21965-92-4Relevant articles and documents
Light-Induced Alkylation of (Hetero)aromatic Nitriles in a Transition-Metal-Free C-C-Bond Metathesis
Lipp, Benjamin,Lipp, Alexander,Detert, Heiner,Opatz, Till
, p. 2054 - 2057 (2017/04/27)
A light-induced C-C-σ-bond metathesis was achieved through transition-metal-free activation of an unstrained C(sp3)-C(sp3)-σ-bond in 1-benzyl-1,2,3,4-tetrahydroisoquinolines. A photoredox-mediated single-electron oxidation of these precursor amines yield radical cations which undergo a homolytic cleavage of a C(sp3)-C(sp3)-σ-bond rather than the well-known α-C-H-scission. The resulting carbon-centered radicals are used in the ipso-substitution of (hetero)aromatic nitriles proceeding through another single-electron transfer-mediated C-C-bond cleavage and formation.
Visible Light-Mediated Direct Decarboxylative C-H Functionalization of Heteroarenes
Garza-Sanchez, R. Aleyda,Tlahuext-Aca, Adrian,Tavakoli, Ghazal,Glorius, Frank
, p. 4057 - 4061 (2017/06/19)
The direct visible light-mediated C-H alkylation of heteroarenes using aliphatic carboxylic acids is reported. This mild method proceeds at low catalyst loadings (0.5 mol %) and has a high functional group tolerance and a broad substrate scope. Notably, f
Sunflow: Sunlight Drives Fast and Green Photochemical Flow Reactions in Simple Microcapillary Reactors – Application to Photoredox and H-Atom-Transfer Chemistry
Nauth, Alexander M.,Lipp, Alexander,Lipp, Benjamin,Opatz, Till
supporting information, p. 2099 - 2103 (2017/04/24)
“Sunflow“ – The combination of a microcapillary reactor in continuous flow mode with sunlight as the most sustainable energy source imaginable was applied to a range of photoredox and H-atom-transfer reactions making them both fast and green.
Ruthenium-Mediated Dual Catalytic Reactions of Isoquinoline via C?H Activation and Dearomatization for Isoquinolone
Wang, Ting-Hsuan,Lee, Wei-Chih,Ong, Tiow-Gan
supporting information, p. 2751 - 2758 (2016/09/13)
We have unraveled the ruthenium-promoted prototype reaction based on C(sp2)?C(sp3) bond formation through the reigoselective C?H activation of isoquinoline and pyridine derivatives with various alkyl halides, leading to 1-substituted isoquinoline products in good yield. This C?H catalytic reaction did not rely on chelation assistance of the directing group of the substrates. The dimer [RuCl2(p-cymene)]2in combination with an N-heterocyclic carbene ligand, adamantanecarboxylic acid and K2CO3base in N-methyl-2-pyrrolidone solution at 150 °C are the best conditions. Simultaneously, we are also able to chemically tune the reaction mode to dearomatization by adding water, leading to isoquinolone products. This reaction methodology is not suitable for other nitrogen-containing heteroarenes such as pyridazines and pyrimidines. (Figure presented.).
Transition-Metal-Free Decarboxylative Photoredox Coupling of Carboxylic Acids and Alcohols with Aromatic Nitriles
Lipp, Benjamin,Nauth, Alexander M.,Opatz, Till
, p. 6875 - 6882 (2016/08/16)
A transition-metal-free protocol for the redox-neutral light-induced decarboxylative coupling of carboxylic acids with (hetero)aromatic nitriles at ambient temperature is presented. A broad scope of acids and nitriles is accepted, and alcohols can be coupled in a similar fashion through their oxalate half esters. Various inexpensive sources of UV light and even sunlight can be used to achieve this C-C bond formation proceeding through a free radical mechanism.
Regioselective photochemical C-OMe bond formation initiated by one-electron transfer and N-OMe bond fragmentation in electron donor-acceptor systems
Collado, Daniel,Perez-Inestrosa, Ezequiel
, p. 1800 - 1808 (2012/05/04)
Compounds that integrate electron donor-acceptor subunits with N-methoxyisoquinolinium as acceptors and substituted (methoxy)benzenes as donors were synthesized and their luminescent and photochemical properties studied. Photolysis yielded the corresponding photomethoxylation products in a two-step process that involves N-OMe bond scission followed by C-OMe bond formation. Homolysis of the N-OMe bond restores the aromatic isoquinoline nucleus and produces a methoxy radical that can couple to the required ring carbon atom in the benzene cation radical to give the products in a regioselective process controlled by the spin density of the cation radical. This photoprocess involves two different pathways: methoxylation of the acceptor (intracomponent methoxylation) or the donor (intercomponent metoxylation). Both methoxy-transfer pathways are controlled by the donoating ability (redox potential) of the donor subunit, consistent with the emission observed upon excitation of the charge-transfer state in systems that undergo intermethoxylation.
Covalently linked acceptor - Donor systems based on isoquinoline N-oxide acceptor: Photoinduced electron transfer produces dual-channel luminescent systems that evolve chemically to photohydroxylation of the aromatic donor
Collado, Daniel,Perez-Inestrosa, Ezequiel,Suau, Rafael
, p. 3574 - 3584 (2007/10/03)
Acceptor-donor compounds containing the isoquinoline N-oxide acceptor and (methoxy)nbenzene (n = 0, 1, 2, 3) electron donors were studied. The two chromophores are connected by a CH2 bridging unit. All acceptor-donor compounds exhibi
Substituted isoquinolines and methods of using same
-
, (2008/06/13)
Novel substituted isoquinoline compounds are disclosed together with novel 2-phenylethylamides useful as precursors or intermediates for the production of the isoquinolines. The substituted isoquinolines exhibit activity in antagonizing the effects of platelet activating factor (PAF).
