Raney Nickel Hydrogenolysis of Thioamides: A New Amine Synthesis

Kornfeld, Edmund C.

doi:10.1021/jo01141a020

Cited by 54 publications

(17 citation statements)

References 7 publications

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“…The residue was made basic with NaOH, extracted with chloroform, dried (MgS04), and evaporated to yield a brown oil. Distillation (110 °C, 10-3 mm) afforded (RS)-4-methylnicotine (1.66 g) as a colorless oil: IR (neat) 1600 cm-1 (C=N); 13C NMR18 (CDCI3) ppm from Me4Si, 151.1 (C-2), 150.0 (6), 147.4 (4), 139.3 (3), 127.1 (5), 67.1 (2'), 57.9 (5'), 41.2 (NMe), 34.1 (3'), (b) From 4-Methylpyridine-3-carboxaldehyde. o>(4-Methyl-3-pyridyl)-a-morpholinoacetonitrile (2).…”

Section: References and Notesmentioning

confidence: 99%

Aberrant syntheses in higher plants. 3. Synthesis of 4-methylnicotine and an examination of its possible biosynthesis from 4-methylnicotinic acid in Nicotiana tabacum

Leete¹,

Leete²

1978

J. Org. Chem.

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Section: References and Notesmentioning

confidence: 99%

Aberrant syntheses in higher plants. 3. Synthesis of 4-methylnicotine and an examination of its possible biosynthesis from 4-methylnicotinic acid in Nicotiana tabacum

Leete¹,

Leete²

1978

J. Org. Chem.

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“…Based on the observations of other groups on N-alkylation of amines with alcohols catalyzed by Raney nickel as a side reaction, − Rice and Kohn developed the Raney nickel catalyzed N-alkylation of aniline and benzidine with alcohols in 1955 (Scheme ). The reactions proceed under reflux with an excess of the alcohol.…”

Section: Nickel-catalyzed C–n and C–c Coupling Reactionsmentioning

confidence: 99%

3d-Metal Catalyzed N- and C-Alkylation Reactions via Borrowing Hydrogen or Hydrogen Autotransfer

2018

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The conservation of our element resources is a fundamental challenge of mankind. The development of alcohol refunctionalization reactions is a possible fossil carbon conservation strategy since alcohols can be obtained from indigestible and abundantly available biomass. The conservation of our rare noble metals, frequently used in key technologies such as catalysis, might be feasible by replacing them with highly abundant metals. The alkylation of amines by alcohols and related C–C coupling reactions are early examples of alcohol refunctionalization reactions. These reactions follow mostly the borrowing hydrogen or hydrogen autotransfer catalysis concept, and many 3d-metal catalysts have been disclosed in recent years. In this review, we summarize the progress made in developing Cu, Ni, Co, Fe, and Mn catalysts for C–N and C–C bond formation reactions with alcohols and amines using the borrowing hydrogen or hydrogen autotransfer concept. We expect that the findings in this field will inspire others to develop new efficient and selective earth-abundant metal catalysts for borrowing hydrogen or hydrogen autotransfer applications or to develop novel alcohol refunctionalization reactions that can be mediated by such metals.

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“…The scope of the reduction of thioamides with Raney nickel is illustrated by the successful desulfurization of the constrained b-thiolactam 121 to give the azetidine 122 without ring opening, and by the reduction of the pentacyclic thioamide 123 to give pseudovincadifformine (124) (Scheme 33). [218][219][220] Scheme 33 Reduction of Thioamides by Raney Nickel [219,220] In his original experiments, Kulinkovich treated carboxylic acid esters with a Grignard reagent and titanium(IV) isopropoxide to obtain cyclopropanol derivatives. [221][222][223] The scope of this transformation was expanded by de Meijere, who demonstrated that N,N-disubstituted amides of carboxylic acids also undergo cyclopropanation upon treatment with Grignard reagents and titanium(IV) isopropoxide.…”

Section: Variation 3: Reduction With Hydrosilanesmentioning

confidence: 99%