Formation of Nitriles, Carboxylic Acids, and Derivatives by Oxidation, Substitution, and Addition

Larock, Richard C.; Yao, Tuanli

doi:10.1002/9781118662083.cot09-001

Cited by 7 publications

(6 citation statements)

References 1,132 publications

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“…Nitriles are a ubiquitous class of compounds present in many pharmaceuticals, secondary metabolites, and polymers . Owing to their unique chemical reactivity, nitriles often serve as precursors to numerous additional important functional groups in organic synthesis, including N -heterocycles, carbonyl compounds, and amines . Although nitriles can be accessed by many methods, the conversion of olefins to alkyl nitriles via transition metal-catalyzed olefin hydrocyanation represents one of the most conceptually straightforward processes.…”

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confidence: 99%

Enantioselective Olefin Hydrocyanation without Cyanide

2019

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The enantioselective hydrocyanation of olefins represents a conceptually straightforward approach to prepare enantiomerically enriched nitriles. These, in turn, comprise or are intermediates in the synthesis of many pharmaceuticals and their synthetic derivatives. Herein, we report a cyanide-free dual Pd/CuH-catalyzed protocol for the asymmetric Markovnikov hydrocyanation of vinyl arenes and the anti-Markovnikov hydrocyanation of terminal olefins in which oxazoles function as nitrile equivalents. After an initial hydroarylation process, the oxazole substructure was deconstructed using a [4+2]/retro-[4+2] sequence to afford the enantioenriched nitrile product under mild reaction conditions.

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confidence: 99%

Enantioselective Olefin Hydrocyanation without Cyanide

2019

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“…In particular to the Knoevenagel condensation reaction, a variety of heterogeneous catalysts have been used, that is, zeolites, − clays, − organic-functionalized molecular sieves, silicate–organic composite materials, and PCPs, ,− which demonstrated vast significant advantages over homogeneous catalysts. Remarkably, it is noteworthy to mention that PCP-based heterogeneous catalysts are quite limited toward oxidative conversion of benzaldehyde into benzoic anhydride (C–H activation) which is a very advantageous reagent in organic synthesis, − for instance, silyl ester’s lactonization, − asymmetric esterifcations, and synthesis of peptides and drugs. − Employing homogeneous catalysts, Knoevenagel condensation reactions and oxidative conversion of benzaldehyde into benzoic anhydrides involve various difficulties such as low catalyst loading, poor recyclability, tedious work-up process, longtime consumption, and catalyst contamination, whereas heterogeneous catalysts are easily recoverable and reusable and minimize the undesired waste. − …”

Section: Introductionmentioning

confidence: 99%

Catalytic C–H Bond Activation and Knoevenagel Condensation Using Pyridine-2,3-Dicarboxylate-Based Metal–Organic Frameworks

et al. 2021

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Three 1D coordination polymers (CPs) [M(pdca)-(H 2 O) 2 ] n (M = Zn, Cd, and Co; 1−3), and a 3D coordination framework {[(CH 3 ) 2 NH 2 ][CuK(2,3-pdca)(pa)(NO 3 ) 2 ]} n (4) (2,3-pdca = pyridine-2,3-dicarboxylate and pa = picolinic acid), have been synthesized adopting a solvothermal reaction strategy. The CPs have been thoroughly characterized using various spectral techniques, that is, elemental analyses, FT-IR, TGA, DSC, UV/vis, and luminescence. Structural information on 1−4 was obtained by PXRD and X-ray singlecrystal analyses, whereas morphological insights were attained through FESEM, AFM, EDX, HRTEM, and BET surface area analyses. Roughness parameters were calculated from AFM analysis, whereas dimensions of small domains and interplanar spacing were defined with the aid of HRTEM. CPs 1−3 are 1D isostructural networks, whereas 4 is a 3D framework. Moreover, 1−4 display moderate luminescence at rt. In addition, 1−4 have been applied as economic and efficient porous catalysts for the Knoevenagel condensation reaction and C−H bond activation under mild conditions with good yields (95−98 and 97−99%), respectively. Notably, 1−3 can be reused up to seven cycles, whereas 4 can be reused up to five catalytic cycles with retained catalytic efficiency. Relative catalytic efficacy toward the Knoevenagel condensation reaction follows in the order 2 > 1 > 3 > 4, whereas 2 > 4 > 1 > 3 for C−H activation. The present result demonstrates synthetic, structural, optical, morphological, and catalytic aspects of 1−4.

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“…The former is not only the well-known reactant in Passerini and Ugi multicomponent coupling reactions but also frequently occurring in natural products . The latter is also found in biologically active compounds and the valuable synthetic intermediate for amines and carbonyl compounds . Therefore, their selective synthesis has been one of the long-standing research subjects in synthetic communities.…”

Section: Introductionmentioning

confidence: 99%

Divergent Synthesis of Isonitriles and Nitriles by Palladium-Catalyzed Benzylic Substitution with TMSCN

2020

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Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP-or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.

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Formation of Nitriles, Carboxylic Acids, and Derivatives by Oxidation, Substitution, and Addition

Abstract: Alkanes Arenes Alkenes Dienes Alkynes Alkyl Halides Amines Imines and Derivatives Azides Nitro Compounds Nitrothioalkenes Ethers … Show more

Cited by 7 publications

References 1,132 publications

Enantioselective Olefin Hydrocyanation without Cyanide

Enantioselective Olefin Hydrocyanation without Cyanide

Catalytic C–H Bond Activation and Knoevenagel Condensation Using Pyridine-2,3-Dicarboxylate-Based Metal–Organic Frameworks

Divergent Synthesis of Isonitriles and Nitriles by Palladium-Catalyzed Benzylic Substitution with TMSCN

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