in cross-couplings of alkyl electrophiles: sonogashira reactions of unactivated alkyl bromides and iodides.
M. Eckhardt (2003)
10.1021/ol501540w
Sonogashira couplings catalyzed by collaborative (N-heterocyclic carbene)-copper and -palladium complexes.
Christopher W. D. Gallop (2014)
10.1039/C5GC00528K
Efficient bromination of olefins, alkynes, and ketones with dimethyl sulfoxide and hydrobromic acid
Song Song (2015)
10.1039/c3cc41576g
Synthesis of (E)-nitroolefins via decarboxylative nitration using t-butylnitrite (t-BuONO) and TEMPO.
Srimanta Manna (2013)
10.1021/cr900085j
Organic radical reactions associated with nitrogen monoxide.
J. Hartung (2009)
10.1021/ol102858u
Copper(I) 1,2,3-triazol-5-ylidene complexes as efficient catalysts for click reactions of azides with alkynes.
T. Nakamura (2011)
10.1021/ol103134c
A copper(I) isonitrile complex as a heterogeneous catalyst for azide-alkyne cycloaddition in water.
M. Liu (2011)
10.1021/ol401426p
Stereoselective nitration of olefins with (t)BuONO and TEMPO: direct access to nitroolefins under metal-free conditions.
Soham Maity (2013)
10.1021/ja809403e
[(NHC)Au(I)]-catalyzed acid-free alkyne hydration at part-per-million catalyst loadings.
N. Marion (2009)
10.1021/cr100359d
Radical cascades initiated by intermolecular radical addition to alkynes and related triple bond systems.
U. Wille (2013)
10.1021/ja311942e
Efficient and stereoselective nitration of mono- and disubstituted olefins with AgNO2 and TEMPO.
Soham Maity (2013)
10.1021/cr400628s
Recent advances in transition-metal-catalyzed functionalization of unstrained carbon-carbon bonds.
F. Chen (2014)
10.1021/ol5032359
Mild Palladium-Catalyzed Cyanation of (Hetero)aryl Halides and Triflates in Aqueous Media
Daniel T. Cohen (2015)
10.1021/JA072678L
Benzimidazole and related ligands for Cu-catalyzed azide-alkyne cycloaddition.
V. Rodionov (2007)
10.1039/A804370A
Nitrile-containing natural products
F. Fleming (1999)
10.1021/ja3036543
Amphiphilic self-assembled polymeric copper catalyst to parts per million levels: click chemistry.
Yoichi M. A. Yamada (2012)
10.1021/ol702790w
Heterogeneous copper catalyst for the cycloaddition of azides and alkynes without additives under ambient conditions.
I. S. Park (2008)
10.1021/IC061997V
Palladium-catalyzed aerobic oxidative amination of alkenes: development of intra- and intermolecular aza-Wacker reactions.
Vasily V. Kotov (2007)
10.1002/ADSC.201400895
Nitrative Spirocyclization Mediated by TEMPO: Synthesis of Nitrated Spirocycles from N-Arylpropiolamides, tert-Butyl Nitrite and Water
Xu‐Heng Yang (2015)
10.1039/B703164P
Alkene metathesis: the search for better catalysts.
P. Deshmukh (2007)
10.1002/ANIE.200353015
Efficient palladium-catalyzed coupling of aryl chlorides and tosylates with terminal alkynes: use of a copper cocatalyst inhibits the reaction.
D. Gelman (2003)
10.1021/ol401311h
Cleavage of carbon-carbon triple bond: direct transformation of alkynes to nitriles.
Noriko Okamoto (2013)
10.1021/JA062610Q
Cleavage of a carbon-carbon triple bond via gold-catalyzed cascade cyclization/oxidative cleavage reactions of (Z)-enynols with molecular oxygen.
Y. Liu (2006)
10.1021/jacs.5b06793
Remote para-C-H Functionalization of Arenes by a D-Shaped Biphenyl Template-Based Assembly.
Sukdev Bag (2015)
10.1021/JA051875M
Copper- or phosphine-catalyzed reaction of alkynes with isocyanides. Regioselective synthesis of substituted pyrroles controlled by the catalyst.
S. Kamijo (2005)
10.1021/MA201662H
Flexible Solid Polymer Electrolytes Based on Nitrile Butadiene Rubber/Poly(ethylene oxide) Interpenetrating Polymer Networks Containing Either LiTFSI or EMITFSI
Laurent J. Goujon (2011)
10.1021/ol900344g
Wacker-type oxidation of alkynes into 1,2-diketones using molecular oxygen.
Wei Ren (2009)
10.1039/c2cc33706a
Copper-catalyzed direct oxidative annulation of N-iminopyridinium ylides with terminal alkynes using O2 as oxidant.
S. Ding (2013)
10.1021/cr900346r
Ruthenium-based olefin metathesis catalysts derived from alkynes.
A. M. Lozano-Vila (2010)
10.1021/jacs.5b05415
Synergistic Gold and Iron Dual Catalysis: Preferred Radical Addition toward Vinyl-Gold Intermediate over Alkene.
Haihui Peng (2015)
10.1002/anie.200906755
Formal inverse Sonogashira reaction: direct alkynylation of arenes and heterocycles with alkynyl halides.
A. Dudnik (2010)
10.1021/OL070527H
Efficient conversion of aromatic amines into azides: a one-pot synthesis of triazole linkages.
Karine Barral (2007)
10.1021/JO00982A044
Intramolecular addition of 4-alkynyloxy radicals
J. Surzur (1972)
10.1002/ADSC.200600476
Alkyne Metathesis: Catalysts and Synthetic Applications
W. Zhang (2007)
10.1021/JO051793G
Practical Method for Transforming Alkynes into α-Diketones
Z. Wan (2006)
10.5012/BKCS.2011.32.6.2083
An Organic Nitrile Dye with Strong Donor and Acceptor Groups for Dye-Sensitized Solar Cells
M. An (2011)
10.1021/JA036246W
A new ruthenium-catalyzed cleavage of a carbon-carbon triple bond: efficient transformation of ethynyl alcohol into alkene and carbon monoxide.
S. Datta (2003)
10.1021/ja908911n
Dioxygen activation under ambient conditions: Cu-catalyzed oxidative amidation-diketonization of terminal alkynes leading to alpha-ketoamides.
C. Zhang (2010)
10.1002/ANIE.200603726
Heterogeneous copper-in-charcoal-catalyzed click chemistry.
B. Lipshutz (2006)
10.1039/C5GC00302D
Facile synthesis of (E)-β-nitroolefinic alkoxyamines via silver-catalyzed decarboxylative nitroaminoxylation of phenylpropiolic acids
H. Yan (2015)
10.1021/ol502071g
Direct synthesis of α-trifluoromethyl ketone from (hetero)arylacetylene: design, intermediate trapping, and mechanistic investigations.
A. Maji (2014)
10.1021/ol9018776
A highly active catalyst for Huisgen 1,3-dipolar cycloadditions based on the tris(triazolyl)methanol-Cu(I) structure.
Salih Ozçubukçu (2009)
10.1021/ol500592m
Synthesis of α-Diketones from Alkylaryl- and Diarylalkynes Using Mercuric Salts
M. Jung (2014)
10.1021/CR050992X
The Sonogashira reaction: a booming methodology in synthetic organic chemistry.
R. Chinchilla (2007)
10.1021/ar400259e
Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.
T. Wang (2014)
10.1002/anie.201508347
Splitting a Substrate into Three Parts: Gold-Catalyzed Nitrogenation of Alkynes by C-C and C≡C Bond Cleavage.
C. Qin (2016)
10.1021/jm100762r
Nitrile-containing pharmaceuticals: efficacious roles of the nitrile pharmacophore.
F. Fleming (2010)
10.1021/JA034105O
Carbon-carbon bond cleavage of diynes through the hydroamination with transition metal catalysts.
Tomohiro Shimada (2003)
10.1021/jo400598p
A predictably selective nitration of olefin with Fe(NO3)3 and TEMPO.
T. Naveen (2013)
10.1021/JA0119292
Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes: insight into anti-Markovnikov regiochemistry.
M. Tokunaga (2001)
10.1021/ja806249n
1,3-Dipolar cycloaddition of organic azides to alkynes by a dicopper-substituted silicotungstate.
K. Kamata (2008)
10.1021/IC061858D
Recent progress in Wacker oxidations: moving toward molecular oxygen as the sole oxidant.
Candace N. Cornell (2007)
10.1002/anie.201305731
Palladium(II)-catalyzed direct conversion of methyl arenes into aromatic nitriles.
Zhibin Shu (2013)
10.1021/cr200164y
Cyclizations of alkynes: revisiting Baldwin's rules for ring closure.
Kerry Gilmore (2011)
10.1039/b908338c
Gold-catalyzed oxidative cleavage of aryl-substituted alkynyl ethers using molecular oxygen. Simultaneous degradation of C-H and single and triple carbon-carbon bonds under ambient conditions.
A. Das (2009)
10.1002/1521-3757(20010601)113:11<2056::AID-ANGE2056>3.0.CO;2-W
Click-Chemie: diverse chemische Funktionalität mit einer Handvoll guter Reaktionen
H. Kolb (2001)
10.1021/ja8002217
Palladium-catalyzed cleavage reaction of carbon-carbon triple bond with molecular oxygen promoted by Lewis acid.
A. Wang (2008)
10.1016/J.TETLET.2013.05.021
Palladium and copper catalyzed one-pot Sonogashira reaction of 2-nitroiodobenzenes with aryl acetylenes and subsequent regioselective hydration in water: synthesis of 2-(2-nitrophenyl)-1-aryl ethanones
S. Ahammed (2013)
10.1002/1521-3773(20020715)41:14<2596::AID-ANIE2596>3.0.CO;2-4
A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes.
V. Rostovtsev (2002)
10.1021/ol502823c
Meta-selective arene C-H bond olefination of arylacetic acid using a nitrile-based directing group.
M. Bera (2014)



This paper is referenced by
10.1021/acs.joc.7b00626
Transition-Metal-Free Conversion of Trifluoropropanamides into Cyanoformamides through C-CF3 Bond Cleavage and Nitrogenation.
F. Wang (2017)
10.1002/ASIA.201901072
tert-Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis.
A. Dahiya (2019)
10.1002/ADSC.201800592
Oxidative Radical Cyclization of N‐methyl‐N‐arylpropiolamide to Isatins via Cleavage of the Carbon‐carbon Triple Bond
Yan-yan Liao (2018)
10.1016/j.polymer.2020.123133
Cobalt-catalyzed [2 + 2 + 2] cycloaddition copolymerization of diyne and internal alkyne monomers to highly branched polymers
Nana Kikuta (2020)
10.1039/C7QO00690J
Chemoselective C(α)–C(β) bond cleavage of saturated aryl ketones with amines leading to α-ketoamides: a copper-catalyzed aerobic oxidation process with air
Chengkou Liu (2017)
10.1021/acs.orglett.7b01840
A Direct Cycloaminative Approach to Imidazole Derivatives via Dual C-H Functionalization.
Sagar Arepally (2017)
10.1039/C6OB01912A
Transformations of alkynes to carboxylic acids and their derivatives via C[triple bond, length as m-dash]C bond cleavage.
Shivalinga Kolle (2016)
10.1039/c8ob01950a
tert-Butyl nitrite mediated nitrogen transfer reactions: synthesis of benzotriazoles and azides at room temperature.
Sadaf Azeez (2018)
10.1002/AJOC.201700418
Cu(TFA)2‐Catalyzed Picolinamido‐Directed C(sp2)−H Cyanation of Naphthalenes by Using Benzoyl Cyanide as a Cyano Source
He Song (2017)
10.1002/ADSC.201700456
Bis(dibenzylideneacetone)palladium(0)/tert‐Butyl Nitrite‐ Catalyzed Cyclization of o‐Alkynylanilines with tert‐Butyl Nitrite: Synthesis and Applications of Indazole 2‐Oxides
G. C. Senadi (2017)
10.1039/C9QO00619B
Utilization of nitriles as the nitrogen source: practical and economical construction of 4-aminopyrimidine and β-enaminonitrile skeletons
Yingzu Zhu (2019)
10.1039/c9ob00169g
tert-Butyl nitrite-mediated radical cyclization of tetrazole amines and alkynes toward tetrazolo[1,5-a]quinolines.
Teng Liu (2019)
10.1002/cssc.201901856
Dual Roles of tert-Butyl Nitrite in the Transition Metal- and External Oxidant-Free Trifluoromethyloximation of Alkenes.
Ya Wu (2019)
10.1039/C6CC07119H
A facile strategy for accessing 3-alkynylchromones through gold-catalyzed alkynylation/cyclization of o-hydroxyarylenaminones.
Manjur O Akram (2016)
10.1039/c7ob01553d
tert-Butyl nitrite (TBN) as the N atom source for the synthesis of substituted cinnolines with 2-vinylanilines and a relevant mechanism was studied.
Xiaobo Pang (2017)
10.1039/C8GC02708K
TBN-mediated regio- and stereoselective sulfonylation & oximation (oximosulfonylation) of alkynes with sulfonyl hydrazines in EtOH/H2O
Bin Wang (2019)
10.1021/acs.orglett.7b03204
Radical Enamination of Vinyl Azides: Direct Synthesis of N-Unprotected Enamines.
Y. Ning (2017)
10.1002/EJOC.201700992
Synthesis of Celecoxib, Mavacoxib, SC‐560, Fluxapyroxad, and Bixafen Enabled by Continuous Flow Reaction Modules
Joshua Britton (2017)
10.1021/ACS.OPRD.6B00229
A Homogeneous Method for the Conveniently Scalable Palladium- and Nickel-Catalyzed Cyanation of Aryl Halides
F. Burg (2016)
10.22034/CRL.2018.85118
Nanocatalysts for conversion of aldehydes/alcohols/amines to nitriles: A review
Sheritasadat Shahidi (2018)
10.1016/J.TETLET.2016.04.108
Direct synthesis of nitriles from cleavage of CC double bond with nitrite as the nitrogen source and oxidant
Q. Liu (2016)
10.1002/CHIN.201626106
Aryl Nitriles from Alkynes Using tert-Butyl Nitrite: Metal-Free Approach to CC Bond Cleavage.
Uttam Dutta (2016)
10.1039/c9ra10555g
Visible light-mediated photocatalytic oxidative cleavage of activated alkynes via hydroamination: a direct approach to oxamates
Narenderreddy Katta (2020)
10.1039/C9NJ00776H
Cu(OAc)2-Mediated benzimidazole-directed C–H cyanation using 2-(4-methylpiperazin-1-yl)acetonitrile as the cyano source
T. Zhang (2019)
10.1002/EJOC.201600438
Cleavage of the Carbon–Carbon Triple Bonds of Arylacetylenes for the Synthesis of Arylnitriles without a Metal Catalyst
Yuanguang Lin (2016)
10.1021/acs.orglett.7b02885
Coupling Reaction of Cu-Based Carbene and Nitroso Radical: A Tandem Reaction To Construct Isoxazolines.
Rongxiang Chen (2017)
10.1039/c7cc04433j
Co-catalyzed highly selective C(sp3)-H nitration.
Y. Zhou (2017)
10.1002/chem.201705728
Synthesis of Functionalized Nitriles by Microwave-Promoted Fragmentations of Cyclic Iminyl Radicals.
M. Jackman (2018)
10.1002/chem.202002511
Highly Conjugated π‐Systems Arising from Cannibalistic Hexadehydro‐Diels–Alder Couplings: Cleavage of C−C Single and Triple Bonds
Jan Maier (2020)
10.1039/d0cc05363e
Arylacetylenes as two-carbon synthons: synthesis of eight-membered rings via C[triple bond, length as m-dash]C bond cleavage.
Peng Zhao (2020)
10.1002/9781119304197.ch7
Green Oxidative Synthesis of Nitriles
Laura M. Dornan (2019)
10.1007/978-981-10-2813-7_2
Nitrogenation Strategy for the Synthesis of Amines
Wang Zhou (2017)
See more
Semantic Scholar Logo Some data provided by SemanticScholar