Copper‐Catalyzed Cyanation of Aryl Iodides with Malononitrile: An Unusual Cyano Group Transfer Process from C(sp3) to C(sp2)

Jiang, Zhaoqiong; Huang, Qing; Chen, Si; Liu, Long; Zhou, Xiangge

doi:10.1002/adsc.201100836

Cited by 91 publications

(28 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…For cyanation of aryl halides, the Rosenmund‐von Braun reaction mediated by copper (I) cyanide has been widely used . Recent methodologies have been developed for this reaction using palladium as catalyst, and different sources of nitriles as malononitrile, potassium hexacyanoferrate (II), and ammonium bicarbonate …”

Section: Introductionmentioning

confidence: 99%

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (ⁿJ_HH, n = 4, 5, and 6) proton–proton and proton–carbon (ⁿJ_CH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Dusso

Ramírez

Parise

et al. 2019

Magnetic Reson in Chemistry

View full text Add to dashboard Cite

A free‐catalyst microwave‐assisted cyanation of brominated Tröger's base derivatives (2a‐f) is reported. The procedure is simple, efficient, and clean affording the nitrile compounds (3a‐e, I) in very good yields. Complete assignment of 1H and 13C chemical shifts of 2a‐f, I and 3a‐d, I was achieved using gradient selected 1D nuclear magnetic resonance (NMR) techniques (1D zTOCSY, PSYCHE, DPFGSE NOE, and DEPT), homonuclear 2D NMR techniques (gCOSY and zTOCSY), and heteronuclear 2D NMR techniques (gHSQCAD/or pure‐shift gHSQCAD, gHMBCAD, bsHSQCNOESY, and gHSQCAD‐TOCSY) with adiabatic pulses. Determination of the long‐range proton–proton coupling constants nJHH (n = 4, 5, 6) was accomplished by simultaneous irradiation of two protons at appropriate power levels. In turn, determined coupling constants were tested by an iterative simulation program by calculating the 1H NMR spectrum and comparing it to the experimental spectrum. The excitation‐sculptured indirect‐detection experiment (EXSIDE) and 1H‐15N CIGARAD‐HMBC (constant time inverse‐detection gradient accordion rescaled heteronuclear multiple bond correlation) were applied for determination of long‐range carbon–proton coupling constants nJCH (n = 2, 3, and 4) and for assignment of 15N chemical shift at natural abundance, respectively. DFT/B3LYP optimization studies were performed in order to determine the geometry of 2c using 6‐31G(d,p), 6‐311G(d,p), and 6–311 + G(d,p) basis sets. For calculation of 1H and 13C chemical shifts, nJHH (n = 2, 3, 4, 5, and 6), and nJCH (n = 1, 2, 3, and 4) coupling constants, the GIAO method was employed at the B3LYP/6‐31G(d,p), B3LYP/6‐31+G(d,p), B3LYP/6‐311+G(d,p), B3LYP/6‐311++G(2d,2p), B3LYP/cc‐pVTZ), and B3LYP/aug‐cc‐pVTZ) levels of theory. For the first time, a stereochemical dependence magnitude of the long‐range nJHH (n = 4, 5, and 6) and nJCH (n = 1, 2, 3, 4, and 5) have been found in bromo‐substituted analogues of Tröger's bases.

show abstract

Section: Introductionmentioning

confidence: 99%

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (ⁿJ_HH, n = 4, 5, and 6) proton–proton and proton–carbon (ⁿJ_CH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Dusso

Ramírez

Parise

et al. 2019

Magnetic Reson in Chemistry

View full text Add to dashboard Cite

show abstract

“…Very recently, Zhou and co-workers developed the Cucatalyzed cyanation of aryl iodides with malononitrile (Scheme 9). [23] Although malononitrile was previously known to react with aryl halides to give aryl malononitriles [24] or arene carboxylic acids [25] under copper catalysis, cyanation of aryl halides with malononitrile was first achieved with Cu(OAc) 2 in the presence of 1,10-phenanthroline, KF, and tBuONa in DMF. Without copper or 1,10-phenanthroline, the cyanation did not occur.…”

Section: Carbon-bound Cyano-group Sourcesmentioning

confidence: 99%

Synthesis of Aromatic Nitriles Using Nonmetallic Cyano‐Group Sources

2012

View full text Add to dashboard Cite

Aromatic nitriles are prepared efficiently through transition-metal-mediated cyanation of aryl (pseudo)halides with metallic cyano-group sources, such as CuCN, KCN, NaCN, Zn(CN)(2), TMSCN, or K(4) [Fe(CN)(6)]. However, this approach often suffers from drawbacks, such as the formation of stoichiometric amounts of metal waste, the poisoning of the metal catalysts, or the generation of toxic HCN gas. As a result, a range of "nonmetallic" organic cyano-group sources have been explored for the cyanation of aryl halides and arene C-H bonds. This Minireview summarizes types of nonmetallic cyano-group sources and their applications in the preparation of aryl nitriles.

show abstract

“…[23] Während zuvor Cu-katalysierte Reaktionen von Malonsäurenitril mit Arylhalogeniden nur zu Arylmalonsäurenitrilen [24] oder Arencarbonsäuren [25] geführt hatten, wurden nun in der Gegenwart von 1, 10 [23] Während zuvor Cu-katalysierte Reaktionen von Malonsäurenitril mit Arylhalogeniden nur zu Arylmalonsäurenitrilen [24] oder Arencarbonsäuren [25] geführt hatten, wurden nun in der Gegenwart von 1, 10 …”

Section: Kohlenstoffgebundene Cn-quellenunclassified

“…[22] Bei dieser Reaktion sind die Kürzlich entwickelten Zhou und Mitarbeiter eine Cukatalysierte Cyanierung von Aryliodiden mit Malonsäurenitril (Schema 9). [23] Während zuvor Cu-katalysierte Reaktionen von Malonsäurenitril mit Arylhalogeniden nur zu Arylmalonsäurenitrilen [24] oder Arencarbonsäuren [25] geführt hatten, wurden nun in der Gegenwart von 1, 10…”

Section: Kohlenstoffgebundene Cn-quellenunclassified

Synthese aromatischer Nitrile mithilfe nichtmetallischer CN‐Quellen

Kim

Chang

2012

Angewandte Chemie

View full text Add to dashboard Cite

Aromatische Nitrile werden effizient durch die übergangsmetallkatalysierte Cyanierung von Aryl(pseudo)halogeniden mit metallischen CN‐Quellen wie CuCN, KCN, NaCN, Zn(CN)2, TMSCN oder K4[Fe(CN)6] synthetisiert. Nachteilig an diesen Verfahren sind jedoch die stöchiometrischen Mengen von Metallabfall, die Vergiftung des Metallkatalysators oder die Bildung von toxischem HCN‐Gas. Für die Cyanierung von Aryl‐Halogen‐ und Aryl‐H‐Bindungen wird daher seit einiger Zeit auch eine Reihe von “nichtmetallischen” organischen CN‐Quellen erkundet. Dieser Kurzaufsatz stellt verschiedene nichtmetallische CN‐Quellen und ihre Anwendung für die Synthese von Arylnitrilen vor.

show abstract

Copper‐Catalyzed Cyanation of Aryl Iodides with Malononitrile: An Unusual Cyano Group Transfer Process from C(sp³) to C(sp²)

Abstract: An unusual copper‐catalyzed cyanation of aryl iodides to form aryl nitriles by cyano group transfer from C(sp3) to C(sp2) carbon atoms is reported and proceeds to give yields of up to 86%.

Cited by 91 publications

References 45 publications

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (ⁿJ_HH, n = 4, 5, and 6) proton–proton and proton–carbon (ⁿJ_CH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (ⁿJ_HH, n = 4, 5, and 6) proton–proton and proton–carbon (ⁿJ_CH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Synthesis of Aromatic Nitriles Using Nonmetallic Cyano‐Group Sources

Synthese aromatischer Nitrile mithilfe nichtmetallischer CN‐Quellen

Contact Info

Product

Resources

About

Copper‐Catalyzed Cyanation of Aryl Iodides with Malononitrile: An Unusual Cyano Group Transfer Process from C(sp3) to C(sp2)

Abstract: An unusual copper‐catalyzed cyanation of aryl iodides to form aryl nitriles by cyano group transfer from C(sp3) to C(sp2) carbon atoms is reported and proceeds to give yields of up to 86%.

Cited by 91 publications

References 45 publications

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (nJHH, n = 4, 5, and 6) proton–proton and proton–carbon (nJCH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (nJHH, n = 4, 5, and 6) proton–proton and proton–carbon (nJCH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Synthesis of Aromatic Nitriles Using Nonmetallic Cyano‐Group Sources

Synthese aromatischer Nitrile mithilfe nichtmetallischer CN‐Quellen

Contact Info

Product

Resources

About

Copper‐Catalyzed Cyanation of Aryl Iodides with Malononitrile: An Unusual Cyano Group Transfer Process from C(sp³) to C(sp²)

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (ⁿJ_HH, n = 4, 5, and 6) proton–proton and proton–carbon (ⁿJ_CH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds

Synthesis of new cyano‐substituted analogues of Tröger's bases from bromo‐derivatives. A stereochemical dependence of long‐range (ⁿJ_HH, n = 4, 5, and 6) proton–proton and proton–carbon (ⁿJ_CH, n = 1, 2, 3, 4, and 5) coupling constants of these compounds